Carbon nanotubes (CNTs) are often suspended in Pluronic® surfactants by sonication, which may confound toxicity studies because sonication of surfactants can create degradation products that are toxic to mammalian cells. Here, we present a toxicity assessment of Pluronic® F-108 with and without suspended CNTs using embryonic zebrafish as an in vivo model. Pluronic® sonolytic degradation products were toxic to zebrafish embryos just as they were to mammalian cells. When the toxic Pluronic® fragments were removed, there was little effect of pristine multi-walled CNTs (pMWNTs), carboxylated MWNTs (cMWNTs) or pristine single-walled carbon nanotubes (pSWNTs) on embryo viability and development, even at high concentrations. A gel electrophoretic method coupled with Raman imaging was developed to measure the bioaccumulation of CNTs by zebrafish embryos, and dose-dependent uptake of CNTs was observed. These data indicate that embryos accumulate pMWNTs, cMWNTs and pSWNTs yet there is very little embryo toxicity.
Few manufacturers provide elemental analysis information on the certificates of analysis of their single-walled carbon nanotube (SWCNT) soot products, and those who do primarily perform surface sensitive analyses that may not accurately represent the bulk properties of heterogeneous soot samples. Since the accurate elemental analysis of SWCNT soot is a requisite for exacting assessments of product quality and environmental health and safety (EH&S) risk, the purpose of this work was to develop a routine laboratory procedure for an extensive elemental analysis of SWCNT soot using bulk methods of analyses. Herein, a combination of carbon, hydrogen, nitrogen, sulfur, and oxygen (CHNS/O) combustion analyses, oxygen flask combustion/anion chromatography (OFC/AC), graphite furnace-atomic absorption spectroscopy (GF-AAS), and inductively coupled plasma-mass spectroscopy (ICP-MS) were used to generate a 77-element analysis of two as-received CoMoCAT® SWCNT soot products. Fourteen elements were detected in one product, nineteen in the other, and each data set was compared to its respective certificate of analysis. The addition of the OFC/AC results improved the accuracy of elements detected by GF-AAS and ICP-MS, and an assessment was performed on the results that concluded that the trace elemental impurities should not pose an EH&S concern if these soot products became airborne.
Carbon nanotubes (CNTs) are cylindrical molecules of carbon with diverse commercial applications. CNTs are also lightweight, easily airborne, and have been shown to be released during various phases of production and use. Therefore, as global CNT production increases, so do concerns that CNTs could pose a safety threat to those who are exposed to them. This makes it imperative to fully understand CNT release scenarios to make accurate risk assessments and to implement effective control measures. However, the current suite of direct-reading and off-line instrumentation used to monitor the release of CNTs in workplaces lack high chemical specificity, which complicates risk assessments when the sampling and/or measurements are performed at a single site where multiple CNT types are handled in the presence of naturally-occurring background particles, or dust. Herein, we demonstrate the utility of Raman spectroscopy to unequivocally identify whether particulate matter collected from a multi-user analytical balance workstation comprised CNTs, as well as, whether the contamination included CNTs that were synthesized by a Ni/Y-catalyzed electric-arc method or a Co/Mo-catalyzed chemical vapor deposition method. Identifying the exact CNT type generated a more accurate risk assessment by knowing the metallic impurities involved, and it also led to the identification of the users who handled these CNTs, a review of their handling techniques, and an improved protocol for safely weighing CNTs.
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