Hyperbranched polymers are nanomaterials belonging to the class of dendritic architectures with increasing applications in many diverse fields. We studied the toxicity of two hyperbranched polymers to the freshwater crustacean Daphnia magna. A hyperbranched hydroxyl-terminated polyester and a commercial hyperbranched polyamidoamine, Helux-3316 were tested for the acute immobilization of daphnids, the overproduction of reactive oxygen species and the activity of the antioxidant enzymes catalase and glutathione S-transferase. The effect for D. magna immobilization was higher for the hyperbranched polyamidoamine Helux-3316, which was attributed to the presence of primary amino groups on its surface. Following exposure to both hyperbranched polymers, a clear overproduction of reactive oxygen species took place accompanied by concentration-dependent enzymatic antioxidant response. Our results showed that the overproduction of reactive oxygen species activated antioxidant defence mechanisms and was responsible for the immobilization of daphnids exposed to both hyperbranched polymers. We showed evidence of the uptake of fluorescently labelled Helux-3316 that accumulated into the gastrointestinal tract of D. magna, and its removal via excretion within fecal pellets. This is the first work reporting the internalization of hyperbranched polymers in aquatic organisms.

Reduced graphene oxide (rGO) is one of the most widely used carbon nanomaterials. When it is released into the environment, rGO can markedly affect the transformation of many pollutants, and change their fate and risk. In this work, the synergetic effects of rGO and Cu(II) on the oxidation of 2-naphthol were examined in water in the dark. It was found that the coexistence of rGO and Cu(II) significantly promoted the oxidation of 2-naphthol. Corresponding products were identified as the coupling oligomers of 2-naphthol (dimer, trimer and tetramer) and hydroxylated compounds (OH-2-naphthol, OH-dimer, di–OH–dimer and naphthoquinone derivatives). In the oxidation reaction, rGO played dual roles, i.e. adsorbent and electron-transfer mediator. rGO firstly adsorbed Cu(II) and 2-naphthol on its surface, and then transferred electrons from 2-naphthol to Cu(II) to yield 2-naphthol radicals and Cu(I). 2-Naphthol radicals coupled to each other to form different oligomers of 2-naphthol. Cu(I) was re-oxidized back to Cu(II) by dissolved oxygen, which sustained the continuous oxidation of 2-naphthol. During the autoxidation of Cu(I), reactive oxygen species were generated, which further reacted with 2-naphthol to form hydroxylated products. These findings provide new insights into the risk assessment of rGO and 2-naphthol in aquatic environments.

Nickel nanoparticles (NiNPs) have an estimated production of ca. 20 tons per year in the US. Nickel has been risk-assessed for long in Europe, but not NiNPs, hence the concern for the environment. In the present study, we focused on investigating the mechanisms of toxicity of NiNPs and the comparison to NiNO3. The high-throughput microarray for the soil ecotox model Enchytraeus crypticus (Oligochaeta) was used. To anchor gene to phenotype effect level, organisms were exposed to reproduction effect concentrations EC20 and EC50, for 3 and 7 days. Results showed commonly affected pathways between NiNPs and NiNO3, including increase in proteolysis, apoptosis and inflammatory response, and interference with the nervous system. Mechanisms unique to NiNO3 were also observed (e.g. glutathione synthesis). No specific mechanisms for NiNPs were found, which could indicate that longer exposure period (>7 days) is required to capture the peak response to NiNPs. A mechanisms scheme is assembled, showing both common and unique mechanisms to NiNO3 and NiNPs, providing an important framework for further, more targeted, studies.

Agricultural soil is one of the main sink for both heavy metals and nanomaterials (NMs). Whether NMs can impact heavy metals uptake or bioaccumulation in plants is unknown. Here, cucumber plants were cultivated in a multi-heavy metals contaminated soil amended with four types of NMs (SiO2, TiO2, ZnS and MoS2) separately for four weeks. Physiological and biochemical parameters were determined to investigate the impact of NMs on plant growth. Inductively coupled plasma mass spectrometry was employed to determine the metal content in plants. Results showed that none of the tested NMs impacted plants biomass, but all the NMs showed different degrees of reduction in heavy metals bioaccumulation in plant roots, stems and leaves. However, four NMs showed different degrees of reduction in macro and micro nutrients uptake. MoS2 decreased the bioaccumulation of heavy metals (As, Cd, Cr, Cu, Ni, Al, Ti and Pb) for 36.4–60.6% and nutrients (Mg, Fe, K, Si and Mn) for 40.1%–50.1% in roots. Exposure to MoS2 NMs also significantly increased 23.4% of Si in leaves, 205.6% and 83.9% of Mo in roots and stems, respectively. In general, the results of this study showed promising potential for NMs to reduce uptake of heavy metals in crop plants, especially MoS2 NMs. However, the negative impacts of perturbing nutrients uptake should be paid attention as well.

Our previous study showed heritable reproductive toxicity in the nematode Caenorhabditis elegans after multigenerational exposure to AgNO₃ and silver nanoparticles (Ag-NPs). The aim of this study was to determine whether such inheritable effects are correlated with induced germline mutations in C. elegans. Individual C. elegans lineages were exposed for 10 generations to equitoxic concentrations at EC₃₀ of AgNO₃, Ag-NPs, and sulfidized Ag-NPs (sAg-NPs), a predominant environmentally transformed product of pristine Ag-NPs. The mutations were detected via whole genome DNA sequencing approach by comparing F₀ and F₁₀ generations. An increase in the total number of variants, though not statistically significant, was observed for all Ag treatments and the variants were mainly contributed by single nucleotide polymorphisms (SNPs). This potentially contributed towards reproductive as well as growth toxicity shown previously after ten generations of exposure in every Ag treatment. However, despite Ag-NPs and AgNO₃ inducing stronger reproductive toxicity than sAg-NPs, exposure to sAg-NPs resulted in higher mutation accumulation with significant increase in the number of transversions. Thus our results suggest that other mechanisms of inheritance, such as epigenetics, may be at play in Ag-NP- and AgNO₃-induced multigenerational and transgenerational reproductive toxicity.

Antibiotics as emerging pharmaceutical pollutants have seriously not only threatened human life and animal health security, but also caused environmental pollution. It has drawn enormous attention and research interests in the study of antibiotics removal from aqueous environments. Graphene, an interesting one-atom-thick, 2D single-layer carbon sheet with sp² hybridized carbon atoms, has become an important agent for removal of antibiotic, owing to its unique physiochemical properties. Recently, a variety of graphene-based nanomaterials (GNMs) are reported to efficiently remove antibiotics from aqueous solutions by different technologies. In this review, we summarize different structure and properties of GNMs for the removal of antibiotics by adsorption. Meanwhile, advanced oxidation processes (AOPs), such as photocatalysis, Fenton process, ozonation, sulfate radical and combined AOPs by the aid of GNMs are summarized. Finally, the opportunities and challenges on the future scope of GNMs for removal of antibiotics from aqueous environments are proposed.

Nanotechnology and use of nanomaterials (NMs) improve life quality, economic growth and environmental health. However, the increasing production and use of NMs in commercial products has led to concerns about their potential toxicity on human and environment health, as well as its toxicological classification and regulation. In this context, there is an urgent need to standardize and validate procedures for nanotoxicity testing. Since the zebrafish embryotoxicity test (ZET) has been indicated as a suitable approach for the toxicity assessment of traditional and emergent pollutants, the aim of this review is to summarize the existing literature on embryotoxic and teratogenic effects of NMs on zebrafish. In addition, morphological changes in zebrafish embryos induced by NMs were classified in four reaction models, allowing classification of the mode of action and toxicity of different types of NM. Revised data showed that the interaction and bioaccumulation of NMs on zebrafish embryos were associated to several toxic effects, while the detoxification process was limited. In general, NMs induced delayed hatching, circulatory changes, pigmentation and tegumentary alterations, musculoskeletal disorders and yolk sac alterations on zebrafish embryos. Recommendations for nanotoxicological tests are given, including guidance for future research. This review reinforces the use of the ZET as a suitable approach to assess the health risks of NM exposure.

Graphene with atomic layer of sp²-hybridized carbon atoms in a hexagonal structure has attracted multidisciplinary attention since its discovery. Due to the inherent advantages of large specific surface area and abundant functional groups, its derivative graphene oxide (GO) nanomaterials have achieved large-scale development in effective pollution treatment. In the past few years, novel GO-based nanomaterials through coupling with other nanomaterials have been synthesized with significant process and applied for efficient elimination of different kinds of pollutants. This paper aims to summarize recent research results on the excellent removal ability of GO-based nanomaterials for various heavy metal ions in aqueous solutions. The synthesis, adsorption process characteristics and interaction mechanism of the adsorbent are emphasized and discussed. The effects of various environmental conditions are outlined. At last, a brief summary, perspective and outlook are presented. This review is intended to provide some thrilling information for the design and manufacture of GO-based nanomaterials for the elimination of heavy metal ions from wastewater in environmental pollution management.

Recently, novel-nanomaterials with excellent sorption capacities, mild stability, and environmental-friendly performance, have enabled massive developments in capturing heavy metal ions. This review firstly introduces the preparation and modification of novel-nanomaterials (e.g., MOFs, nZVI, MXenes, and g-C₃N₄). Then, the heavy metal ions’ sorption properties and the impact of environmental conditions have been discussed. Subsequently, the sorption mechanisms are verified through batch experiments, spectral analysis, surface complexation models, and theoretical calculations. Finally, the applications prospects of novel-nanomaterials in removing heavy metal ion polluted water have also been discussed, which provide perspective for future in-depth research and practical applications.

The increasing production and use of graphene-based nanomaterials (e.g., graphene oxide (GO) and reduced graphene oxide (RGO)) will lead to their environmental release. To date, transport of RGOs in saturated porous media is poorly understood. Here, we examined the transport behaviors of three RGO materials obtained by reducing a GO product with commonly used reducing agents – N₂H₄, NaBH₄ and L-ascorbic acid (referred to as N₂H₄-RGO, NaBH₄-RGO and VC-RGO, respectively). When the dominant background cation was Na⁺, K⁺ or Mg²⁺, the mobility of the RGOs and GO in saturated quartz sand correlated well with their surface C/O ratio. Interestingly, the lower mobility of the more reduced materials (the ones with higher C/O values) was not only the results of their less negative surface charges and larger particle sizes, but also the outcome of their greater hydrophobicity, in line with the calculated extended Derjaguin–Landau–Verwey–Overbeek (XDLVO) profiles. Counterintuitively, when the background cation was Ca²⁺, the least reduced material among the three RGOs, VC-RGO, exhibited the lowest mobility. Analysis of electrophoretic and aggregation properties, as well as pH-effect experiments, indicated that the surprisingly low mobility of VC-RGO was attributable to the strong cation-bridging effect (primarily Ca²⁺-bridging between RGO and quartz sand) associated with this material, as VC-RGO contained the highest amount of surface carboxyl group (a strong metal-binding moiety). Notably, enhanced attachment (due to increased hydrophobic effect and cation-bridging) and particle aggregation appeared to work synergistically to increase RGO retention, as the attachment of large RGO aggregates significantly enhanced particle straining by narrowing the flow path. These observations reveal a largely overlooked link between the mobility of graphene-based materials and their key physicochemical properties.