FORMIC ACID: DEVELOPMENT OF AN ANALYTICAL METHOD AND USE AS A PROCESS INDICATOR IN ANAEROBIC SYSTEMS A Special Research Problem Report Presented to the Faculty of the Division of Graduate Studies by Sharon L. Perkins In Partial Fulfillment of the Requirements for the Degree Master of Science in the School of Civil Engineering Georgia Institute of Technology March 1992 T256373 ?33?Z FORMIC ACID: DEVELOPMENT OF AN ANALYTICAL METHOD AND USE AS A PROCESS INDICATOR IN ANAEROBIC SYSTEMS by Sharon L. Perkins ACKNOWLEDGEMENT The completion of this research has been a very difficult, but at the same time rewarding task. I wish to express my appreciation to Dr. Wendall Cross for his continuous support and guidance throughout the course of my research. I would also like to recognize the Environmental Engineering faculty of the Georgia Institute of Technology, School of Civil Engineering for the role they played in my education process. However, most of my success in this program can be attributed to the constant encouragement, love and attention I received from my husband, Armond Perkins. To all of you I would like to say thank you. in TABLE OF CONTENTS PAGE ACKNOWLEDGEMENT iii LIST OF TABLES v LIST OF FIGURES vii LIST OF APPENDICES xi ABSTRACT xii INTRODUCTION 1 GENERAL 1 BIOCHEMISTRY 4 OBJECTIVES OF RESEARCH 5 LITERATURE REVIEW 9 PROCESS INHIBITION 9 PROCESS INDICATORS 12 FORMIC ACID 14 Biochemistry 14 Methods of detection 18 ANALYTICAL METHODS AND MATERIALS 26 DEVELOPMENT OF FORMIC ACID ANALYTICAL METHOD 26 .... ANAEROBIC BATCH REACTOR SETUP AND OTHER ANALYSES 43 RESULTS 52 TEST 1 - SUBSTRATE CONCENTRATION INCREASE 52 TEST 2 - CHLOROFORM TOXICITY 59 TEST 3 - AMMONIA TOXICITY NUMBER 1 66 TEST 4 - AMMONIA TOXICITY 80 TEST 5 - AMMONIA TOXICITY 80 TEST 6 - AMMONIA TOXICITY NUMBER 4 82 TEST 7 - SEED REACTOR DURING UPSET 88 CONCLUSIONS 98 FINDINGS 98 AREAS OF FUTURE RESEARCH 98 ENGINEERING SIGNIFICANCE 99 REFERENCES 100 IV LIST OF TABLES TABLE PAGE 1.1 ENERGY METABOLISM OF METHANOGENIC BACTERIA 6 1.2 SOLE ELECTRON SOURCE FOR METHANOGENESIS AND GROWTH 8 2.1 ENZYMES THAT ACT ON FORMIC ACID 15 3.1 DATA FROM CHROMATOGRAPHIC ANALYSIS OF CHEMICALS THAT HAVE ELUTION TIMES SIMILAR TO FORMIC ACID 27 3.2 DATA FROM CHROMATOGRAPHIC ANALYSIS OF ACETIC AND FORMIC ACIDS 28 3.3 DATA FROM ION CHROMATOGRAPHIC REPRODUCIBILITY ANALYSIS OF LEACHATE FROM EXPERIMENTAL LANDFILL COLUMN 1, SPIKED WITH 10 MG/L FORMIC ACID AND PRETREATED WITH RP AND AG CARTRIDGES 36 3.4 DATA FROM ION CHROMATOGRAPHIC ANALYSIS TO DETERMINE THE LOWEST CONCENTRATION OF FORMIC ACID DETECTABLE 38 3.5 FORMIC ACID ANALYSIS OF EFFLUENT FROM VARIOUS ANAEROBIC REACTORS 39 3.6 SEED REACTOR SUBSTRATE 44 3.7 TEST REACTOR SUBSTRATES 4 9 3.8 TEST CONDITIONS 51 4.1 PH ANALYSIS OF EFFLUENT FROM REACTORS FED VARIOUS CONCENTRATIONS OF SUBSTRATE 52 4.2 PH ANALYSIS OF EFFLUENT FROM REACTORS FED SUBSTRATE CONTAINING VARIOUS CONCENTRATIONS OF CHLOROFORM 66 4.3 PH ANALYSIS OF EFFLUENT FROM REACTORS FED SUBSTRATE CONTAINING VARIOUS CONCENTRATIONS OF NH AMMONIA TOXICITY ANALYSIS #1 74 3,