Substantial research efforts are under way to optimize the production of composites enhanced by the incorporation of nanomaterial fillers such as multiwall carbon nanotubes (MWCNTs). It is therefore ...critical to develop robust methods to detect and characterize MWCNTs in nanocomposites to measure product performance and potential risks from release of the MWCNTs. In this study, the effectiveness of X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and scanning electron microscopy (SEM) methods is assessed on a series of MWCNT-epoxy nanocomposites samples. A general trend of positive correlation between signal intensity and MWCNT mass loading was observed by both Raman spectroscopy and XPS. Raman spectroscopy was capable of detecting MWCNTs at the lowest nominal concentration tested (0.01%), while for XPS, MWCNTs were detected down to a threshold of approximately 0.5%. Analysis of the same locations of two nanocomposite samples with nominal MWCNT mass fractions of 0.3% and 1% using Raman chemical imaging and SEM revealed a similar detectability of MWCNT clusters and with the higher mass loading sample having a greater number of MWCNT-rich domains. Overall, these results show a good comparability among the different techniques and therefore provide comprehensive, nondestructive microscopy methods to characterize nanocomposites.
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Novel physicochemistries of engineered nanomaterials (ENMs) offer considerable commercial potential for new products and processes, but also the possibility of unforeseen and negative consequences ...upon ENM release into the environment. Investigations of ENM ecotoxicity have revealed that the unique properties of ENMs and a lack of appropriate test methods can lead to results that are inaccurate or not reproducible. The occurrence of spurious results or misinterpretations of results from ENM toxicity tests that are unique to investigations of ENMs (as opposed to traditional toxicants) have been reported, but have not yet been systemically reviewed. Our objective in this manuscript is to highlight artifacts and misinterpretations that can occur at each step of ecotoxicity testing: procurement or synthesis of the ENMs and assessment of potential toxic impurities such as metals or endotoxins, ENM storage, dispersion of the ENMs in the test medium, direct interference with assay reagents and unacknowledged indirect effects such as nutrient depletion during the assay, and assessment of the ENM biodistribution in organisms. We recommend thorough characterization of initial ENMs including measurement of impurities, implementation of steps to minimize changes to the ENMs during storage, inclusion of a set of experimental controls (e.g., to assess impacts of nutrient depletion, ENM specific effects, impurities in ENM formulation, desorbed surface coatings, the dispersion process, and direct interference of ENM with toxicity assays), and use of orthogonal measurement methods when available to assess ENMs fate and distribution in organisms.
Understanding the colloidal stability of graphene is essential for predicting its transport and ecological risks in aquatic environments. We investigated the agglomeration of 14C-labeled few-layer ...graphene (FLG) at concentrations spanning nearly four orders of magnitude (2 μg/L to 10 mg/L) using dynamic light scattering and sedimentation measurements. FLG agglomerates formed rapidly in deionized water at concentrations >3 mg/L. From 1 mg/L to 3 mg/L, salt-induced agglomeration was decreased with dilution of FLG suspensions; the critical coagulation concentration of the more concentrated suspension (3 mg/L) was significantly lower than the dilute suspension (1 mg/L) in the presence of NaCl (1.6 mmol/L and 10 mmol/L, respectively). In contrast, FLG underwent slow agglomeration and settling at concentrations ≤0.1 mg/L in NaCl solutions and ambient waters with low ionic strength (<10 mmol/L). FLG nanoparticles with smaller lateral sizes (25 nm–75 nm) were shown to agglomerate more slowly than larger FLG, and these small FLG particles exhibited greater bioaccumulation in zebrafish embryo and stronger chorion penetration ability than larger FLG particles. These findings suggest that FLG at more environmentally relevant concentration is relatively stable and may have implications for exposure of small FLG to ecological receptors.
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•Dilution retards the attachment, agglomeration and sedimentation of FLG.•FLG agglomerates rapidly in deionized water at concentrations >3 mg/L.•FLG (≤0.1 mg/L) is relatively stable in electrolyte solutions and ambient waters.•Ionic strength affects FLG stability in a manner consistent with the DLVO theory.•Suspended small FLG has strong chorion penetration ability in zebrafish embryos.
To fully understand the potential ecological and human health risks from nanoplastics and microplastics (NMPs) in the environment, it is critical to make accurate measurements. Similar to past ...research on the toxicology of engineered nanomaterials, a broad range of measurement artifacts and biases are possible when testing their potential toxicity. For example, antimicrobials and surfactants may be present in commercially available NMP dispersions, and these compounds may account for toxicity observed instead of being caused by exposure to the NMP particles. Therefore, control measurements are needed to assess potential artifacts, and revisions to the protocol may be needed to eliminate or reduce the artifacts. In this paper, we comprehensively review and suggest a next generation of control experiments to identify measurement artifacts and biases that can occur while performing NMP toxicity experiments. This review covers the broad range of potential NMP toxicological experiments, such as in vitro studies with a single cell type or complex 3-D tissue constructs, in vivo mammalian studies, and ecotoxicity experiments testing pelagic, sediment, and soil organisms. Incorporation of these control experiments can reduce the likelihood of false positive and false negative results and more accurately elucidate the potential ecological and human health risks of NMPs.
An increase in production of commercial products containing graphene-family nanomaterials (GFNs) has led to concern over their release into the environment. The fate and potential ecotoxicological ...effects of GFNs in the environment are currently unclear, partially due to the limited analytical methods for GFN measurements. In this review, the unique properties of GFNs that are useful for their detection and quantification are discussed. The capacity of several classes of techniques to identify and/or quantify GFNs in different environmental matrices (water, soil, sediment, and organisms), after environmental transformations, and after release from a polymer matrix of a product is evaluated. Extraction and strategies to combine methods for more accurate discrimination of GFNs from environmental interferences as well as from other carbonaceous nanomaterials are recommended. Overall, a comprehensive review of the techniques available to detect and quantify GFNs are systematically presented to inform the state of the science, guide researchers in their selection of the best technique for the system under investigation, and enable further development of GFN metrology in environmental matrices. Two case studies are described to provide practical examples of choosing which techniques to utilize for detection or quantification of GFNs in specific scenarios. Because the available quantitative techniques are somewhat limited, more research is required to distinguish GFNs from other carbonaceous materials and improve the accuracy and detection limits of GFNs at more environmentally relevant concentrations.
Many of the current investigations on the environmental and human health risks of engineered nanomaterials focus on their short-term acute toxicity. However, the long-term chronic effects of ...nanomaterials on living systems, and in particular, on the genetic components of living systems, also warrant attention. An increasing number of nanomaterial safety studies include an assessment of genotoxicity as part of the overall risk evaluation. The potential of nanomaterials to directly or indirectly promote the formation of reactive oxygen species is one of the primary steps in their genotoxic repertoire. The subsequent modification of genomic DNA by reactive oxygen species could lead to the development of mutagenesis, carcinogenesis, or other age-related diseases if the DNA damage is not repaired. This review focuses on the interactions of nanomaterials with DNA and specifically on the capacity of some nanomaterials to induce oxidative damage to DNA. A critical assessment of the analytical methodology and the potential biochemical mechanisms involved in nanomaterial induction of oxidative damage to DNA is presented, results obtained for the various studies with each nanomaterial are compared, and recommendations for future research are discussed. Researchers should consider, among other experimental recommendations, (1) the application of more chromatography-based and mass-spectrometry-based analytical techniques to the assessment of oxidative damage to DNA to facilitate an enhanced understanding of DNA damage mechanisms and (2) the verification of cellular viability before conducting genotoxicity assays to reduce the impact of fragmented DNA, formed as a consequence of cell death, on DNA damage measurements.
The potential human health risks from graphene inhalation exposure have attracted substantial scientific interest as a result of the numerous exciting potential commercial applications of graphene. ...However, the long-term distribution of graphene in organisms after inhalation is unknown, largely as a result of challenges associated with accurate graphene quantification.
Carbon-14 labeled FLG was used to quantify the in vivo distribution of FLG in mice after oral gavage or intratracheal instillation for up to 3 or 28 days after exposure, respectively.
Intratracheally instilled FLG was mainly retained in the lung with 47% remaining after 4 weeks. Exposure to non-labeled FLG resulted in dose-dependent acute lung injury and pulmonary edema, but these effects were alleviated with time despite the continued presence of FLG in the lungs. One percent and 0.18% of the intratracheally instilled FLG was present in the liver and spleen, respectively, after 14 days by passing through the air-blood barrier, a finding supported by the results of oral gavage experiments which did not show detectable absorption through the gastrointestinal tract. In addition, 46.2% of the intratracheally instilled FLG was excreted through the feces 28 d after exposure.
Quantitative measurements revealed the elimination mechanism for FLG and its biodistribution for two exposure pathways. Graphene persistence in the lung only caused transient pulmonary effects. The in vivo distribution, elimination, and toxicity results provided here measured using a robust quantitative method support the human health risk assessment of graphene.
The exciting commercial application potential of graphene materials may inevitably lead to their increasing release into the environment where they may pose ecological risks. This study focused on ...using carbon-14-labeled few-layer graphene (FLG) to determine whether the size of graphene plays a role in its uptake, depuration, and biodistribution in adult zebrafish. After 48 h exposure to larger FLG (L-FLG) at 250 μg/L, the amount of graphene in the organism was close to 48 mg/kg fish dry mass, which was more than 170-fold greater than the body burden of those exposed to the same concentration of smaller FLG (S-FLG). The amount of uptake for both L-FLG and S-FLG increased by a factor of 2.5 and 16, respectively, when natural organic matter (NOM) was added in the exposure suspension. While the L-FLG mainly accumulated in the gut of adult zebrafish, the S-FLG was found in both the gut and liver after exposure with or without NOM. Strikingly, the S-FLG was able to pass through the intestinal wall and enter the intestinal epithelial cells and blood. The presence of NOM increased the quantity of S-FLG in these cells. Exposure to L-FLG or S-FLG also had a significantly different impact on the intestinal microbial community structure.
Multiwall carbon nanotubes (MWCNTs) are nanofillers used in consumer and structural polymeric products to enhance a variety of properties. Under weathering, the polymer matrix will degrade and the ...nanofillers may be released from the products potentially impacting ecological or human health. In this study, we investigated the degradation of a 0.72% (by mass) MWCNT/amine-cured epoxy nanocomposite irradiated with high intensity ultraviolet (UV) light at various doses, the effects of UV exposure on the surface accumulation and potential release of MWCNTs, and possible mechanisms for the release resistance of the MWCNT surface layer formed on nanocomposites by UV irradiation. Irradiated samples were characterized for chemical degradation, mass loss, surface morphological changes, and MWCNT release using a variety of analytical techniques. Under 295 nm–400 nm UV radiation up to a dose of 4865 MJ/m2, the nanocomposite matrix underwent photodegradation, resulting in formation of a dense, entangled MWCNT network structure on the surface. However, no MWCNT release was detected, even at very high UV doses, suggesting that the MWCNT surface layer formed from UV irradiation of polymer nanocomposites resist release. Four possible release resistance mechanisms of the UV-induced MWCNT surface layer are presented and discussed.
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