Stability, metal leaching, photoactivity and toxicity in freshwater systems of commercial single wall carbon nanotubes.

Carbon nanotubes (CNTs) are exciting new materials that have been intensively researched and are becoming increasingly used in consumer products. With rapid growth in production and use of CNTs in many applications, there is the potential for emissions to the environment and thus research is needed to assess the risks associated with CNTs in the environment. Here we show that commercial CNTs differ in their stability, photoactivity, metal leachate, and toxicity to freshwater algae. The behavior between raw and purified variants of the CNTs differs considerably; for example purified CNTs are generally more photoactive, producing singlet oxygen and superoxide, while raw CNTs show little or no photoactivity. Residual metal catalysts differ based on synthesis method used to prepare CNTs and thus may be comprised of elements with varying degrees of toxic potential. Influenced by pH and other constituents of the natural waters, our work shows that metals can leach out from all the commercial CNTs studied, even purified versions, albeit at different levels in many natural waters. As much as 10% of the total residual nickel leached from a purified CNT after 72 h. Aqueous concentrations of molybdenum leached from a different purified CNT were nearly 0.060 mg L(-1) after 72 h. With little sample preparation, CNTs are dispersible in most freshwaters and stable for several days. Not all tested CNTs were toxic; for those CNTs that did induce toxicity we show that photoactivity, not metal leaching, contributes to the toxicity of commercial CNTs to freshwater algae, with growth rates significantly reduced by as much as 200%.

[1]  Richard D Handy,et al.  Toxicity of single walled carbon nanotubes to rainbow trout, (Oncorhynchus mykiss): respiratory toxicity, organ pathologies, and other physiological effects. , 2007, Aquatic toxicology.

[2]  R. Scholz,et al.  Modeled environmental concentrations of engineered nanomaterials (TiO(2), ZnO, Ag, CNT, Fullerenes) for different regions. , 2009, Environmental science & technology.

[3]  Kenneth A. Smith,et al.  Gas-phase catalytic growth of single-walled carbon nanotubes from carbon monoxide , 1999 .

[4]  Arjun G. Yodh,et al.  High Weight Fraction Surfactant Solubilization of Single-Wall Carbon Nanotubes in Water , 2003 .

[5]  Alan J Kennedy,et al.  Influence of nanotube preparation in Aquatic Bioassays , 2009, Environmental toxicology and chemistry.

[6]  S. Curran,et al.  Single-walled carbon nanotube purification, pelletization, and surfactant-assisted dispersion: a combined TEM and resonant micro-raman spectroscopy study. , 2005, The journal of physical chemistry. B.

[7]  Anthony J Bednar,et al.  Release of metal impurities from carbon nanomaterials influences aquatic toxicity. , 2009, Environmental Science and Technology.

[8]  Jae-Hong Kim,et al.  Natural organic matter stabilizes carbon nanotubes in the aqueous phase. , 2007, Environmental science & technology.

[9]  Robert H. Hauge,et al.  Purification and Characterization of Single-Wall Carbon Nanotubes (SWNTs) Obtained from the Gas-Phase Decomposition of CO (HiPco Process) , 2001 .

[10]  Dicksen Tanzil,et al.  Relative risk analysis of several manufactured nanomaterials: an insurance industry context. , 2005, Environmental science & technology.

[11]  Chad T. Jafvert,et al.  Photoreactivity of carboxylated single-walled carbon nanotubes in sunlight: reactive oxygen species production in water. , 2010, Environmental science & technology.

[12]  S. Chellam,et al.  Inactivation of bacteriophages via photosensitization of fullerol nanoparticles. , 2007, Environmental science & technology.

[13]  Tinh Nguyen,et al.  Potential release pathways, environmental fate, and ecological risks of carbon nanotubes. , 2011, Environmental science & technology.

[14]  Lei Zhang Functionalization of single walled carbon nanotubes , 2006 .

[15]  M. Tedetti,et al.  Penetration of Ultraviolet Radiation in the Marine Environment. A Review , 2006, Photochemistry and photobiology.

[16]  B. Nowack,et al.  Influence of the initial state of carbon nanotubes on their colloidal stability under natural conditions. , 2011, Environmental pollution.

[17]  M R Wiesner,et al.  Fullerol-sensitized production of reactive oxygen species in aqueous solution. , 2005, Environmental science & technology.

[18]  Arnaud Magrez,et al.  Are carbon nanotube effects on green algae caused by shading and agglomeration? , 2011, Environmental science & technology.

[19]  James E Hutchison,et al.  Greener nanoscience: a proactive approach to advancing applications and reducing implications of nanotechnology. , 2008, ACS nano.

[20]  Arturo A. Keller,et al.  TiO2 Nanoparticles Are Phototoxic to Marine Phytoplankton , 2012, PloS one.

[21]  W. Choi,et al.  Visible light-induced reactions of humic acids on TiO2 , 2002 .

[22]  R. Kane,et al.  Photoactivated antimicrobial activity of carbon nanotube-porphyrin conjugates. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[23]  A. Sharma,et al.  Spin probe ESR studies of dynamics of single walled carbon nanotubes. , 2008, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[24]  B. Nowack,et al.  Exposure modeling of engineered nanoparticles in the environment. , 2008, Environmental science & technology.

[25]  Annia Galano,et al.  Free Radical Scavenging Activity of Ultrashort Single-Walled Carbon Nanotubes with Different Structures through Electron Transfer Reactions , 2010 .

[26]  E. M. Thurman,et al.  Organic Geochemistry of Natural Waters , 1985, Developments in Biogeochemistry.

[27]  Menachem Elimelech,et al.  Single-walled carbon nanotubes exhibit strong antimicrobial activity. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[28]  Mark R Wiesner,et al.  Comparative photoactivity and antibacterial properties of C60 fullerenes and titanium dioxide nanoparticles. , 2009, Environmental science & technology.

[29]  Elijah J Petersen,et al.  Biological uptake and depuration of carbon nanotubes by Daphnia magna. , 2009, Environmental science & technology.

[30]  EÄ H,et al.  Laboratory Assessment of the Mobility of Nanomaterials in Porous Media , 2022 .

[31]  N. Calace,et al.  The role of organic matter on metal toxicity and bio-availability. , 2004, Annali di chimica.

[32]  Yu-Ying He,et al.  Photo‐induced Reactive Oxygen Species Generation by Different Water‐soluble Fullerenes (C60) and Their Cytotoxicity in Human Keratinocytes , 2008, Photochemistry and photobiology.

[33]  Ryan C. Templeton,et al.  Life-cycle effects of single-walled carbon nanotubes (SWNTs) on an estuarine meiobenthic copepod. , 2006, Environmental science & technology.

[34]  Arturo A. Keller,et al.  Comparative photoactivity of CeO2, γ-Fe2O3, TiO2 and ZnO in various aqueous systems , 2011 .

[35]  Vincent Castranova,et al.  Quantitative techniques for assessing and controlling the dispersion and biological effects of multiwalled carbon nanotubes in mammalian tissue culture cells. , 2010, ACS nano.

[36]  H. O N G T A O W A N G,et al.  Stability and Aggregation of Metal Oxide Nanoparticles in Natural Aqueous Matrices , 2010 .

[37]  R. Kane,et al.  Nanotube-assisted protein deactivation. , 2008, Nature nanotechnology.

[38]  Peng Wang,et al.  Enhanced environmental mobility of carbon nanotubes in the presence of humic acid and their removal from aqueous solution. , 2008, Small.

[39]  F. Gagné,et al.  Ecotoxicity of selected nano‐materials to aquatic organisms , 2008, Environmental toxicology.

[40]  William P. Ball,et al.  Assessing the colloidal properties of engineered nanoparticles in water: case studies from fullerene C60 nanoparticles and carbon nanotubes , 2010 .

[41]  K. Miyashita,et al.  Radical scavenging and singlet oxygen quenching activity of marine carotenoid fucoxanthin and its metabolites. , 2007, Journal of agricultural and food chemistry.

[42]  Philipp Mayer,et al.  Influence of growth conditions on the results obtained in algal toxicity tests , 1998 .

[43]  R. Murugesan,et al.  Photosensitization with anthraquinone derivatives: optical and EPR spin trapping studies of photogeneration of reactive oxygen species , 2004 .

[44]  W. P. Ball,et al.  Colloidal properties of aqueous suspensions of acid-treated, multi-walled carbon nanotubes. , 2009, Environmental science & technology.

[45]  Z. Gu,et al.  Direct Synthesis of High Purity Single-Walled Carbon Nanotube Fibers by Arc Discharge , 2004 .

[46]  Durairaj Baskaran,et al.  Carbon nanotubes with covalently linked porphyrin antennae: photoinduced electron transfer. , 2005, Journal of the American Chemical Society.

[47]  Daniel Morris,et al.  Targeted Removal of Bioavailable Metal as a Detoxification Strategy for Carbon Nanotubes. , 2008, Carbon.

[48]  K. Chen,et al.  Influence of surface oxidation on the aggregation and deposition kinetics of multiwalled carbon nanotubes in monovalent and divalent electrolytes. , 2011, Langmuir : the ACS journal of surfaces and colloids.