Increasing the pollution rate of water sources is one of the most severe issues that the world faces. This issue has stimulated researchers to investigate different treatment methods such as adsorption, chemical precipitation, membrane filtration, flocculation, ion exchange, flotation, and electrochemical methods. Among them, adsorption has gained broad interest due to its ease of operation, low cost, and high efficiency. The critical factor of the successful adsorption treatment process is finding attractive adsorbents with attractive criteria such as low cost and high adsorption capacity. In the last few decades, nanotechnology has attracted much attention, and numerous nanomaterials have been synthesized for water and wastewater treatment. This work provides a quick overview of nanomaterials, which have been investigated for water remediation as adsorbent and photocatalyst. This work reviewed more than 100 articles to provide a critical review that would determine the limitation of using nanomaterials in water treatment at the commercial scale.

Incessant release of a large spectrum of agro-industrial pollutants into environmental matrices remains a serious concern due to their potential health risks to humans and aquatic animals. Existing remediation techniques are unable to remove these pollutants, necessitating the development of novel treatment approaches. Due to its unique structure, physicochemical properties, and broad application potential, graphene has attracted a lot of attention as a new type of two-dimensional nanostructure. Given its chemical stability, large surface area, electron mobility, superior thermal conductivity, and two-dimensional structure, tremendous research has been conducted on graphene and its derived composites for environmental remediation and pollution mitigation. Various methods for graphene functionalization have facilitated the development of different graphene derivatives such as graphene oxide (GO), functional reduced graphene oxide (frGO), and reduced graphene oxide (rGO) with novel attributes for multiple applications. This review provides a comprehensive read on the recent progress of multifunctional graphene-based nanocomposites and nanohybrids as a promising way of removing emerging contaminants from aqueous environments. First, a succinct overview of the fundamental structure, fabrication techniques, and features of graphene-based composites is presented. Following that, graphene and GO functionalization, i.e., covalent bonding, non-covalent, and elemental doping, are discussed. Finally, the environmental potentials of a plethora of graphene-based hybrid nanocomposites for the abatement of organic and inorganic contaminants are thoroughly covered.

Presently, graphenic nanomaterials are being studied as candidates for wastewater pollutant removal. In this study, two graphite oxides produced from natural graphite with different grain sizes (325 and 10 mesh), their respective reduced graphene oxides and one reduced graphene oxide with nitrogen functional groups were synthesized and tested to remove a surfactant model substrate, Triton X-100, from an aqueous solution. Kinetic experiments were carried out and adjusted to pseudo-first order equation, pseudo-second order equation, Elovich, Chain-Clayton and intra-particle diffusion models. Reduced graphene oxides displayed an instantaneous adsorption due to their accessible and hydrophobic surfaces, while graphite oxides hindered the TX100 adsorption rate due to their highly superficial oxygen content. Results from the adsorption isotherms showed that the Sips model perfectly described the TX100 adsorption behavior of these materials. Higher adsorption capacities were developed with reduced graphene oxides, being maximum for the material produced from the lower graphite grain size (qₑ = 3.55·10⁻⁶ mol/m²), which could be explained by a higher surface area (600 m²/g), a lower amount of superficial oxygen (O/C = 0.04) and a more defected structure (ID/IG = 0.85). Additionally, three commercial high surface area graphites in the range of 100–500 m²/g were evaluated for comparison purposes. In this case, better adsorption results were obtained with a more graphitic material, HSAG100 (qₑ = 1.72·10⁻⁶ mol/m²). However, the best experimental results of this study were obtained using synthesized graphenic materials.

Glyphosate (GLY) is a broad-spectrum herbicide used worldwide to control broadleaf sedge, and grass weeds to control non-specific vegetation. Although it was evaluated as non-toxic agent in 20ᵗʰ century, its carcinogenic and genotoxic potential has being intensively investigated all over the world in the last decade. Moreover, the combination of GLY and 2,4-dichlorophenoxyacetic acid (2,4-D) has been widely applied. Although genotoxicity of GLY has been evaluated in vivo studies, there is no report in the literature for the monitoring of in vitro biointeraction of GLY and double stranded DNA, or how effect the combination of GLY and 2,4-D onto DNA. Herein, an electrochemical biosensor platform was developed for detection of the pesticide-DNA interaction by using disposable pencil graphite electrodes (PGEs). First, voltammetric detection of the interaction between GLY and DNA was investigated and the electrochemical characterization of the interaction was achieved. Taking a step further, the synergistic genotoxic effect of the mixture of GLY and 2,4-dichlorophenoxyacetic acid (2,4-D) or the mixture of their herbicide forms onto DNA could be monitored. This effect was concentration dependent, and the herbicide of GLY or the use of mixture of herbicides of GLY and 2,4-D had more genotoxic effect than analytical grade of the active molecules, GLY and 2,4-D. The single-use PGEs provided to fabricate robust, eco-friendly and time saver recognition platform for monitoring of herbicide-DNA interaction with the sensitive and reliable results. It is expected that this study will lead to be designed miniaturized lab-on-a chip platforms for on-line analysis of the pesticide-nucleic acid interactions.

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.

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.

Despite the large number of studies reporting the phytotoxicity of graphene-based materials, the effects of these materials on nutrient uptake in plants remain unclear. The present study showed that nitrate concentrations were significantly decreased in the roots of wheat plants treated with graphene oxide (GO) at 200–800 mg L⁻¹. Non-invasive microelectrode measurement demonstrated that GO could significantly inhibit the net NO₃⁻ influx in the meristematic, elongation, and mature zones of wheat roots. Further analysis indicated that GO could be trapped in the root vacuoles, and that the maximal root length and the number of lateral roots were significantly reduced. Additionally, root tip whitening, creases, oxidative stress, and weakened respiration were observed. These observations indicate that GO is highly unfavorable for vigorous root growth and inhibits increase in root uptake area. At the molecular level, GO exposure caused DNA damage and inhibited the expression of most nitrate transporters (NRTs) in wheat roots, with the most significantly downregulated genes being NRT1.3, NRT1.5, NRT2.1, NRT2.3, and NRT2.4. We concluded that GO exposure decreased the root uptake area and root activity, and decreased the expression of NRTs, which may have consequently suppressed the NO₃⁻ uptake rate, leading to adverse nitrate accumulation in stressed plants.

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.

Removal of dissolved sulfide contaminants from aqueous model solution using bio-derived porous graphitic carbon (PGC) impregnated with δ-MnO₂ was investigated. The composite adsorbent was synthesized using the chemical wet deposition method wherein MnO₂ was deposited on carbon walls through an in-situ reaction between permanganate and ethanol. Formation of transition metal oxide of manganese in the form of birnessite nanoparticles on interconnected PGC cell structure was confirmed by transmission electron microscopy, scanning electron microscopy, elemental analysis, and X-Ray diffraction characterization studies. The composite nanomaterial was tested for sulfide removal from aqueous solution at various conditions, including the pH, adsorbent dosage, initial solution concentration, and contact time. Adsorption results demonstrated an excellent adsorption capacity of ca. 90% within 20 min of contact time at 298 K. Equilibrium data collected from batch adsorption experiments fitted well with the Langmuir isotherm model (KL = 190 L/mg; R² = 0.99). The maximum adsorption capacity of the composite was estimated as 526.3 mg S²⁻/g at highly alkaline conditions compared to ca. 340 mg/g for a δ-MnO₂ adsorbent. Adsorptive oxidation of sulfides on composite MnO₂-PGC adsorbent was found to be controlled by the chemisorption process in accordance with the pseudo-second-order reaction model. Characterization of spent adsorbents revealed that sulfide was removed through adsorptive oxidation resulting in the formation of agglomerated particles of metal sulfate complexes and elemental sulfur. Analysis of reaction mechanism revealed that both MnO₂ and PGC played a role in the adsorptive oxidation of sulfides to CaSO₄ and elemental sulfur.

The growing use of graphene-based nanomaterials (GBNs) for various applications increases the probability of their environmental releases and calls for a systematic assessment of their potential impacts on soil invertebrates that serve as an important link along terrestrial food chains. Here, we investigated the response of earthworms (Eisenia fetida) to three types of multi-layer graphenes (MLGs) (G1, G2 and G3 with 12–15 layers) with variable morphology (lateral sizes: 7.4 ± 0.3, 6.4 ± 0.1 and 2.8 ± 0.1 μm; thicknesses: 5.0 ± 0.1, 4.2 ± 0.1 and 4.0 ± 0.2 nm, respectively) and hydrophobicity ((O + N)/C ratios: 0.029, 0.044 and 0.075; contact angles: 122.8, 118.8 and 115.1°, respectively). Exposure to these materials was conducted for 28 days (except for 48-h avoidance test) separately in potting or farm soil at 0.2% and 1% by weight. Earthworms avoided both soils when amended with 1% of the smaller and more hydrophilic MLGs (G2 and G3), leading to a decreased trend in worm cocoon formation. The smallest and most hydrophilic MLG (G3), which was easier to assimilate, also significantly inhibited the viability (20.2–56.0%) and mitochondrial membrane potential (32.0–48.5%) of worm coelomocytes in both soils. In contrast, oxidative damage (indicated by lipid peroxides) was more pronounced upon exposure to more hydrophobic and larger graphenic materials (G1 and G2), which were attributed to facilitated adhesion to and disruption of worm membranes. These findings highlight the importance of MLG morphology and hydrophobicity in their potential toxicity and mode of action, as well as ecological risks associated with incidental and accidental releases.