12/20/2013 Transformation of Perfluorinated Compounds during Enzyme Catalyzed Oxidative Humification Reactions Qi Luo1,2, Rashmi Singh Sidhu2, Qingguo Huang1,2 1Interdisplinary Toxicology Program, University of Georgia Athens, GA 30605 2Department of Crop and Soil Sciences, University of Georgia Griffin, GA 30223 1 12/20/2013 Background • Perfluorinated compounds (PFCs) are used in various applications due to its special properties • PFCs are persistent 2 12/20/2013 Background • Toxicity – Increase liver and kidney weight in rats – Carcinogenic to liver and pancreas in rats – etc. • EPA emerging contaminants list • No practical remediation approaches • enzyme- catalyzed oxidative humification reactions (ECOHR) may provide feasible solution 3 12/20/2013 Objective • Determine the optimal reaction condition for removal of PFCs by enzyme- catalyzed oxidative humification reactions (ECOHR) 4 12/20/2013 1. Background 2. Objective 3. Enzyme-catalyzed humification reaction 4. Experiment – batch study 5. Thoughts 5 12/20/2013 ECOHR • Enzyme-catalyzed oxidative reactions systems Radical • • • • ECOHR Lignin White rot fungi Lignolytic enzymes Mediator –Peroxidases –Laccase 6 12/20/2013 ECOHR • Enzyme-catalyzed oxidative reactions systems • Persistent organic pollutants • PAHs • PCBs • PFOA 7 12/20/2013 ECOHR – Induced PFOA Reaction Perfluorooctane acid (PFOA) • Three Components for ECOHR Process • Laccase • Mediator • O2 Colosi et al., Environ. Tox. Chem., 2009 8 12/20/2013 1. Background 2. Objective 3. Enzyme-catalyzed humification reaction 4. Experiment –batch study 5. Thoughts 9 12/20/2013 PFOA Removal Under Different Conditions pH 3 (citrate buffer) 1-20 pH 4 (citrate buffer) 1-20 1-0 120 PFOA Residue (%) PFOA Residue (%) 120 1-0 90 60 30 0 10 20 30 Time (d) 40 50 90 60 30 0 10 20 30 40 50 Time (d) 10 12/20/2013 PFOA Removal Under Different Conditions pH 4.5 (culture medium) 1-20 pH 4 (citrate buffer) 1-0 1-20 120 PFOA Residue (%) 120 PFOA Residue (%) 1-0 90 60 90 60 30 30 0 10 20 30 Time (d) 40 50 0 10 20 30 40 50 Time (d) 11 12/20/2013 PFOA Residue (%) 1-20 Mediator Concentration 60 30 10 20 40 Enzyme Activity 50 Time (d) 1-20 1-2 30 20 10 0 10 30 20 30 Time (d) 40 50 Laccase activity (U/mL) HBT Concentrationm (µM) 90 40 0 PFOA Residue 1-0 120 0 1-20 50 1-2 1-2 1-0 1.6 1.2 0.8 0.4 0 0 10 20 30 40 50 Time (d) 12 12/20/2013 1. Background 2. Objective 3. Enzyme-catalyzed humification reaction 4. Experiment – batch study 5. Thought 13 12/20/2013 Thoughts… • PFOA can be degraded gradually in aqueous solution via laccase-mediated ECOHR with the presence of mediator. • Removal efficiency of PFOA is highly dependent on the reaction conditions such as cation, and mediator concentration. • Current work is needed to carry on to monitoring further degradation of PFOA and other factors such as ion strength, mediator species need to be tested. 14 12/20/2013 Acknowledgments • SERDP: ERSON-11-02 “IN SITU REMEDIATION OF PERFLUOROALKYL CONTAMINATED GROUNDWATER” • AFCEC: “IN-SITU ENZYMATIC OXIDATIVE TREATMENT FOR PERFLUORINATED COMPOUNDS” • Dr. Qingguo (Jack) Huang (University of Georgia) • Dr. Dora Chiang (AECOM) • Mr. Dave Woodward (AECOM) • Dr. Junhe Lu (Nanjing Agricultural University) 15 12/20/2013 Questions & Suggestions 16
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