Slow biotransformation of carbon nanotubes by horseradish peroxidase

Due to steady increase in use and mass production carbon nanotubes (CNTs) will inevitably end up in the environment. Because of their chemical nature CNTs are expected to be recalcitrant and biotransform only at very slow rates. Degradation of CNTs within days has recently been reported, but excluding one study, conclusions relied solely on qualitative results. We incubated 13 different types of CNTs and subjected them to enzymatic oxidation with horseradish peroxidase and concluded that the analytical methods commonly employed for studying degradation of CNTs did not have the sensitivity to unequivocally demonstrate degradation of these materials. To obtain unambiguous results with regard to the biotransformability of CNTs in the horseradish peroxidase system we incubated: (a) (14)C-labeled multiwalled CNTs, homologous to Baytubes CNTs; and (b) (13)C-depleted single-walled CNTs, used in previous studies. Our results show that (14)C-CO2 evolved linearly at a rate of about 0.02‰ per day, and at the end of the 30-day incubations the CO2 evolved amounted to about 0.5‰ of both initial substrates, the (14)C-labeled multiwalled and (13)C-depleted single-walled CNTs. These results clearly show that CNT material is oxidized in the horseradish peroxidase system but with half-lives of about 80 years and not a few days as has been reported before. Adequately addressing biotransformation rates of CNTs is key toward a better understanding of the fate of these materials in the environment.