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ABSTRACT This research was conducted in three sets of field-scale composting experiments. Also presented are two brief economic models that compare processing costs of an in- vessel system to a windrow biosolids and to a biopile treatment operation. The first set of experiments quantified hydrocarbons, organic sulfur compounds, and ammonia produced by an in-vessel system composting sewage sludge. Cumulative hydrocarbons, organosulfur compounds, and ammonia gas emissions were compared to published emissions from two commercial windrow operations. For a similar dry mass fraction of sewage sludge, the in-vessel emissions were ten-fold lower for non-methane hydrocarbons, organosulfur compounds, and ammonia. Additionally, methane concentrations in the in-vessel exhaust gas were negligible, whereas the windrow systems generated 1.8-g to 26.6-g methane per dry-kg. In regions with stringent air emission regulations, a properly operated in-vessel system could overcome the need for exhaust gas treatment. The effect of C/N ratio on ammonia generation was evaluated, as was the variability of hydrocarbon emissions from batch to batch. The second set of experiments compared in-vessel performance to a windrow and a static pile in remediating explosives-contaminated soil. Based on these experiments, preferred conditions for remediating HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7- tetrazocine) in soil were at saturated moisture content with infrequent mixing to promote ii reductive transformations. Operating under low moisture content and at a 50% soil mass fraction decreased HMX removal efficiency. The third test set consisted of constructing and operating a 400-m3 and a 1,000-m3 biopile to remediate soils contaminated with total petroleum hydrocarbons (TPH). The TPH removals were 62% and 77% after 7 and 27 months, respectively. Initial TPH levels averaged 1,550 and 3,200 mg/kg, and final average values were 590 and 740 mg/kg. Grinding and blending soil prior to treatment would have distributed TPH contamination more evenly and reduced agglomeration of TPH-saturated soil in which oxygen, water, and hydrocarbon transport were limited. Enhanced ex-situ soil treatment options for smaller volumes of contaminated soil (approx. 200 to 1,500-m3) were proposed. An in-vessel system could provide periodic mixing and could sustain process conditions that approach the control possible in laboratory systems. Future research focused on validating an in-vessel approach is recommended. iii Dedicated to Lauri for staying with me through this effort. iv ACKNOWLEDGMENTS I thank Dr. Olli Tuovinen for his steadfast support through several research topics and for his insight. Additionally, I acknowledge my committee members, Dr. Harold Keener, Dr. Sam Traina, and Dr. S.T. Yang for their patience and flexibility. The management at Battelle provided financial, laboratory, and scheduling assistance. In particular I thank Dr. Jeff Means who for several years enabled me to devote a portion of my work toward my academic goal and who has continued to serve as a mentor. I owe gratitude to Ms. Vicki Paddock for volunteering her time to painstakingly format the dissertation draft. To Lauri I owe more than can be spelled out here for enduring a long circuitous journey toward the completion of this document. v VITA February 27, 1965 ....................................Born – Greenville, OH 1987..........................................................B.S. Chemical Engineering, California State Polytechnic University, Pomona 1994..........................................................M.S. Chemical Engineering, The Ohio State University 1987 – 1991..............................................Chemical Officer, U.S. Army, Aberdeen Proving Ground, MD 1991 – 1992..............................................Graduate Teaching Associate, The Ohio State University 1992 – 2001..............................................Research Engineer, Battelle Memorial Institute, Columbus, OH 2001 – 2003 .............................................Executive Officer, U.S. Army Pueblo Chemical Depot, CO 2003 – present..........................................Senior Research Scientist, Battelle Memorial Institute, Columbus, OH PUBLICATIONS Research Publications 1. V.S. Magar, F.M. von Fahnestock, A. Leeson (editors). 2001. Ex Situ Biological Treatment Technologies. Battelle Press, Columbus, OH. ISBN 1-57477-116-7. 2. F.M. von Fahnestock, G.B. Wickramanayake, R.J. Kratzke, W.R. Major. 1998. Biopile Design, Operation, and Maintenance Handbook for Treating Hydrocarbon- Contaminated Soils. Battelle Press, Columbus, OH. ISBN 1-57477-035-7. 3. F.M. von Fahnestock, T.L. Forney. 1995. Biodegradation of Explosives Using a Known Herbicide Degrader. In: Bioremediation of Recalcitrant Organics. Vol. 3. R.E. Hinchee, D.B. Anderson, R.E. Hoeppel (editors). Battelle Press, Columbus, OH. ISBN 1- 57477-008-X. pp. 259 – 266. vi 4. Roche, A., F. Gaillard, M. Romand, F.M. von Fahnestock. 1991. Metal-Based Bonding Joints: Adhesion Measurement Using a Three Point Flexure Test. Journal of Adhesion Science. Vol. 1(1). pp. 147 – 157. FIELDS OF STUDY Major Field: Environmental Science vii TABLE OF CONTENTS Page ABSTRACT........................................................................................................................ ii ACKNOWLEDGMENTS .................................................................................................. v VITA.................................................................................................................................. vi LIST OF TABLES............................................................................................................. xi LIST OF FIGURES ......................................................................................................... xiv Chapters: 1. GENERAL INTRODUCTION............................................................................... 1 2. CHARACTERIZATION OF EXHAUST GAS FROM A FULL-SCALE IN- VESSEL COMPOSTING SYSTEM ...................................................................... 5 2.1 Summary..................................................................................................... 5 2.2 Introduction................................................................................................. 7 2.2.1 Background..................................................................................... 7 2.2.2 Gas Emissions During Composting.............................................. 16 2.2.3 Objective....................................................................................... 17 2.2.4 Scope............................................................................................. 19 2.3 Materials & Methods................................................................................ 19 2.3.1 Feed Material Preparation............................................................. 19 2.3.2 Reactor .......................................................................................... 20 2.3.3 Off-Gas Sampling......................................................................... 22 2.3.4 Method for Hydrocarbon Gas Analysis ........................................ 26 2.4 Results and Discussion............................................................................. 27 2.4.1 Hydrocarbon Exhaust Gas Concentrations ................................... 27 2.4.2 Hydrocarbon Emission Estimates................................................. 35 2.4.3 Ammonia Exhaust Gas Profiles.................................................... 48 2.4.4 Comparison of In-Vessel Emissions to Those of a Commercial Windrow Process .......................................................................... 52 viii 2.4.5 Example Correlation of Organic Compound Exhaust Gas Concentrations to Corresponding Concentrations in Building Air at a Representative In-Vessel Composting Plant.......................... 55 2.5 Conclusions............................................................................................... 57 3. IN VESSEL COMPOSTING OF EXPLOSIVE-CONTAMINATED SOIL: A PILOT-SCALE EVALUATION FOR PROCESS IMPROVEMENT OPTIONS.............................................................................................................. 61 3.1 Summary................................................................................................... 61 3.2 Introduction............................................................................................... 63 3.2.1 Objective....................................................................................... 65 3.2.2 Technology Background............................................................... 65 3.2.3 Project Overview.......................................................................... 69 3.2.4 Site Description............................................................................. 69 3.2.5 System Installation........................................................................ 71 3.2.6 Windrow ....................................................................................... 75 3.3 Materials and Methods.............................................................................. 76 3.3.1 Compost Feed Material Storage.................................................... 76 3.3.2 Feed Preparation and Test Cell Loading....................................... 76 3.3.3 Test Cell Operating Conditions .................................................... 77 3.3.4 Field Sampling.............................................................................