Biodegradation of Carbon Nanotube/Polymer Nanocomposites using a Monoculture.

The biodegradation rates of carbon nanotube (CNT)/ polymer nanocomposites (PNCs) containing poly-ε-caprolactone (PCL) were investigated using Pseudomonas aeruginosa, a microorganism commonly found in the environment. CNT/PCL nanocomposite mass loss profiles revealed that the rate of PCL matrix biodegradation decreased systematically as the CNT loading increased from 0.1 to 10% w/w. Addition of even a low CNT loading (<1% w/w) caused the CNT/PCL biodegradation rate constant to decrease by more than 50%. Similar trends in biodegradation rate were observed for both pristine and oxidized multiwall CNTs embedded in PCL. During PCL matrix biodegradation, CNT accumulation was observed at the surface of CNT/PCL nanocomposites and single particle inductively coupled-mass spectrometry experiments revealed no measurable CNT release to the culture fluid. Experimental data indicated that biodegradation proceeded as a result of biofilm formation on the CNT/PCL nanocomposites and decreased as a function of CNT loading due to the cytotoxicity of CNTs toward P. aeruginosa and the physical barrier presented by the surface-accumulated CNTs to the underlying PCL substrate. As the CNT loading in the CNT/PCL nanocomposites increased, the microbial proliferation of planktonic cells in the surrounding media also decreased as did the biodegradation rate of PCL samples present in the same reactors. Results from this study demonstrate that the inclusion of CNTs into polymer matrices could increase the environmental persistence of polymers in lakes, landfills, and surface waters.

Evaluation of bioaccumulation of nanoplastics, carbon nanotubes, fullerenes, and graphene family materials.

Bioaccumulation is a key factor in understanding the potential ecotoxicity of substances. While there are well-developed models and methods to evaluate bioaccumulation of dissolved organic and inorganic substances, it is substantially more challenging to assess bioaccumulation of particulate contaminants such as engineered carbon nanomaterials (CNMs; carbon nanotubes (CNTs), graphene family nanomaterials (GFNs), and fullerenes) and nanoplastics. In this study, the methods used to evaluate bioaccumulation of different CNMs and nanoplastics are critically reviewed. In plant studies, uptake of CNMs and nanoplastics into the roots and stems was observed. For multicellular organisms other than plants, absorbance across epithelial surfaces was typically limited. Biomagnification was not observed for CNTs and GFNs but were observed for nanoplastics in some studies. However, the reported absorption in many nanoplastic studies may be a consequence of an experimental artifact, namely release of the fluorescent probe from the plastic particles and subsequent uptake. We identify that additional work is needed to develop analytical methods to provide robust, orthogonal methods that can measure unlabeled (e.g., without isotopic or fluorescent labels) CNMs and nanoplastics.

Quantitative evaluation of released nanomaterials from carbon nanotube epoxy nanocomposites during environmental exposure and mechanical treatment.

Carbon nanotubes (CNTs) are promising nanomaterials exhibiting high thermal and electrical conductivities, significant stiffness, and high tensile strength. As a result, CNTs have been utilized as additives to enhance properties of various polymeric materials in a broad range of fields. In this study, we investigated the release of CNTs from CNT epoxy nanocomposites exposed to environmental weathering and mechanical stresses. The presence and amount of CNTs released from degraded polymer nanocomposites is important because CNTs can impact physiological systems in humans and environmental organisms. The weathering experiments in this study included nanocomposite exposure to both UV and a water spray, to simulate sunlight and rain exposure, whereas mechanical stresses were induced by shaking and ultrasonication. CNT release from epoxy nanocomposites was quantified by a 14C-labeling method that enabled measurement of the CNT release rates after different weathering and mechanical treatments. In this study, a sample oxidizer was used prior to liquid scintillation counting, because it was shown to reduce interferences from the presence of polymeric materials and achieve a high recovery (95%). Polymer nanocomposite degradation was confirmed by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), and light microscopy. A continuous release of 14C-labeled nanomaterials was observed after each UV and simulated rain exposure period, with 0.23% (mass/mass) of the total embedded mass of CNTs being released from the CNT nanocomposite during the full weathering process, suggesting that the water spray induced sufficient mechanical stress to eliminate the protective effect of the surface agglomerated CNT network. Importantly, additional mechanical stresses imposed on the weathered nanocomposites by shaking and ultrasonication resulted in further release of approximately 0.27% (mass /mass).

Influence of polymer type and carbon nanotube properties on carbon nanotube/polymer nanocomposite biodegradation.

The interaction of anaerobic microorganisms with carbon nanotube/polymer nanocomposites (CNT/PNC) will play a major role in determining their persistence and environmental fate at the end of consumer use when these nano-enabled materials enter landfills and encounter wastewater. Motivated by the need to understand how different parameters (i.e., polymer type, microbial phenotype, CNT characteristics) influence CNT/PNC biodegradation rates, we have used volumetric biogas measurements and kinetic modeling to study biodegradation as a function of polymer type and CNT properties. In one set of experiments, oxidized multiwall carbon nanotubes (O-MWCNTs) with a range of CNT loadings 0-5% w/w were incorporated into poly-ε-caprolactone (PCL) and polyhydroxyalkanoates (PHA) matrices and subjected to biodegradation by an anaerobic microbial community. For each CNT/PNC, complete polymer biodegradation was ultimately observed, although the rate of biodegradation was inhibited above certain critical CNT loadings dependent upon the polymer type. Higher loadings of pristine MWCNTs were needed to decrease the rate of polymer biodegradation compared to O-MWCNTs, an effect ascribed principally to differences in CNT dispersion within the polymer matrices. Above certain CNT loadings, a CNT mat of similar shape to the initial PNC was formed after polymer biodegradation, while below this threshold, CNT aggregates fragmented in the media. In situations where biodegradation was rapid, methanogen growth was disproportionately inhibited compared to the overall microbial community. Analysis of the results obtained from this study indicates that the inhibitory effect of CNTs on polymer biodegradation rate is greatest under conditions (i.e., polymer type, microbial phenotype, CNT dispersion) where biodegradation of the neat polymer is slowest. This new insight provides a means to predict the environmental fate, persistence, and transformations of CNT-enabled polymer materials.

Biodegradability of carbon nanotube/polymer nanocomposites under aerobic mixed culture conditions.

The properties and commercial viability of biodegradable polymers can be significantly enhanced by the incorporation of carbon nanotubes (CNTs). The environmental impact and persistence of these carbon nanotube/polymer nanocomposites (CNT/PNCs) after disposal will be strongly influenced by their microbial interactions, including their biodegradation rates. At the end of consumer use, CNT/PNCs will encounter diverse communities of microorganisms in landfills, surface waters, and wastewater treatment plants. To explore CNT/PNC biodegradation under realistic environmental conditions, the effect of multi-wall CNT (MWCNT) incorporation on the biodegradation of polyhydroxyalkanoates (PHA) was investigated using a mixed culture of microorganisms from wastewater. Relative to unfilled PHA (0% w/w), the MWCNT loading (0.5-10% w/w) had no statistically significant effect on the rate of PHA matrix biodegradation. Independent of the MWCNT loading, the extent of CNT/PNC mass remaining closely corresponded to the initial mass of CNTs in the matrix suggesting a lack of CNT release. CNT/PNC biodegradation was complete in approximately 20 days and resulted in the formation of a compressed CNT mat that retained the shape of the initial CNT/PNC. This study suggests that although CNTs have been shown to be cytotoxic towards a range of different microorganisms, this does not necessarily impact the biodegradation of the surrounding polymer matrix in mixed culture, particularly in situations where the polymer type and/or microbial population favor rapid polymer biodegradation.

Block copolymer lithography of rhodium nanoparticles for high temperature electrocatalysis.

We present a method for forming ordered rhodium nanostructures on a solid support. The approach makes use of a block copolymer to create and assemble rhodium chloride nanoparticles from solution onto a surface; subsequent plasma and thermal processing are employed to remove the polymer and fully convert the nanostructures to metallic rhodium. Films cast from a solution of the triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) dissolved in toluene with rhodium(III) chloride hydrate were capable of producing a monolayer of rhodium nanoparticles of uniform size and interparticle spacing. The nanostructures were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. The electrocatalytic performance of the nanoparticles was investigated with AC impedance spectroscopy. We observed that the addition of the particles to a model solid oxide fuel cell anode provided up to a 14-fold improvement in the anode activity as evidenced by a decrease in the AC impedance resistance. Examination of the anode after electrochemical measurement revealed that the basic morphology and distribution of the particles were preserved.