Metal-based nanomaterials in aquatic environments: What do we know so far about their ecotoxicity?

The wide range of applications of nanomaterials (NM) in different fields has led to both uncontrolled production and release into environmental compartments, such as aquatic systems, where final disposal occurs. Some efforts have been made to estimate their concentrations in environmental matrices; however, little is known about the actual effects of environmental NM concentrations on biota. The aims of the present review are to (i) expose the state of the art of the most applied NM and their actual concentrations regarding how much is being released to the aquatic environment and which are the predicted ones; (ii) analyze the current literature to elucidate if the aforementioned conditions were proven to cause deleterious effects on the associated organisms; and (iii) identify gaps in the knowledge regarding whether the actual NM concentrations are harmful to aquatic biota. These novel materials are expected to being released into the environment in the range of hundreds to thousands of tons per year, with Si- and Ti-based NM being the two most important. The estimated environmental NM concentrations are in the low range of ng to µg/L, except for Ti-based ones, which concentrations reach values on the order of mg/L. Empirical information regarding the ecotoxicity of environmental NM concentrations mainly focused on metal-based NM, however, it resulted poor and unbalanced in terms of materials and test species. Given its high predicted environmental concentration in comparison with the others, the ecotoxicity of Ti-based NM has been well assessed in algae and fish, while little is known regarding other NM types. While only a few marine species were addressed, the freshwater species Daphnia magna and Danio rerio accounted for the majority of studies on invertebrate and fish groups, respectively. Most of the reported responses are related to oxidative stress. Overall, we consider that invertebrate groups are the most vulnerable, with emphasis on microcrustaceans, as environmentally realistic metal-based NM concentration even caused mortality in some species. In the case of fish, we assumed that environmental concentrations of Ti-based NM represent a growing concern and threat; however, further studies should be carried out by employing other kinds of NM. Furthermore, more ecotoxicological information is needed in the case of carbon-based NM, as they are expected to considerably increase in terms of released amounts and applications in the near future.

Exposure modes determined the effects of nanomaterials on antibiotic resistance genes: The different roles of oxidative stress and quorum sensing.

The effects of co-occurrent pollutants on antibiotic resistance genes (ARGs) in wastewater treatment plants (WWTPs) have raised attentions. However, how the different realistic exposure scenarios determining the effects of nanomaterials (NMs) on ARGs, was still unknown. Herein, the effects of NMs on ARGs under two realistic scenarios was investigated by short-term and long-term exposure modes. The presence of NMs with two different exposure modes could both promote the dissemination of ARGs, and the results were dose-, type- and duration-dependent. Compared to short-term exposure, the long-term exposure increased the abundances of ARGs with a greater extent except nano-ZnO. The long-term exposure increased the overall abundances of target ARGs by 2.9%-20.4%, while shot-term exposure caused the 3.4%-10.5% increment. The mechanisms of ARGs fates driven by NMs exposure were further investigated from the levels of microbial community shift, intracellular oxidative stress, and gene abundance. The variations of several potential bacterial hosts did not contribute to the difference in the ARGs transmission with different exposure modes because NMs types played more vital roles in the shift of microbial community compared to the exposure modes. For the short-term exposure, NMs were capable of triggering the QS by upregulating relevant genes, and further activated the production of surfactin and increased membrane permeability, resulting in the facilitation of ARGs transfer. However, NMs under long-term exposure scenario preferentially stimulated oxidative stress by generating more ROS, which then enhanced ARGs dissemination. Therefore, the exposure mode of NMs was one of the pivotal factors determining the ARGs fates by different triggering mechanisms. This study highlighted the importance of exposure scenario of co-occurrent pollutants on ARGs spread, which will benefit the comprehensive understanding of the actual environmental fates of ARGs.

Biodistribution of cerium dioxide and titanium dioxide nanomaterials in rats after single and repeated inhalation exposures.

BACKGROUND: Physiologically based kinetic models facilitate the safety assessment of inhaled engineered nanomaterials (ENMs). To develop these models, high quality datasets on well-characterized ENMs are needed. However, there are at present, several data gaps in the systemic availability of poorly soluble particles after inhalation. The aim of the present study was therefore to acquire two comparable datasets to parametrize a physiologically-based kinetic model. METHOD: Rats were exposed to cerium dioxide (CeO2, 28.4 ± 10.4 nm) and titanium dioxide (TiO2, 21.6 ± 1.5 nm) ENMs in a single nose-only exposure to 20 mg/m3 or a repeated exposure of 2 × 5 days to 5 mg/m3. Different dose levels were obtained by varying the exposure time for 30 min, 2 or 6 h per day. The content of cerium or titanium in three compartments of the lung (tissue, epithelial lining fluid and freely moving cells), mediastinal lymph nodes, liver, spleen, kidney, blood and excreta was measured by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) at various time points post-exposure. As biodistribution is best studied at sub-toxic dose levels, lactate dehydrogenase (LDH), total protein, total cell numbers and differential cell counts were determined in bronchoalveolar lavage fluid (BALF). RESULTS: Although similar lung deposited doses were obtained for both materials, exposure to CeO2 induced persistent inflammation indicated by neutrophil granulocytes influx and exhibited an increased lung elimination half-time, while exposure to TiO2 did not. The lavaged lung tissue contained the highest metal concentration compared to the lavage fluid and cells in the lavage fluid for both materials. Increased cerium concentrations above control levels in secondary organs such as lymph nodes, liver, spleen, kidney, urine and faeces were detected, while for titanium this was found in lymph nodes and liver after repeated exposure and in blood and faeces after a single exposure. CONCLUSION: We have provided insight in the distribution kinetics of these two ENMs based on experimental data and modelling. The study design allows extrapolation at different dose-levels and study durations. Despite equal dose levels of both ENMs, we observed different distribution patterns, that, in part may be explained by subtle differences in biological responses in the lung.

Machine Learning Allowed Interpreting Toxicity of a Fe-Doped CuO NM Library Large Data Set─An Environmental In Vivo Case Study.

The wide variation of nanomaterial (NM) characters (size, shape, and properties) and the related impacts on living organisms make it virtually impossible to assess their safety; the need for modeling has been urged for long. We here investigate the custom-designed 1-10% Fe-doped CuO NM library. Effects were assessed using the soil ecotoxicology model Enchytraeus crypticus (Oligochaeta) in the standard 21 days plus its extension (49 days). Results showed that 10%Fe-CuO was the most toxic (21 days reproduction EC50 = 650 mg NM/kg soil) and Fe3O4 NM was the least toxic (no effects up to 3200 mg NM/kg soil). All other NMs caused similar effects to E. crypticus (21 days reproduction EC50 ranging from 875 to 1923 mg NM/kg soil, with overlapping confidence intervals). Aiming to identify the key NM characteristics responsible for the toxicity, machine learning (ML) modeling was used to analyze the large data set [9 NMs, 68 descriptors, 6 concentrations, 2 exposure times (21 and 49 days), 2 endpoints (survival and reproduction)]. ML allowed us to separate experimental related parameters (e.g., zeta potential) from particle-specific descriptors (e.g., force vectors) for the best identification of important descriptors. We observed that concentration-dependent descriptors (environmental parameters, e.g., zeta potential) were the most important under standard test duration (21 day) but not for longer exposure (closer representation of real-world conditions). In the longer exposure (49 days), the particle-specific descriptors were more important than the concentration-dependent parameters. The longer-term exposure showed that the steepness of the concentration-response decreased with an increased Fe content in the NMs. Longer-term exposure should be a requirement in the hazard assessment of NMs in addition to the standard in OECD guidelines for chemicals. The progress toward ML analysis is desirable given its need for such large data sets and significant power to link NM descriptors to effects in animals. This is beyond the current univariate and concentration-response modeling analysis.

Graphene Oxide Nanosheets Toxicity in Mice Is Dependent on Protein Corona Composition and Host Immunity.

Two-dimension graphene oxide (GO) nanosheets with high and low serum protein binding profiles (high/low hard-bound protein corona/HChigh/low) are used in this study as model materials and screening tools to investigate the underlying roles of the protein corona on nanomaterial toxicities in vivo. We proposed that the in vivo biocompatibility/nanotoxicity of GO is protein corona-dependent and host immunity-dependent. The hypothesis was tested by injecting HChigh/low GO nanosheets in immunocompetent ICR/CD1 and immunodeficient NOD-scid II2rγnull mice and performed histopathological and hematological evaluation studies on days 1 and 14 post-injection. HClow GO induced more severe acute lung injury compared to HChigh GO in both immunocompetent and immunodeficient mice, with the effect being particularly pronounced in immunocompetent animals. Additionally, HClow GO caused more significant liver injury in both types of mice, with immunodeficient mice being more susceptible to its hepatotoxic effects. Moreover, administration of HClow GO resulted in increased hematological toxicity and elevated levels of serum pro-inflammatory cytokines in immunocompromised and immunocompetent mice, respectively. Correlation studies were conducted to explore the impact of distinct protein corona compositions on resulting toxicities in both immunocompetent and immunodeficient mice. This facilitated the identification of consistent patterns, aligning with those observed in vitro, thus indicating a robust in vitro-in vivo correlation. This research will advance our comprehension of how hard corona proteins interact with immune cells, leading to toxicity, and will facilitate the development of improved immune-modulating nanomaterials for therapeutic purposes.

Engineered nanomaterials exert sublethal bacterial stress at very low doses: Effects of concentration, light, and media on cell membrane permeability.

Engineered nanomaterials (ENMs) can alter surface properties of cells and disturb cellular functions and gene expression through direct and indirect contact, exerting unintended impacts on human and ecological health. However, the effects of interactions among environmental factors, such as light, surrounding media, and ENM mixtures, on the mechanisms of ENM toxicity, especially at sublethal concentrations, are much less explored and understood. Therefore, we evaluated cell viability and outer membrane permeability of E. coli as a function of exposure to environmentally relevant concentrations of ENMs, including metal (n-Ag) and metal oxide (n-TiO2, n-Al2O3, n-ZnO, n-CuO, and n-SiO2) nanoparticles under dark and simulated sunlight illumination in MOPS, a synthetic buffer, and Lake Michigan Water (LMW), a freshwater medium. We found that light activates the phototoxicity of n-TiO2 and n-Ag by inducing significant increases in bacterial outer membrane permeability at sublethal doses (< 1 mg/L). Other ENMs, including n-ZnO, n-CuO, n-Al2O3, and n-SiO2, have small to minimal impacts. Toxicities of ENMs were greater in LMW than MOPS due to their different ionic strength and chemical composition. Physical and chemical interactions between n-TiO2 and n-Ag lead to amplified toxic effects of the ENM mixtures that are greater than the additive effects of individual ENMs acting alone. Our results revealed the significant sublethal bacterial stress exerted by ENMs and ENM mixtures at the cell surface in natural environments at low doses, which can potentially lead to further cellular damage and eventually impact overall ecological health.

Microbial response to the chronic toxicity effect of graphene and graphene oxide nanomaterials within aerobic granular sludge systems.

Nanomaterials present in wastewater can pose a significant threat to aerobic granular sludge (AGS) systems. Herein, we found that compared to graphene nanomaterials (G-NMs), the long-term presence (95 days) of graphene oxide nanomaterials (GO-NMs) resulted in an increased proliferation of filamentous bacteria, poorer sedimentation performance (SVI30 of 74.1 mL/g) and smaller average particle size (1224.4 µm) of the AGS. In particular, the GO-NMs posed a more significant inhibitory effect to the total nitrogen removal efficiency of AGS (decreased by 14.3 %), especially for the denitrification process. The substantial accumulation of GO-NMs within the sludge matrix resulted in a higher level of reactive oxygen species in AGS compared to G-NMs, thereby inducing lactate dehydrogenase release, and enhancing superoxide oxidase and catalase activities. Such excessive oxidative stress could potentially result in a significant reduction in the activity of nitrogen metabolism enzymes (e.g., nitrate reductase and nitrite reductase) and the expression of key functional genes (e.g., nirS and nirK). Altogether, compared to G-NMs, prolonged exposure to GO-NMs had a more significant chronic toxicity effect on AGS systems. These findings implied that the presence of G-NMs and GO-NMs is a hidden danger to biological nitrogen removal and should receive more attention.

Pro-inflammatory and genotoxic responses by metal oxide nanomaterials in alveolar epithelial cells and macrophages in submerged condition and air-liquid interface: An in vitro-in vivo correlation study.

Studies on in vitro-in vivo correlations of inflammatory and genotoxic responses are needed to advance new approach methodologies. Here, we assessed pro-inflammatory and genotoxic responses by 13 nanosized metal oxides (nMeOx) and quartz (DQ12) in alveolar epithelial cells (A549) and macrophages (THP-1a) exposed in submerged conditions, and in A549:THP-1a co-cultures in air-liquid interface (ALI) system. Soluble nMeOx produced the highest IL-8 expression in A549 and THP-1a cells in submerged conditions (≥2-fold, p < 0.05), whereas only CuO caused a strong response in co-cultures exposed in the ALI system (13-fold, p < 0.05). IL-8 expression in A549 cells with concentrations as nMeOx specific surface area (SSA) correlated with neutrophil influx in mice (r = 0.89-0.98, p < 0.05). Similarly, IL-8 expression in THP-1a cell with concentrations as mass and SSA (when excluding soluble nMeOx) correlated with neutrophil influx in mice (r = 0.81-0.84, p < 0.05). DNA strand breaks (SB) was measured by the comet assay. We used a scoring system that categorizes effects in standard deviation units for comparison of genotoxicity in different models. Concordant genotoxicity was observed between SB levels in vitro (A549 and co-culture) and in vivo (broncho-alveolar lavage fluid cells and lung tissue). In conclusion, this study shows in vitro-in vivo correlations of nMeOx-induced inflammatory and genotoxic responses.

Unravelling the toxicity of carbon nanomaterials - From cellular interactions to mechanistic understanding.

The application of carbon nanomaterials in diverse fields has substantially increased their demand for commercial usage. Within the earliest decade, the development of functional materials has further increased the significance of this element. Despite the advancements recorded, the potential harmful impacts of embracing carbon nanomaterials for biological applications must be balanced against their advantages. Interestingly, many studies have neglected the intriguing and dynamic cellular interaction of carbon nanomaterials and the mechanistic understanding of their property-driven behaviour, even though common toxicity profiles have been reported. Reiterating the toxicity issue, several researchers conclude that these materials have minimal toxicity and may be safe for contact with biological systems at certain dosages. Here, we aim to provide a report on the significance of some of the properties that influence their toxicity. After that, a description of the implication of nanotoxicology in humans and living systems, revealing piece by piece their exposure routes and possible risks, will be provided. Then, an extensive discussion of the mechanistic puzzle modulating the interface between various human cellular systems and carbon nanomaterials such as carbon nanotubes, carbon dots, graphene, fullerenes, and nanodiamonds will follow. Finally, this review also sheds light on the organization that handles the risk associated with nanomaterials.

Overview of in vitro-in vivo extrapolation approaches for the risk assessment of nanomaterial toxicity.

Nanomaterials are increasingly used in many applications due to their enhanced properties. To ensure their safety for humans and the environment, nanomaterials need to be evaluated for their potential risk. The risk assessment analysis on the nanomaterials based on animal or in vivo studies is accompanied by several concerns, including animal welfare, time and cost needed for the studies. Therefore, incorporating in vitro studies in the risk assessment process is increasingly considered. To be able to analyze the potential risk of nanomaterial to human health, there are factors to take into account. Utilizing in vitro data in the risk assessment analysis requires methods that can be used to translate in vitro data to predict in vivo phenomena (in vitro-in vivo extrapolation (IVIVE) methods) to be incorporated, to obtain a more accurate result. Apart from the experiments and species conversion (for example, translation between the cell culture, animal and human), the challenge also includes the unique properties of nanomaterials that might cause them to behave differently compared to the same materials in a bulk form. This overview presents the IVIVE techniques that are developed to extrapolate pharmacokinetics data or doses. A brief example of the IVIVE methods for chemicals is provided, followed by a more detailed summary of available IVIVE methods applied to nanomaterials. The IVIVE techniques discussed include the comparison between in vitro and in vivo studies, methods to rene the dose metric or the in vitro models, allometric approach, mechanistic modeling, Multiple-Path Particle Dosimetry (MPPD), methods using organ burden data and also approaches that are currently being developed.

Next Generation Risk Assessment approaches for advanced nanomaterials: Current status and future perspectives.

This manuscript discusses the challenges of applying New Approach Methodologies (NAMs) for safe by design and regulatory risk assessment of advanced nanomaterials (AdNMs). The authors propose a framework for Next Generation Risk Assessment of AdNMs involving NAMs that is aligned to the conventional risk assessment paradigm. This framework is exposure-driven, endpoint-specific, makes best use of pre-existing information, and can be implemented in tiers of increasing specificity and complexity of the adopted NAMs. The tiered structure of the approach, which effectively combines the use of existing data with targeted testing will allow safety to be assessed cost-effectively and as far as possible with even more limited use of vertebrates. The regulatory readiness of state-of-the-art emerging NAMs is assessed in terms of Transparency, Reliability, Accessibility, Applicability, Relevance and Completeness, and their appropriateness for AdNMs is discussed in relation to each step of the risk assessment paradigm along with providing perspectives for future developments in the respective scientific and regulatory areas.

Bioinformatics and machine learning to support nanomaterial grouping.

Nanomaterials (NMs) offer plenty of novel functionalities. Moreover, their physicochemical properties can be fine-tuned to meet the needs of specific applications, leading to virtually unlimited numbers of NM variants. Hence, efficient hazard and risk assessment strategies building on New Approach Methodologies (NAMs) become indispensable. Indeed, the design, the development and implementation of NAMs has been a major topic in a substantial number of research projects. One of the promising strategies that can help to deal with the high number of NMs variants is grouping and read-across. Based on demonstrated structural and physicochemical similarity, NMs can be grouped and assessed together. Within an established NM group, read-across may be performed to fill in data gaps for data-poor variants using existing data for NMs within the group. Establishing a group requires a sound justification, usually based on a grouping hypothesis that links specific physicochemical properties to well-defined hazard endpoints. However, for NMs these interrelationships are only beginning to be understood. The aim of this review is to demonstrate the power of bioinformatics with a specific focus on Machine Learning (ML) approaches to unravel the NM Modes-of-Action (MoA) and identify the properties that are relevant to specific hazards, in support of grouping strategies. This review emphasizes the following messages: 1) ML supports identification of the most relevant properties contributing to specific hazards; 2) ML supports analysis of large omics datasets and identification of MoA patterns in support of hypothesis formulation in grouping approaches; 3) omics approaches are useful for shifting away from consideration of single endpoints towards a more mechanistic understanding across multiple endpoints gained from one experiment; and 4) approaches from other fields of Artificial Intelligence (AI) like Natural Language Processing or image analysis may support automated extraction and interlinkage of information related to NM toxicity. Here, existing ML models for predicting NM toxicity and for analyzing omics data in support of NM grouping are reviewed. Various challenges related to building robust models in the field of nanotoxicology exist and are also discussed.

Worse pulmonary function in association with cumulative exposure to nanomaterials. Hints of a mediation effect via pulmonary inflammation.

BACKGROUND: Today, nanomaterials are broadly used in a wide range of industrial applications. Such large utilization and the limited knowledge on to the possible health effects have raised concerns about potential consequences on human health and safety, beyond the environmental burden. Given that inhalation is the main exposure route, workers exposed to nanomaterials might be at risk of occurrence of respiratory morbidity and/or reduced pulmonary function. However, epidemiological evidence regarding the association between cumulative exposure to nanomaterials and respiratory health is still scarce. This study focused on the association between cumulative exposure to nanomaterials and pulmonary function among 136 workers enrolled in the framework of the European multicentric NanoExplore project. RESULTS: Our findings suggest that, independently of lifelong tobacco smoking, ethnicity, age, sex, body mass index and physical activity habits, 10-year cumulative exposure to nanomaterials is associated to worse FEV1 and FEF25 - 75%, which might be consistent with the involvement of both large and small airway components and early signs of airflow obstruction. We further explored the hypothesis of a mediating effect via airway inflammation, assessed by interleukin (IL-)10, IL-1ß and Tumor Necrosis Factor alpha (TNF-α), all quantified in the Exhaled Breath Condensate of workers. The mediation analysis results suggest that IL-10, TNF-α and their ratio (i.e., anti-pro inflammatory ratio) may fully mediate the negative association between cumulative exposure to nanomaterials and the FEV1/FVC ratio. This pattern was not observed for other pulmonary function parameters. CONCLUSIONS: Safeguarding the respiratory health of workers exposed to nanomaterials should be of primary importance. The observed association between cumulative exposure to nanomaterials and worse pulmonary function parameters underscores the importance of implementing adequate protective measures in the nanocomposite sector. The mitigation of harmful exposures may ensure that workers can continue to contribute productively to their workplaces while preserving their respiratory health over time.

Nanostructured Magnetic Particles for Removing Cyanotoxins: Assessing Effectiveness and Toxicity In Vitro.

The rise in cyanobacterial blooms due to eutrophication and climate change has increased cyanotoxin presence in water. Most current water treatment plants do not effectively remove these toxins, posing a potential risk to public health. This study introduces a water treatment approach using nanostructured beads containing magnetic nanoparticles (MNPs) for easy removal from liquid suspension, coated with different adsorbent materials to eliminate cyanotoxins. Thirteen particle types were produced using activated carbon, CMK-3 mesoporous carbon, graphene, chitosan, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidised cellulose nanofibers (TOCNF), esterified pectin, and calcined lignin as an adsorbent component. The particles' effectiveness for detoxification of microcystin-LR (MC-LR), cylindrospermopsin (CYN), and anatoxin-A (ATX-A) was assessed in an aqueous solution. Two particle compositions presented the best adsorption characteristics for the most common cyanotoxins. In the conditions tested, mesoporous carbon nanostructured particles, P1-CMK3, provide good removal of MC-LR and Merck-activated carbon nanostructured particles, P9-MAC, can remove ATX-A and CYN with high and fair efficacy, respectively. Additionally, in vitro toxicity of water treated with each particle type was evaluated in cultured cell lines, revealing no alteration of viability in human renal, neuronal, hepatic, and intestinal cells. Although further research is needed to fully characterise this new water treatment approach, it appears to be a safe, practical, and effective method for eliminating cyanotoxins from water.

A Network Toxicology Approach for Mechanistic Modelling of Nanomaterial Hazard and Adverse Outcomes.

Hazard assessment is the first step in evaluating the potential adverse effects of chemicals. Traditionally, toxicological assessment has focused on the exposure, overlooking the impact of the exposed system on the observed toxicity. However, systems toxicology emphasizes how system properties significantly contribute to the observed response. Hence, systems theory states that interactions store more information than individual elements, leading to the adoption of network based models to represent complex systems in many fields of life sciences. Here, they develop a network-based approach to characterize toxicological responses in the context of a biological system, inferring biological system specific networks. They directly link molecular alterations to the adverse outcome pathway (AOP) framework, establishing direct connections between omics data and toxicologically relevant phenotypic events. They apply this framework to a dataset including 31 engineered nanomaterials with different physicochemical properties in two different in vitro and one in vivo models and demonstrate how the biological system is the driving force of the observed response. This work highlights the potential of network-based methods to significantly improve their understanding of toxicological mechanisms from a systems biology perspective and provides relevant considerations and future data-driven approaches for the hazard assessment of nanomaterials and other advanced materials.

Nanometabolomics Elucidated Biological Prospective of Mo4/3B2-x Nanosheets: Toward Metabolic Reprogramming of Amino Acid Metabolism.

Mo4/3B2-x nanosheets are newly developed, and 2D transition metal borides (MBene) were reported in 2021, but there is no report on their further applications and modification; hence, this article sheds light on the significance of potential biological prospects for future biomedical applications. Therefore, elucidation of the biocompatibility, biotoxicology, and bioactivity of Mo4/3B2-x nanosheets has been an urgent need to be fulfilled. Nanometabolomics (also referred as nanomaterials-based metabolomics) was first proposed and utilized in our previous work, which specialized in interpreting nanomaterials-induced metabolic reprogramming through aqueous metabolomics and lipidomics approach. Hence, nanometabolomics could be considered as a novel concept combining nanoscience and metabolomics to provide bioinformation on nanomaterials' biomedical applications. In this work, the safe range of concentration (<50 mg/L) with good biosafety toward human umbilical vein endothelial cells (HUVECs) was discovered. The low concentration (5 mg/L) and high concentration (50 mg/L) of Mo4/3B2-x nanosheets were utilized for the in vitro Mo4/3B2-x-cell interaction. Nanometabolomics has elucidated the biological prospective of Mo4/3B2-x nanosheets via monitoring its biocompatibility and metabolic shift of HUVECs. The results revealed that 50 mg/L Mo4/3B2-x nanosheets could lead to a stronger alteration of amino acid metabolism with disturbance of the corresponding amino acid-related pathways (including amino acid metabolism, amino acid degradation, fatty acid biosynthesis, and lipid biosynthesis and metabolism). These interesting results were closely involved with the oxidative stress and production of excess ROS. This work could be regarded as a pathbreaking study on Mo4/3B2-x nanosheets at a biological level, which also designates their further biochemical, medical, and industrial application and development based on nanometabolomics bioinformation.

Assessing the role of the graphene family nanomaterials (GFNs: Graphene, GO, rGO) in modifying the toxicity potential and environmental risk of flame retardant, tetrabromobisphenol-A (TBBPA) in the marine microalgae Chlorella sp.

In recent years, a growing concern has emerged regarding the environmental implications of flame retardants (FRs) like tetrabromobisphenol-A (TBBPA) and graphene family nanomaterials (GFNs), such as graphene, graphene oxide (GO), and reduced graphene oxide (rGO), on marine biota. Despite these substances' well-established individual toxicity profiles, there is a notable gap in understanding the physicochemical interactions within the binary mixtures and consequent changes in the toxicity potential. Therefore, our research focuses on elucidating the individual and combined toxicological impacts of TBBPA and GFNs on the marine alga Chlorella sp. Employing a suite of experimental methodologies, including Raman spectroscopy, contact angle measurements, electron microscopy, and chromatography, we examined the physicochemical interplay between the GFNs and TBBPA. The toxicity potentials of individual constituents and their binary combinations were assessed through growth inhibition assays, quantifying reactive oxygen species (ROS) generation and malondialdehyde (MDA) production, photosynthetic activity analyses, and various biochemical assays. The toxicity of TBBPA and graphene-based nanomaterials (GFNs) was examined individually and in combinations. Both pristine TBBPA and GFNs showed dose-dependent toxicity. While lower TBBPA concentrations exacerbated toxicity in binary mixtures, higher TBBPA levels reduced the toxic effects compared to pristine TBBPA treatments. The principal mechanism underlying toxicity was ROS generation, resulting in membrane damage and perturbation of photosynthetic parameters. Cluster heatmap and Pearson correlation were employed to assess correlations between the biological parameters. Finally, ecological risk assessment was undertaken to evaluate environmental impacts of the individual components and the mixture in the algae.

Emerging concern of nano-pollution in agro-ecosystem: Flip side of nanotechnology.

Nanomaterials (NMs) have proven to be a game-changer in agriculture, showcasing their potential to boost plant growth and safeguarding crops. The agricultural sector has widely adopted NMs, benefiting from their small size, high surface area, and optical properties to augment crop productivity and provide protection against various stressors. This is attributed to their unique characteristics, contributing to their widespread use in agriculture. Human exposure from various components of agro-environmental sectors (soil, crops) NMs residues are likely to upsurge with exposure paths may stimulates bioaccumulation in food chain. With the aim to achieve sustainability, nanotechnology (NTs) do exhibit its potentials in various domains of agriculture also have its flip side too. In this review article we have opted a fusion approach using bibliometric based analysis of global research trend followed by a holistic assessment of pros and cons i.e. toxicological aspect too. Moreover, we have also tried to analyse the current scenario of policy associated with the application of NMs in agro-environment.

Investigation of the effects and mechanisms of manganese-based NMs on rice growth.

Manganese-based (Mn-based) nanomaterials (NMs) have great potential as alternatives to conventional Mn fertilizers. Yet, its environmental risks and effects on plant growth are not completely well understood. This study investigated the physiological effects of manganese dioxide (MnO2) and manganese tetroxide (Mn3O4) NMs on inter-root exposure (0-500 mg/L) of hydroponically grown rice. The results showed that on inter-root exposure, 50 mg/L Mn-based NMs promoted the uptake of mineral elements and enhanced the enzymatic activities of antioxidant systems (CAT and SOD) in rice, whereas 500 mg/L Mn3O4 NMs disrupted the mineral element homeostasis and led to phytotoxicity. The promotion effect of MnO2 NMs was better, firstly because MnO2 NMs treatment had lower Mn content in the plant than Mn3O4 NMs. In addition, MnO2 NMs are more transported and absorbed in the plant in ionic form, while Mn3O4 NMs exist in granular form. MnO2 NMs and Mn3O4 NMs both can be used as nano-fertilizers to improve the growth of rice by inter-root application, but the doses should be carefully selected.

Effects of dissolved organic matter on the environmental behavior and toxicity of metal nanomaterials: A review.

Metal nanomaterials (MNMs) have been released into the environment during their usage in various products, and their environmental behaviors directly impact their toxicity. Numerous environmental factors potentially affect the behaviors and toxicity of MNMs with dissolved organic matter (DOM) playing the most essential role. Abundant facts showing contradictory results about the effects of DOM on MNMs, herein the occurrence of DOM on the environmental process change of MNMs such as dissolution, dispersion, aggregation, and surface transformation were summarized. We also reviewed the effects of MNMs on organisms and their mechanisms in the environment such as acute toxicity, oxidative stress, oxidative damage, growth inhibition, photosynthesis, reproductive toxicity, and malformation. The presence of DOM had the potential to reduce or enhance the toxicity of MNMs by altering the reactive oxygen species (ROS) generation, dissolution, stability, and electrostatic repulsion of MNMs. Furthermore, we summarized the factors that affected different toxicity including specific organisms, DOM concentration, DOM types, light conditions, detection time, and production methods of MNMs. However, the more detailed mechanism of interaction between DOM and MNMs needs further investigation.