Microdistribution and Retention of Chloropicrin in Wood
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AN ABSTRACT OF THE THESIS OF Barry Scott Goodell for the degree of Doctor of Philosophy in Forest Products presented on April 8, 1983 Title: Microdistribution and Retention of Chloropicrinin Douglas-fir (Pseudotsuga menziesii (Mirb.) Franco]Heartwood Abstract approved: Redacted for Privacy Le-r-44 Robert L. Krahmer Quantitative and qualitative informationon the retention of chlorinated residues in chloropicrintreated wood is lacking. Retention of chloropicrin and itschemical breakdown products in wood, and the effects of chloropicrintreatment of wood on invading decay fungi are explored in this thesis. Chlorinated residues in amountsup to 1.5% (w/w, as determined by neutron activation analysis) were present in Douglas-firwood exposed to chloropicrin vapors for 240 days. These residues could not be totally removed by aeration,acetoneextraction, heating, or high vacuum treatment. Lesser amounts of chlorinated residueswere detected in wood exposed to chloropicrin forshorter periods of time or treated with smaller quantities of the chemical. Analysis of vaporsdesorbed from chlorpicrin-treated woodsuggests that chemically unaltered chloropicrin can be retained bywood up to 4 years after treatment. Decreased retention of chlorinated residues intreated wood with brown rot decay suggests thathydrogen bonding and van der Waals forces are responsible, at least in part, for this retention. Wood does not swell when treated with chloropicrin.Although a monomolecular layer of chloropicrin may hydrogen bond to wood at some sites, lack of swelling indicates that chloropicrin molecules are retained by forces weaker than the hydrogen bonds which hold the lignocellulose matrix of wood together. Covalent linkages may also form between chloropicrin, or chlori- nated breakdown products of chloropicrin, and wood.Energy dispersive X-ray analysis showed that chloropicrin residues were present in greater concentrations in areas of the wood rich in lignin or extrac- tives. Covalent linkages between chloropicrin breakdown products and vanillin were detected in mass spectrographic analyses of chloropicrin/vanillin mixtures. Thin layer chromatography of extracts from chloropicrin treated wood indicated that chloropicrin may be bonding to dihydroquercetin (a phenolic wood extractive) and to other extractives in wood. Microscopic observation of Douglas-fir wood exposed under severe laboratory decay conditions to Poria carbonica (a brown rot fungus), and to Ganoderma applanatum (a white rot fungus), showed that these fungi will attack chloropicrin treated wood, producing bore holes and erosion of cell lumen surfaces similar to that observed in untreated wood. Lysis and vacuolation of the fungal hyphae, particularly of G. applanatum, indicates that chloropicrin has an inhibitory effect on fungi in wood. Microdistribution and Retention of Chloropicrin in Wood by Barry Scott Goodell A THESIS submitted to Oregon State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy Completed April 8, 1983 Commencement June 1983 APPROVED: Redacted for Privacy Professor of Forest Products in charge of major Redacted for Privacy Head of Department of Forest Products Redacted for Privacy Dean of Graduate c ool Date thesis is presented April 8, 1983 Typed by Julie Cone for Barry Scott Goodell DEDICATED TO JODY ACKNOWLEDGEMENTS My special thanks to Bob Krahmer for his guidance over the past three and one-half years; not only for his assistance with my thesis research but for his help in developing my teaching skills, and for his friendship. Thanks are also due to Mal Corden, Bob Graham and Murray Laver for their insights into pathology, preservation and che- mistry, respectively. Without their research insights and their help in developing my skills as a researcher this work would not have been possible. I would like to acknowledge and thank Bob Graham, Bob Krahmer and Helmuth Resch for the opportunities and funding they pro- vided me, allowing me to carry out not only my thesis research but also other projects which helped to broaden my background in wood technology and wood preservation/pathology.Ted Scheffer and Don Miller also deserve my heartfelt thank you for their friendship and for the opportunities and insights they have given me in research out- side my thesis area. Many people gave me technical assistance in work necessary for the development of the research presented in this thesis. Their excellent assistance is acknowledged below: Electron Microscopy: Alfred Soeldner- Instructor, Botany and Plant Pathology, OSU Christine Weiss Research Assistant, Botany and Plant Pathology, OSU Arnold Schmitt Research Assistant, Mining, Metalurgical and Ceramic Engineering, University of Washington Mass Spectroscopy: Donald Griffin - Chemist, Agricultural Chemistry, OSU Neutron Activation Analysis: Michael Conrady - Chemist, Radiation Center, OSU Roman Schmitt - Professor of Chemistry, Radiation Center, OSU Photography: Grant Mitman - Teaching Assistant, Botany and Plant Pathology, OSU Supplying Fungal Cultures: Robert Zabel - Professor, College of Environmental Science and Forestry, State University of New York Jean Clark - Technologist, Forintek Canada Corporation, Western Laboratory Bradley Kropp - Mycologist, Botany and Plant Pathology, OSU Thin Layer Chromatography: Steven Danko - Research Associate, Agricultural Chemistry, University of Nebraska Finally, I would like to thank my wife, Jody, not only for her patience and understanding during my graduate career, but also for the technical support she offered me while she worked toward her own degree. Thanks to you all! TABLE OF CONTENTS Page INTRODUCTION 1 BACKGROUND 3 Retention of Chloropicrin 3 Bonding of Chloropicrin to Wood 4 Chemical Breakdown of Chloropicrin 6 Other Chemical Reactions of Chloropicrin 8 Fungal Attack of Chloropicrin Treated Wood 8 PROCEDURES 12 I. Sorbtion 12 Dimensional Change Occurring in Wood Treated 12 With Chloropicrin Non-Steady-State Desorbtion and Residue 13 Analysis II. Neutron Activation Analysis 14 Preliminary Analysis of Background Chlorine 16 in Wood Analysis of Treated Samples 16 Sorbtion Samples 16 Non-decayed Wood 17 Decayed Samples 18 III. Energy Dispersive X-ray (EDX) Analysis to 19 Determine the Microdistribution of Chlorinated Residues IV. Infrared and Mass Spectrographic Analysis 20 Analysis of Chloropicrin and Derivitized 20 Wood Components Analysis of Desorbed Gases from Chloropicrin 21 Treated Wood V. Microscopy of Treated Wood Samples Infected With 22 Decay Fungi RESULTS AND DISCUSSION 23 I. Sorbtion 23 Dimensional Change Occurring in Wood Treated 23 With Chloropicrin Non-Steady-State Desorbtion and Residue 23 Analysis Page II. Neutron Activation Studies to Determine the 27 Amount of Chloropicrin Retained by Wood After Treatment Preliminary Analysis for Background Chlorine 27 in Wood Analysis of Treated Wood Samples 27 Sorbtion Samples 27 Non-decayed Wood 29 Decayed Samples 32 III. Energy Dispersive X-ray (EDX) Analysis to 36 Determine the Microdistribution of Chlorinated Residues IV. Infrared and Mass Spectrographic Analysis 50 Analysis of Chloropicrin and Derivitized 50 Wood Components Analysis of Desorbed Gases from Chloropicrin 56 Treated Wood V. Microscopy 58 CONCLUSIONS 68 SUGGESTIONS FOR FUTURE RESEARCH 70 BIBLIOGRAPHY 71 APPENDIX 1 79 APPENDIX 2 80 APPENDIX 3 81 LIST OF FIGURES Figure Page Sorbtion (-11-) and desorbtion (-II-) of chloropicrin 24 from Douglas-fir wafers (A) over time. Sorbtion (--) and desorbtion (-II-) of chloropicrin 25 from Douglas-fir wafers (B) over time. Chlorine retention in samples decayed to a range of 34 weight losses by Poria carbonica prior to treatment with chloropicrin. Chlorine retention in samples decayed by Poria 35 carbonica prior to treatment with chloropicrin. Amount of decay in the samples determined by the percentage of alkalli soluble material. Same regression as shown in Figure 4 minus three 37 data points (> 100 pg chlorine). Scanning electron micrographs of Douglas-fir heartwood 38 treated for two weeks with liquid chloropicrin. Above, split radial surface, 500X; below, razored cross section, 500X. Typical energy dispersive X-ray scan across chloro- 39 picrin-treated wood showing the absence of chloronated material in the sample. Peaks for gold and palladium from the coating material are present in the scan. Representative energy dispersive X-ray spectral scan 41 across acetone extracted or heated control wafers. No detectable chlorine peak is present. Energy dispersive X-ray analysis line scan across one 42 cell wall of an untreated, control wafer. No detect- able amounts of chlorine are present. Representative energy dispersive X-ray spectral scan 43 across extracted or heated, chloropicrin-treated wafers. Energy dispersive X-ray analysis line scan across a 44 cell wall of a heated, chloropicrin-treated sample that was sectioned dry. Energy dispersive X-ray analysis line scan across a 45 cell wall of a heated, chloropicrin-treated sample that was sectioned wet. Figure Page Representative energy dispersive X-ray line scan across 46 an acetone extracted or heated, chloropicrin-treated wood. Energy dispersive X-ray line scan across ray cellwalls, 47 tracheid cell walls, and resin canal parenchyma cells with included deposits in extracted, chloropicrin- treated wood. Energy dispersive X-ray line scan across cellwall 48 material and extractive materials deposited in the lumens of rays in extracted, chloropicrin-treated wood. Energy dispersive X-ray line scan across fusiform 49 ray in heated,