Kinetics of reactions between chlorine and the cyanobacterial toxins microcystins.

Blooms of cyanobacteria can give rise to the production of toxins which contaminate drinking water sources. Among the oxidants and disinfectants typically applied in waterworks, chlorine has been found to be effective for the degradation of microcystins. In the present study, unknown second-order rate constants for the reactions of microcystin-LR (MC-LR), -RR and -YR with chlorine were determined over a wide pH range. It was found that an increase of pH has a negative effect on the microcystin degradation rate. Apparent second-order rate constant for the chlorination of MC-LR at 20 degrees C varied from 475 M(-1)s(-1) at pH 4.8 to 9.8 M(-1)s(-1) at pH 8.8. From these apparent second-order rate constants, rate constants for the reactions of MC-LR with hypochlorous acid (HOCl) and hypochlorite (ClO-) were evaluated. Half-life times ranged from minutes at pH 6 to 1 h at pH 8 for a constant residual chlorine concentration of 1.0-0.5 mgl(-1), typical of oxidation pre-treatment and final disinfection. Similar reactivity with chlorine was found for MC-RR and MC-YR. Therefore, chlorination is a feasible option for microcystin degradation during oxidation and disinfection processes, and can be applied in drinking water treatment in case of cyanobacterial toxin risk if the pH is kept below 8.

[1]  U. Gunten,et al.  Methods for the photometric determination of reactive bromine and chlorine species with ABTS , 2000 .

[2]  O. Levenspiel Chemical Reaction Engineering , 1972 .

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

[4]  H. Mayer,et al.  Lipopolysaccharides of photosynthetic prokaryotes. , 1979, Annual review of microbiology.

[5]  J. Meriluoto,et al.  Isolation and detection of microcystins and nodularins, cyanobacterial peptide hepatotoxins. , 2000, Methods in molecular biology.

[6]  G. Shaw,et al.  Toxicological aspects of treatment to remove cyanobacterial toxins from drinking water determined using the heterozygous P53 transgenic mouse model. , 2003, Toxicon : official journal of the International Society on Toxinology.

[7]  H. Gallard,et al.  Chlorination of natural organic matter: kinetics of chlorination and of THM formation. , 2002, Water research.

[8]  M. D. Gurol,et al.  Kinetic behavior of ozone in aqueous solutions of substituted phenols , 1984 .

[9]  L. Lawton,et al.  Cyanobacterial (Blue‐Green Algal) Toxins and their Significance in UK and European Waters , 1991 .

[10]  S. Faust Principles and Applications of Water Chemistry , 1967 .

[11]  Michael D. Burch,et al.  Destruction of cyanobacterial peptide hepatotoxins by chlorine and chloramine , 1994 .

[12]  C. Luke,et al.  Illness associated with blue‐green algae , 1992, The Medical journal of Australia.

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

[14]  Jamie Bartram,et al.  Toxic Cyanobacteria in Water: a Guide to Their Public Health Consequences, Monitoring and Management Chapter 2. Cyanobacteria in the Environment 2.1 Nature and Diversity 2.1.1 Systematics , 2022 .

[15]  H. Gallard,et al.  Chlorination of phenols: kinetics and formation of chloroform. , 2002, Environmental science & technology.

[16]  E. Styer,et al.  Microcystin toxicosis in cattle due to overgrowth of blue-green algae. , 1998, Veterinary and human toxicology.

[17]  M. Elovitz,et al.  Hydroxyl Radical/Ozone Ratios During Ozonation Processes. II. The Effect of Temperature, pH, Alkalinity, and DOM Properties , 2000 .

[18]  P. Turner,et al.  Pneumonia associated with contact with cyanobacteria. , 1990, BMJ.

[19]  O. Holst Bacterial toxins : methods and protocols , 2000 .

[20]  C. Yao,et al.  Rate constants for reaction of hydroxyl radicals with several drinking water contaminants , 1992 .

[21]  Lise,et al.  LIVER FAILURE AND DEATH AFTER EXPOSURE TO MICROCYSTINS AT A HEMODIALYSIS CENTER IN BRAZIL LIVER FAILURE AND DEATH AFTER EXPOSURE TO MICROCYSTINS AT A HEMODIALYSIS CENTER IN BRAZIL , 2000 .

[22]  B. Nicholson,et al.  Destruction of Cyanobacterial Toxins By Ozone , 1998 .

[23]  L. Ho,et al.  Treatment options for microcystin toxins: Similarities and differences between variants , 2003, Environmental technology.

[24]  W. Carmichael,et al.  Use of a colorimetric protein phosphatase inhibition assay and enzyme linked immunosorbent assay for the study of microcystins and nodularins. , 1994, Toxicon : official journal of the International Society on Toxinology.

[25]  H. Nakazawa,et al.  Stability of microcystins from cyanobacteria--IV. Effect of chlorination on decomposition. , 1997, Toxicon : official journal of the International Society on Toxinology.

[26]  Urs von Gunten,et al.  Determination of iodide and iodate by ion chromatography with postcolumn reaction and UV/visible detection , 1999 .

[27]  T. Olson,et al.  Aqueous Chlorination Kinetics and Mechanism of Substituted Dihydroxybenzenes , 1996 .

[28]  R. L. Valentine,et al.  Monochloramine decay in model and distribution system waters. , 2001, Water research.

[29]  G. Newcombe,et al.  Ozonation of NOM and algal toxins in four treated waters. , 2001, Water research.

[30]  Wayne W. Carmichael,et al.  Inhibition of protein phosphatases by microcystis and nodularin associated with hepatotoxicity , 2005, Journal of Cancer Research and Clinical Oncology.

[31]  J. Meriluoto,et al.  Screening for cyanobacterial hepatotoxins, microcystins and nodularin in environmental water samples by reversed-phase liquid chromatography-electrospray ionisation mass spectrometry. , 2003, Journal of chromatography. A.

[32]  U. von Gunten,et al.  Kinetics and mechanisms of formation of bromophenols during drinking water chlorination: assessment of taste and odor development. , 2005, Water research.

[33]  B. Legube,et al.  Phototransformation of selected organophosphorus pesticides in dilute aqueous solutions. , 2004, Water research.

[34]  Adrien Albert,et al.  The determination of ionization constants : a laboratory manual , 1971 .