Polypropylene-MWCNT composite degradation, release, detection, and toxicity of MWCNT during accelerated aging.

Nanomaterials (NM) are incorporated into polymers to enhance their properties. However, there are a limited number of studies on the aging of these nanocomposites and the resulting potential release of NM. To characterize NM at critical points in their life cycles, polypropylene (PP) and multiwall carbon nanotube filled PP (PP-MWCNT) plates with different thicknesses (from 0.25 mm to 2 mm) underwent accelerated weathering in a chamber that simulates solar irradiation and rainfall. The physicochemical changes of the plates depended on the radiation exposure, the plate thickness, and the presence of CNT fillers. Photodegradation increased with aging time, making the exposed surface more hydrophilic, decreasing the surface hardness and creating surface stress-cracks. Aged surface and cross-section showed crazing due to the polymer bond scission and the formation of carbonyls. The degradation was higher near the UV-exposed surface as the intensity of the radiation and oxygen diffusion decreased with increasing depth of the plates, resulting in an oxidation layer directly proportional to oxygen diffusion. Thus, sample thickness determines the kinetics of the degradation reaction and the transport of reactive species. Plastic fragments, which are less than 1 mm, and free CNTs were released from weathered MWCNT-PP. The concentrations of released NM that were estimated using ICP-MS, increased with prolonged aging time. Various toxicity tests, including reactive oxygen species generation and cell activity/viability, were performed on the released CNTs. The toxicity of the released fragments and CNTs to A594 adenocarcinomic human alveolar basal epithelial cells was observed. The released polymer fragments and CNTs did not show significant toxicity under the experimental conditions in this study. This study will help manufacturers, users of consumer products with nanocomposites and policymakers in the development of testing guidelines, predictive models, and risk assessments and risk based-formulations of NM exposure.

Effectiveness of biosurfactant for the removal of trihalomethanes by biotrickling filter.

In this study, the biodegradation of a mixture of two trihalomethane (THM) compounds, chloroform (CF) and dichlorobromomethane (DCBM), was evaluated using two laboratory-scale biotrickling filters (BTFs). The two BTFs, hereby designated as "BTF-A" and "BTF-B," were run parallel and used ethanol as co-metabolite at different loading rates (LRs), and a lipopeptide-type biosurfactant that was generated by the gram-positive bacteria, Surfactin, respectively. The results using BTF-A showed that adding ethanol at a higher rate of 4.59 g/(m3 h) resulted in removal efficiencies of 85% and 87% for CF and DCBM, respectively. Conversely, for the same LR, the use of Surfactin without ethanol (BTF-B) showed comparable removal efficiencies of 85% and 80% for CF and DCBM, respectively. The maximum rate constant for CF and DCBM for the BTF-A was 0.00203 s-1 and 0.0022 s-1, respectively. For the same THMs LR, similar reaction rate constants resulted for the BTF-B. Further studies were conducted to investigate and understand the microbial diversity within both BTFs. The result indicated that for BTF with co-metabolite, Fusarium sp. was the most dominant fungi over 98% followed by F. Solani with less than 2%. F. oxysporum and Fusarium sp. were instead the dominant fungi for the BTF with Surfactin. Before introducing the Surfactin into the BTF, the batch experiment was conducted to evaluate the effectiveness of synthetic surfactant as compared to a biosurfactant (Surfactin). In this regard, vials with Surfactin showed better performance than vials with Tomadol 25-7 (synthetic surfactant).

Evaluating Weathering of Food Packaging Polyethylene-Nano-clay Composites: Release of Nanoparticles and their Impacts.

Nano-fillers are increasingly incorporated into polymeric materials to improve the mechanical, barrier or other matrix properties of nanocomposites used for consumer and industrial applications. However, over the life cycle, these nanocomposites could degrade due to exposure to environmental conditions, resulting in the release of embedded nanomaterials from the polymer matrix into the environment. This paper presents a rigorous study on the degradation and the release of nanomaterials from food packaging composites. Films of nano-clay-loaded low-density polyethylene (LDPE) composite for food packaging applications were prepared with the spherilene technology and exposed to accelerated weathering of ultraviolet (UV) irradiation or low concentration of ozone at 40 °C. The changes in the structural, surface morphology, chemical and physical properties of the films during accelerated weathering were investigated. Qualitative and quantitative changes in properties of pristine and aged materials and the release of nano-clay proceeded slowly until 130 hr irradiation and then accelerated afterward resulting complete degradation. Although nano-clay increased the stability of LDPE and improved thermal and barrier properties, they accelerated the UV oxidation of LDPE. With increasing exposure to UV, the surface roughness, chemiluminescence index, and carbonyl index of the samples increased while decreasing the intensity of the wide-angle X-ray diffraction pattern. Nano-clay particles with sizes ranging from 2-8 nm were released from UV and ozone weathered composite. The concentrations of released nanoparticles increased with an increase in aging time. Various toxicity tests, including reactive oxygen species generation and cell activity/viability were also performed on the released nano-clay and clay polymer. The released nano-clays basically did not show toxicity. Our combined results demonstrated the degradation properties of nano-clay particle-embedded LDPE composites toxicity of released nano-clay particles to A594 adenocarcinomic human alveolar basal epithelial cells was observed, which will help with future risk based-formulations of exposure.

Performance of Anaerobic Biotrickling Filter and its Microbial Diversity for the Removal of Stripped Disinfection Byproducts.

The objective of this research was to evaluate the biodegradation of chloroform by using biotrickling filter (BTF) and determining the dominant bacteria responsible for the degradation. The research was conducted in three phases under anaerobic condition, namely, in the presence of co-metabolite (Phase I), in the presence of co-metabolite and surfactant (Phase II) and in the presence of surfactant but no co-metabolite (Phase III). The results showed that the presence of ethanol as a co-metabolite provided 49% removal efficiency. The equivalent elimination capacity (EC) was 0.13 g/(m3.hr). The addition of Tomadol 25 - 7 as a surfactant in the nutrient solution increased the removal efficiency of chloroform to 64% with corresponding EC of 0.17 g/(m3.hr). This research also investigated the overall microbial ecology of the BTF utilizing culture-independent gene sequencing alignment of the 16S rRNA allowing identification of isolated species. Taxonomical composition revealed the abundance of deltaproteobacteria and deltaproteobacteria with species level of 97%. A. oryzae (formally dechlorosoma suillum), A. restrica and Geobacter spp. together with other similar groups were the most valuable bacteria for the degradation of chloroform.

NanoRelease: Pilot interlaboratory comparison of a weathering protocol applied to resilient and labile polymers with and without embedded carbon nanotubes.

A major use of multi-walled carbon nanotubes (MWCNTs) is as functional fillers embedded in a solid matrix, such as plastics or coatings. Weathering and abrasion of the solid matrix during use can lead to environmental releases of the MWCNTs. Here we focus on a protocol to identify and quantify the primary release induced by weathering, and assess reproducibility, transferability, and sensitivity towards different materials and uses. We prepared 132 specimens of two polymer-MWCNT composites containing the same grade of MWCNTs used in earlier OECD hazard assessments but without UV stabilizer. We report on a pilot inter-laboratory comparison (ILC) with four labs (two US and two EU) aging by UV and rain, then shipping for analysis. Two labs (one US and one EU) conducted the release sampling and analysis by Transmission Electron Microscopy (TEM), Inductively Coupled Plasma- Mass Spectrometry (ICP-MS), UltravioleteVisible Spectroscopy (UVeVis), Analytical Ultracentrifugation (AUC), and Asymmetric Flow Field Flow Fractionation (AF4). We compare results between aging labs, between analysis labs and between materials. Surprisingly, we found quantitative agreement between analysis labs for TEM, ICP-MS, UVeVis; low variation between aging labs by all methods; and consistent rankings of release between TEM, ICP-MS, UVeVis, AUC. Significant disagreement was related primarily to differences in aging, but even these cases remained within a factor of two.

Interaction of engineered nanomaterials with hydrophobic organic pollutants.

As nanomaterials become an increasing part of everyday consumer products, it is imperative to monitor their potential release during production, use and disposal, and to assess their impact on the health of humans and the ecosystem. This necessitates research to better understand how the properties of engineered nanomaterials (ENMs) lead to their accumulation and redistribution in the environment, and to assess whether they could become novel pollutants or if they can affect the mobility and bioavailability of other toxins. This study focuses on understanding the influence of nanostructured-TiO2 and the interaction of multi-walled carbon nanotubes with organic pollutants in water. We studied the adsorption and water phase dispersion of model pollutants with relatively small water solubility (i.e., two- and three-ring polyaromatic hydrocarbons and insecticides) with respect to ENMs. The sorption of pollutants was measured based on water phase analysis, and by separating suspended particles from the water phase and analyzing dried samples using integrated thermal-chromatographic-mass spectroscopic (TGA/GC/MS) techniques. Solid phase analysis using a combination of TGA/GC/MS is a novel technique that can provide real-time quantitative analysis and which helps to understand the interaction of hydrophobic organic pollutants and ENMs. The adsorption of these contaminants to nanomaterials increased the concentration of the contaminants in the aqueous phase as compared to the 'real' partitioning due to the octanol-water partitioning. The study showed that ENMs can significantly influence the adsorption and dispersion of hydrophobic/low water soluble contaminants. The type of ENM, the exposure to light, and the water pH have a significant influence on the partitioning of pollutants.

Attenuation of methyl tert-butyl ether in water using sunlight and a photocatalyst.

The use of methyl tert-butyl ether (MTBE) as a gasoline additive has resulted in increasing pollution of groundwater. Most of the conventional treatment technologies are inefficient or costly when the initial concentration of MTBE is low (< 200 microg/L). To find an ecology friendly and inexpensive method for MTBE remediation, we used solar radiation with titanium dioxide (TiO2) as a photocatalyst. For synthetic samples, almost complete degradation (99+%) of MTBE was observed at the end of 5-hour test run with 0.05 g/L of slurry TiO2. Intermediate products detected were tertiary butyl formate, tertiary butyl alcohol, and trace amounts of acetone. Studies conducted using contaminated groundwater samples with TiO2 and sunlight showed that aromatic organic species benzene, toluene, ethylbenzene, and xylenes (BTEX) were degraded up to a factor of 10 times faster than MTBE. However, dissolved metals (Fe2+) and chloride ions in contaminated waters decreased the photo-activity of TiO2 for the degradation of MTBE. Reducing the pH of the groundwater samples increased the MTBE degradation rate threefold. Photocatalysis accelerates the solar degradation of MTBE and reduces its half-life by more than 3 orders of magnitude. The study indicated that solar degradation is a low-cost and effective alternative to attenuate MTBE in drinking water supplies.