Remediation of Chemically-Contaminated Waters Using Sulfate Radical Reactions: Kinetic Studies

  • Stephen P. Mezyk*
    Stephen P. Mezyk
    Department of Chemistry and Biochemistry, California State University Long Beach, 1250 Bellflower Blvd., Long Beach, CA 90840
    School of Energy, Environment, Biological and Medical Engineering, University of Cincinnati, Cincinnati, OH 45221-0012
    *Phone: 562-985-4649, Fax: 562-985-8557, Email: [email protected]
  • Kimberly A. Rickman
    Kimberly A. Rickman
    Department of Chemistry and Biochemistry, California State University Long Beach, 1250 Bellflower Blvd., Long Beach, CA 90840
    School of Energy, Environment, Biological and Medical Engineering, University of Cincinnati, Cincinnati, OH 45221-0012
  • Garrett McKay
    Garrett McKay
    Department of Chemistry and Biochemistry, California State University Long Beach, 1250 Bellflower Blvd., Long Beach, CA 90840
    School of Energy, Environment, Biological and Medical Engineering, University of Cincinnati, Cincinnati, OH 45221-0012
  • Charlotte M. Hirsch
    Charlotte M. Hirsch
    Department of Chemistry and Biochemistry, California State University Long Beach, 1250 Bellflower Blvd., Long Beach, CA 90840
    School of Energy, Environment, Biological and Medical Engineering, University of Cincinnati, Cincinnati, OH 45221-0012
  • Xuexiang He
    Xuexiang He
    Department of Chemistry and Biochemistry, California State University Long Beach, 1250 Bellflower Blvd., Long Beach, CA 90840
    School of Energy, Environment, Biological and Medical Engineering, University of Cincinnati, Cincinnati, OH 45221-0012
    More by Xuexiang He
  • , and 
  • Dionysios D. Dionysiou
    Dionysios D. Dionysiou
    Department of Chemistry and Biochemistry, California State University Long Beach, 1250 Bellflower Blvd., Long Beach, CA 90840
    School of Energy, Environment, Biological and Medical Engineering, University of Cincinnati, Cincinnati, OH 45221-0012
DOI: 10.1021/bk-2011-1071.ch012
Publication Date (Web):September 2, 2011
Aquatic Redox Chemistry
Chapter 12pp 247-263
ACS Symposium SeriesVol. 1071
ISBN13: 9780841226524eISBN: 9780841226531
Copyright © 2011 American Chemical Society
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Abstract

The quantitative removal of chemical contaminants in water is one of the most pressing problems facing water utilities today. To augment traditional water treatments that are usually based on adsorptive and chemical-physical processes, radical-based advanced oxidation and reduction processes (AO/RPs) are now being considered. While most AO/RPs utilize the hydroxyl radical in treatment the use of oxidizing sulfate radicals is also gaining interest. To help assess the applicability of sulfate radical based AO/RPs in remediating contaminated waters, here we have determined absolute rate constants and reaction mechanisms for SO4-• reaction with four β-lactam antibiotics (amoxicillin, penicillin-G, piperacillin, tircarcillin), three estrogenic steroids (ethynylestradiol, estradiol, and progesterone) and one personal care product (isoborneol). For the four antibiotics of this study the relatively fast rate constant values suggests that the majority of the SO4-• oxidation occurs at the sulfur atom in the ring adjacent to the β-lactam moiety, as opposed to the hydroxyl radical reaction which occurs at peripheral aromatic rings. The measured sulfate radical rate constants for estradiol and progesterone are identical, with the slightly faster value for ethynylestradiol suggesting significant oxidation occurring at its ethynyl moiety. For isoborneol, the sulfate radical reactivity was slightly lower, but still fast enough that AO/RP treatment utilizing this radical might be feasible at large-scale. Piperacillin was also chosen for a detailed investigation of its degradation by both SO4-• and OH in a laboratory scale homogeneous UV photochemical system. It was found that although the absolute reaction rate constant for piperacillin reaction with SO4-• was lower than for OH, the overall removal of this antibiotic was more effective when using UV/S2O82- than UV/H2O2. For an initial oxidant dose of 1 mM and an antibiotic concentration of 50 µM, percentage removals of 65.2% and 33.0%, respectively, at a UV fluence of 320 mJ/cm2 were obtained. This difference was attributed to the higher quantum yield of sulfate radical production from persulfate under UV 254 nm irradiation.