Photocatalytic degradation and mineralization of microcystin-LR under UV-A, solar and visible light using nanostructured nitrogen doped TiO2.

In an attempt to face serious environmental hazards, the degradation of microcystin-LR (MC-LR), one of the most common and more toxic water soluble cyanotoxin compounds released by cyanobacteria blooms, was investigated using nitrogen doped TiO(2) (N-TiO(2)) photocatalyst, under UV-A, solar and visible light. Commercial Degussa P25 TiO(2), Kronos and reference TiO(2) nanopowders were used for comparison. It was found that under UV-A irradiation, all photocatalysts were effective in toxin elimination. The higher MC-LR degradation (99%) was observed with Degussa P25 TiO(2) followed by N-TiO(2) with 96% toxin destruction after 20 min of illumination. Under solar light illumination, N-TiO(2) nanocatalyst exhibits similar photocatalytic activity with that of commercially available materials such as Degussa P25 and Kronos TiO(2) for the destruction of MC-LR. Upon irradiation with visible light Degussa P25 practically did not show any response, while the N-TiO(2) displayed remarkable photocatalytic efficiency. In addition, it has been shown that photodegradation products did not present any significant protein phosphatase inhibition activity, proving that toxicity is proportional only to the remaining MC-LR in solution. Finally, total organic carbon (TOC) and inorganic ions (NO(2)(-), NO(3)(-) and NH(4)(+)) determinations confirmed that complete photocatalytic mineralization of MC-LR was achieved under both UV-A and solar light.

[1]  Ying Yang,et al.  Photocatalytic mechanisms of modified titania under visible light , 2011 .

[2]  T. Waite,et al.  Photocatalytic Degradation of the Blue Green Algal Toxin Microcystin-LR in a Natural Organic-Aqueous Matrix , 1999 .

[3]  Jincai Zhao,et al.  Fate of amino acids upon exposure to aqueous titania irradiated with UV-A and UV-B radiation Photocatalyzed formation of NH3, NO3−, and CO2 , 1997 .

[4]  D. Dionysiou,et al.  Unveiling new degradation intermediates/pathways from the photocatalytic degradation of microcystin-LR. , 2008, Environmental science & technology.

[5]  H. Yan,et al.  Photocatalytic degradation of trace-level of Microcystin- LR by nano-film of titanium dioxide , 2006 .

[6]  David F. Ollis,et al.  Photocatalytic purification and treatment of water and air : proceedings of the 1st International Conference on TiO[2] Photocatalytic Purification and Treatment of Water and Air, London, Ontario, Canada, 8-13 November, 1992 , 1993 .

[7]  Peter K. J. Robertson,et al.  Hydrogen peroxide enhanced photocatalytic oxidation of microcystin-lR using titanium dioxide , 2000 .

[8]  T. Waite,et al.  Kinetic modeling of TiO2-catalyzed photodegradation of trace levels of microcystin-LR. , 2003, Environmental science & technology.

[9]  Sung-Chul Kim,et al.  Photocatalytic oxidation of microcystin-LR in a fluidized bed reactor having TiO2-coated activated carbon , 2004 .

[10]  S. Goldstein,et al.  Nature of the Oxidizing Species Formed upon UV Photolysis of C-TiO2 Aqueous Suspensions , 2009 .

[11]  D. Dionysiou,et al.  LC/MS/MS structure elucidation of reaction intermediates formed during the TiO(2) photocatalysis of microcystin-LR. , 2008, Toxicon : official journal of the International Society on Toxinology.

[12]  Jungju Lee,et al.  Effect of process variables and natural organic matter on removal of microcystin-LR by PAC-UF. , 2006, Environmental science & technology.

[13]  B. K. Hodnett Photocatalytic purification and treatment of water and air : by D.F. Ollis and H. Al-Ekabi (Editors), Elsevier Science Publishers BV, Amsterdam, 1993, ISBN 0-444-89855-7, xiv + 820 pp., f450.00/$257.25 , 1994 .

[14]  N. Serpone,et al.  Processes of formation of NH4+ and NO3− ions during the photocatalyzed oxidation of N-containing compounds at the titania/water interface , 1997 .

[15]  C. Minero,et al.  The fate of organic nitrogen in photocatalysis: an overview , 2005 .

[16]  R M Dawson,et al.  The toxicology of microcystins. , 1998, Toxicon : official journal of the International Society on Toxinology.

[17]  Peter Bradshaw,et al.  Using activated carbon to remove toxicity from drinking water containing cyanobacterial blooms , 1989 .

[18]  Miguel Pelaez,et al.  Mesoporous nitrogen-doped TiO2 for the photocatalytic destruction of the cyanobacterial toxin microcystin-LR under visible light irradiation. , 2007, Environmental science & technology.

[19]  Kimberly A. Gray,et al.  Explaining the Enhanced Photocatalytic Activity of Degussa P25 Mixed-Phase TiO2 Using EPR , 2003 .

[20]  J. Meriluoto,et al.  Selective oxidation of key functional groups in cyanotoxins during drinking water ozonation. , 2007, Environmental science & technology.

[21]  L. Lawton,et al.  Mechanistic studies of the photocatalytic oxidation of microcystin-LR: an investigation of byproducts of the decomposition process. , 2003, Environmental science & technology.

[22]  L. Lawton,et al.  Destruction of cyanobacterial toxins by semiconductor photocatalysis , 1997 .

[23]  Peter K. J. Robertson,et al.  Detoxification of microcystins (cyanobacterial hepatotoxins) using TiO2 photocatalytic oxidation , 1999 .

[24]  S. Martin,et al.  Environmental Applications of Semiconductor Photocatalysis , 1995 .

[25]  Julián Blanco,et al.  Decontamination and disinfection of water by solar photocatalysis: Recent overview and trends , 2009 .

[26]  Peter K. J. Robertson,et al.  The Involvement of Phycocyanin Pigment in the Photodecomposition of the Cyanobacterial Toxin, Microcystin-LR , 1999 .

[27]  P. Falaras,et al.  Nitrogen modified nanostructured titania: electronic, structural and visible‐light photocatalytic properties , 2008 .

[28]  K. Sivonen,et al.  Removal of cyanobacterial toxins in water treatment processes: Laboratory and pilot‐scale experiments , 1988 .

[29]  Philip R. Cohen,et al.  Cyanobacterial microcystin‐LR is a potent and specific inhibitor of protein phosphatases 1 and 2A from both mammals and higher plants , 1990, FEBS letters.

[30]  André M. Braun,et al.  Photochemical processes for water treatment , 1993 .

[31]  L. Lawton,et al.  The Destruction of Cyanobacterial Toxins by Titanium Dioxide , 1999 .

[32]  P. Kamat PHOTOCHEMISTRY ON NONREACTIVE AND REACTIVE (SEMICONDUCTOR) SURFACES , 1993 .

[33]  W. Garrison REACTION MECHANISMS IN THE RADIOLYSIS OF PEPTIDES, POLYPEPTIDES AND PROTEINS II REACTIONS AT SIDE-CHAIN LOCI IN MODEL SYSTEMS , 1982 .

[34]  C. Baiocchi,et al.  Photo-induced transformation of methylguanidine derivatives on titanium dioxide , 2006 .

[35]  I. Falconer Cyanobacterial Toxins of Drinking Water Supplies , 2004 .

[36]  D. Dionysiou,et al.  Can we effectively degrade microcystins?--Implications on human health. , 2011, Anti-cancer agents in medicinal chemistry.

[37]  E. Stathatos,et al.  Chapter 8 TiO2-Based Advanced Oxidation Nanotechnologies for Water Purification and Reuse , 2010 .

[38]  D. Dionysiou,et al.  Sources and Occurrence of Cyanotoxins Worldwide , 2010 .

[39]  Horst Kisch,et al.  The nature of nitrogen-modified titanium dioxide photocatalysts active in visible light. , 2008, Angewandte Chemie.

[40]  S. Goldstein,et al.  Mechanism of Visible Light Photocatalytic Oxidation of Methanol in Aerated Aqueous Suspensions of Carbon-Doped TiO2 , 2008 .

[41]  R. Asahi,et al.  Visible-Light Photocatalysis in Nitrogen-Doped Titanium Oxides , 2001, Science.