REMOVAL OF GEOSMIN AND 2-METHYLISOBORNEOL USING ALGAECIDES AND CHEMICALS IN POTABLE WATER By Hanbai Park Bachelor of Science in Chemical Engineering Daegu University Daegu, South Korea 2004 Master of Science in Chemical Engineering Oklahoma State University Stillwater, Oklahoma 2007 Submitted to the Faculty of the Graduate College of the Oklahoma State University in partial fulfillment of the requirements for the Degree of DOCTOR OF PHILOSOPHY July, 2013 REMOVAL OF GEOSMIN AND 2-METHYLISOBORNEOL USING ALGAECIDES AND CHEMICALS IN POTABLE WATER Dissertation Approved: Dee Ann Sanders Gregory G. Wilber John N. Veenstra Gary L. Foutch ii Name: Hanbai Park Institution: Oklahoma State University Title of Study: REMOVAL OF GEOSMIN AND 2-METHYLISOBORNEOL USING ALGAECIDES AND CHEMICALS IN POTABLE WATER Candidate for the Degree of: Doctor of Philosophy Major Field: Environmental Engineering Date of Degree: July, 2013 Common taste and odor compounds in drinking water include 2-methylisoborneol (2-MIB) and trans-1,10-dimethyl-trans-9-decalol (geosmin). These compounds are difficult to remove through conventional water treatment. Thus, additional research is necessary to find cost-effective methods for removal of geosmin and MIB. The effects of algaecides and chemicals in various conditions (dosage, pH, temperature, turbulence, biodegradation) on geosmin and MIB were investigated, and compounds were analyzed through gas chromatograph and mass spectrometric methods (GC/MS) with solid-phase microextraction (SPME). The experiments were performed using both deionized water and lake water samples. At the recommended manufacturer’s dosages of six chemicals (Earth Tec® , Cutrine Plus, Algimycin PWF, Sulfuric Acid, Phycomycin SCP, Calcium chloride dehydrate), removals of geosmin and MIB were unsatisfactory. Acidic conditions were shown to remove the compounds through dehydration. In pH experiments, MIB started to be removed as pH was reduced and was completely removed at pH 3.0. Geosmin showed removal at pH 3.5 and complete removal at pH 2.0. When the samples were returned to neutral (pH=7.5) using sodium hydroxide, geosmin was recovered around 50%, while MIB remained dehydrated. For biodegradation experiments, geosmin was volatilized around 10 -30% and MIB was volatilized around 5-10% for 8 days, but there was negligible impact of biodegradation. In temperature and turbulence experiments, geosmin and MIB removals showed negligible impacts of temperature and turbulence. In futher experiments, three chemicals were found to remove geosmin and MIB as follows: sodium sulfate 70-80%, calcium chloride dehydrate 40-50%, copper sulfate 40%-70%, all at high dosages. ADVISER’S APPROVAL: Dee Ann Sanders iii TABLE OF CONTENTS Chapter Page I. INTRODUCTION .........................................................................................1 1.1 Overview ..............................................................................................1 1.2 History of water treatment in the United States ...................................2 1.3 Taste and odor problems .......................................................................3 1.4 Cyanobacteria and actinomyecte .............................................................5 1.5 Geosmin .................................................................................................7 1.6 MIB .......................................................................................................8 1.7 Health Effect………………………………………………………….11 II. REVIEW OF LITERATURE ....................................................................12 2.1 Biofiltration ........................................................................................12 2.1.1 Activated Carbon .............................................................................13 2.1.2 Other biofiltration for removal of geosmin and MIB ......................18 2.2 Advanced oxidation process (AOP) ...................................................19 2.3 Integrated Technologies .....................................................................21 2.4 Algaecides and chemicals ...................................................................22 III. METHODOLOGY ...................................................................................25 3.1 Objectives ...........................................................................................25 3.2 Analysis of Geosmin and MIB ...........................................................26 3.2.1 Analytical Method ...........................................................................26 3.2.2 Solid Phase Microextration (SPME) ...............................................27 3.2.3 GC/MS Condition ............................................................................31 3.3 Experimental Setup.............................................................................31 3.4 Geosmin and MIB Chromatogram .....................................................32 3.5 Calibration ..........................................................................................34 iv Chapter Page IV. FINDINGS ...............................................................................................37 4.1 Experiments for algaecide dosage changes ........................................38 4.1.1 Experimental Set-up ........................................................................38 4.1.2 Removal of Geosmin ..........................................................................41 4.1.3 Removal of MIB ..............................................................................52 4.1.4 Conclusion .......................................................................................57 4.2 The effect of pH on Geosmin and MIB ..............................................59 4.2.1 Lowering pH for MIB and geosmin by Earth Tec® ........................63 4.2.2 pH effects on MIB and geosmin using various acids ......................67 4.2.3 Geosmin and MIB concentration in lake and deionized water ................71 4.2.4 Conclusion .......................................................................................79 4.3 Biodegradation....................................................................................81 4.3.1 Geosmin and MIB in Filtered and Unfiltered Lake water ...............81 4.3.2 Comparison by Unfiltered, Filtered lake water and Deionized water . …………………………………………………………………………....84 4.3.3 Conclusion .......................................................................................87 4.4 Temperature and Pipeline Flow turbulence ........................................88 4.4.1 Temperature effects on Geosmin and MIB ......................................88 4.4.2 Pipeline turbulence effects on Geosmin and MIB ..................................90 4.4.3 Conclusion .......................................................................................92 4.5 Potential Chemicals for removal of geosmin and MIB ......................94 4.5.1 Cupric sulfate ...................................................................................94 4.5.2 Drying process .................................................................................99 4.5.2.1 Sodium Sulfate ...........................................................................100 4.5.2.2 Low dosages of Sodium Sulfate and Magnesium Sulfate ..................105 4.5.2.3 Phosphorous pentoxide ...............................................................111 4.5.3 Conclusion .....................................................................................117 V. CONCLUSION .....................................................................................119 5.1 Summary of experiments ..................................................................119 5.2 Investigate the optimum chemical for removal of MIB and GSM .. 120 5.3 Development of the effective removal of geosmin and MIB ...........125 5.4 Future work.......................................................................................126 REFERENCES .............................................................................................128 v LIST OF TABLES Table Page Table 1 Common Drinking Water Problems ...................................................................... 4 Table 2 GSM and MIB Characteristics .............................................................................. 9 Table 3 Cyanobacteria species to produce geosmin and MIB ......................................... 10 Table 4 GAC studies of Geosmin and MIB ..................................................................... 15 Table 5 PAC studies of Geosmin and MIB ...................................................................... 17 Table 6 Biological Treatment Studies for Geosmin and MIB removal ........................... 18 Table 7 AOP studies for Geosmin and MIB .................................................................... 20 Table 8 Integrated technologies for Geosmin and MIB removal..................................... 22 Table 9 Testing Algaecides and chemicals ...................................................................... 24 Table 10 GC/MS Condition for GSM and MIB analysis ............................................... 31 Table 11 Optimized Calibration Curve Data from 3 split method experiments .............. 35 Table 12 Optimized Calibration Curve Data from 3 split method experiments .............. 36 Table 13 Six used Algaecides Information ...................................................................... 39 Table 14 Different