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University Microfilms 300 North Zoob Road Ann Arbor, Michigan 481 OB A Xarox Education Company IFEADI, Christopher Ngozi, 1939- QUANTXTATIVE MEASUREMENT AND SENSORY EVALUATION OF DAIRY WASTE ODOR. The Ohio State University, Ph.D., 1972 Environmental Sciences University Microfilms, A XEROX Company, Ann Arbor, Michigan QUANTITATIVE MEASUREMENT AND SENSORY EVALUATION OF DAIRY WASTE ODOR DISSERTATION Presented In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy In the Graduate School of The Ohio State University by Christopher Ngozi Ifeadi, B.S., M.S, The Ohio State University 1972 Approved by ^ ■m l E. Paul Taiganides Adviser Agricultural Engineering Department PLEASE NOTE: Some pages may have i nd i s t inet print. Filmed as received. University Microfilms, A Xerox Education Company ACKNOWLEDGMENTS Dr. E, Paul Taiganides is gratefully acknowledged for his counsel and encouragement during my doctoral studies. Dr. R.K. White is acknowledged for his useful suggestions in the design of the experiments. Dr. R. Foltz of Battelle Memorial Institute, Columbus, Ohio, is acknowledged for the chemical ionization mass spectrometer analysis and interpretations. Dr. K.S. Shumate and Dr. T.L. Sweeney are acknowledged for their interest, advice, and suggestions during my study. Acknowledgment is made of the financial support from the Ohio Agricultural Research and Development Center, and from the Live" stock Engineering and Farm Structures Research Branch of the United States Department of Agriculture, R.G. Yeck, Chief. VITA 1939 ....................Born at Ubulu” Okiti, Nigeria 1955-1959 ............ Okongwu Memorial Grammar School, Nnewi Nigeria 1962-1963 . ........... Greenville College, Greenville, Illinois U.S.A. 1963-1967 ....... B.S. Agricultural Engineering, University of California, Davis, California 1967-1969.. ............ Research Assistant, University of Nebraska, Lincoln, Nebraska 1969 .................... M.S. Agricultural Engineering, University of Nebraska, Lincoln, Nebraska 1969-1972.. ............ Graduate Research Associate, The Ohio State University, Columbus, Ohio PUBLICATIONS Ventilation systems for controlling gases produced in confined swine housing. M.S. Thesis. Effects of slotted floors on airflow characteristics in swine confinement housing. ASAE Paper No. 68-9^5* American Society of Agricultural Engineers, St. Joseph, Michigan. 1968 . A model study to determine the Effect of ventilation systems upon NHj concentrations in swine confinement housing. ASAE Paper No. MC-71-103. American Society of Agricultural Engineers, St. Joseph, Michigan. 1971• iii FIELDS OF STUDY Major Field: Agricultural Environmental Engineering Studies in Waste Management: Drs. E. Paul Taiganides and Richard K. White Studies in Air Pollution: Drs. Thomas L. Sweeney and Ross D. Brazee Studies in Water Pollution: Dr. Kenesaw S. Shumate TABLE OF CONTENTS Page ACKNOWLEDGMENTS.............................................. ii VITA ......................................................... iii LIST OF T A B L E S ................... V LIST OF F I G U R E S .............................................. vii INTRODUCTION ................................................ 1 OBJECTIVES .................................................. 8 LITERATURE REVIEW ............................................ 9 Nature of Odor and Theories of Sense of Smell Odor Measurement Methods Odor Production from Anaerobic Decomposition of Organic Wastes EXPERIMENTAL PROCEDURES.......................................... 60 Instrumentation Set-Up for the Objective Measurement Instrumentation Set-Up for Sensory Evaluation Equipment Calibration and Standardization of Procedures Test Procedures v Page EXPERIMENTAL RESULTS, ANALYSIS, AND DISCUSSION . ......... 100 Equipment Performance Chemical Ionization Mass Spectrometer of Dairy Waste Volatiles Diffusion Cell Calibration and GC Calibration Curves for (CH3 )2S and (C2H,-)2S Quantitative Measurement of Dimethyl Sulfide and Diethyl Sulfide in Dairy Waste Volatiles Sensory Evaluations Dairy Waste Odor Units SUMMARY ........................................................... 144 CONCLUSIONS .......................... 149 RECOMMENDATIONS FOR FURTHER R E S E A R C H ...........................151 APPENDICES ..................... 152 A. Equipment Diagrams B. Calibration of Equipment C. GC Calibration of Pure Compounds REFERENCES .................................................... 3,77 vi LIST OF TABLES Table Page 1 Reported Legal Cases of Odor Nuisance from Animal Production Units 2 2 Theories on Odor“Producing Attributes of Odorous Molecules 11 3 Properties of Ammonia aitl Hydrogen Sulfide and Their Physiological Effects 26 4 Mechanical Devices for the Detection of Odors 28 5 Methods of Sampling and Concentrating Odorous Gases 34 6 Composition of Typical Rations Fed to Swine, Poultry, Dairy, and Beef Animals from which Waste Samples for Tests Were Collected 51 7 Percentage Composition of Dry Material in Animal Manure 53 8 Compounds Identified in Decomposing Animal Wastes and Their Odor Characteristics 57 9 Serial Dilution of Dimethyl Sulfide 94 10 Serial Dilution of Diethyl Sulfide 97 11 Identification of Peaks Produced by Contaminants in the Equipment of the Sampling Train 101 12 Retention Times for (CH3)2S and (C2 H 5 )2 S 104 13 First Series of the Quantitative Measurements of (CH3)2S and CC2h 5^2® D a *ry Waste Volatiles 119 14 Second Series of the Quantitative Measurements of (CH3 >2 S and (C^,-)^ in Dairy Waste Volatiles 122 15 Third Series of the Quantitative Measurements of (0 1 3 ) 2 1 5 and ( C ^ ) ^ in Dairy Waste Volatiles 126 vii Table I*age 16 Rotameter Setting for Serial Dilution of Dairy Waste Volatiles . 17 Odor Intensity Ranking for the First Series of Tests 133 18 Odor Intensity Ranking for Second Series of Tests 134 19 Odor Intensity Ranking for Third Series of Tests 135 20 Odor Units Associated with Dimethyl Sulfide in Hundreds of Odor Units 138 21 Odor Units Associated with Diethyl Sulfide in Hundreds of Odor Units . - 140 22 Summary: Average Concentration and Odor Units Associ“ ated with Dimethyl and Diethyl Sulfides 141 23 Dimensions of the Diffusion Cells 161 24 Diffusion Cell Calibrations for Diethyl Sulfide 165 25 Diffusion Cell Calibration for Dimethyl Sulfide 168 26 GC Calibration Table for Dimethyl Sulfide at 25°C 172 27 GC Calibration Table for Diethyl Sulfide at 40°C 172 viii LIST OF FIGURES Figure Page 1 Approximate Amounts of Air that Must Be Exhaustively Sampled to Supply Enough Odorant for Identification by Various Techniques 29 2 Schematic Representation of the Main Parts of the Anaerobic Digestion Process 56 3 Block Diagram for the Objective Measurement 60 4 Instrumentation for Odor Generation and Collection 62 5 Diffusion Cell 63 6 Sample Collector 65 7 Apparatus for Purifying and Conditioning Sample Collector 67 8 Apparatus for the Transfer of Sample into the Injection Needle 68 9 Cold/Hot Block Scissors Mechanism 69 10 Initiating Injection Process - Transfer of Samples from the Needle to the GC 72 11 Odor Analysis Instrumentation 74 12 The Sniffing Hood 76 13 Sample Transfer to Injection Needle 88 14 Serial Dilution of Diffused Pure Compounds 95 15 Evaluating the Dairy Odor 99 16 Similarity of Peaks Produced Using Pure Compounds 106 17 Mass Spectrometer Figures 107 18 Chemical Ionization Spectra of Reference Compounds 108 ix Figure Page 19 Dairy Waste Volatile Chromatogram 110 20 Chemical Ionization Spectra of (ClO-S and ^2H5^2S *n Dairy Waste Volatiles 111 21 GC Calibration Curve for Dimethyl Sulfide (Semi~Calculated) 114 22 GC Calibration Curve for Diethyl Sulfide (Semi"Calculated) 115 23 GC Calibration Curve for Dimethyl Sulfide (Measured) 116 24