Chromated Copper Arsenate (Cca) Treatment for Rubber Wood Preservation and Its Impact on the Aquatic Biota
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CHROMATED COPPER ARSENATE (CCA) TREATMENT FOR RUBBER WOOD PRESERVATION AND ITS IMPACT ON THE AQUATIC BIOTA Thesis submitted to the Cochin University of Science and Technology in partial fulfillment of the requirement for the award of the degree of DOCTOR OF PHILOSOPHY in MARINE BIOLOGY by SREEJA A. (Reg. No. 2965) Fishing Technology Division Central Institute of Fisheries Technology (Indian Council of Agricultural Research) Cochin - 682 029, India Faculty of Marine Sciences Cochin University of Science and Technology Cochin - 682 019, India August 2008 DDeedidiccaatteedDedicatedd ttooto mmyymy family & friendsfriends……..…….……...…….. CERTIFICATE This is to Certify that this thesis entitled “Chromated Copper Arsenate (CCA) Treatment for Rubber Wood Preservation and its Impact on the Aquatic Biota” is an authentic record of independent bonafide research work carried out by Miss. Sreeja A. M.Sc., under my guidance and supervision in the Fishing Technology Division of Central Institute of Fisheries Technology, Cochin, in partial fulfillments of the requirements for the degree of Doctor of Philosophy (Faculty of Marine Sciences) and that no part thereof has previously formed the basis for the award of any degree, diploma, associateship, fellowship or any other similar title of any University or Institution. Cochin - 29 Dr. Leela Edwin August, 2008 (Supervising Guide) Dr. Leela Edwin Principal Scientist Central Institute of Fisheries Technology (Indian Council of Agricultural Research) P.O. Matsyapuri, Cochin - 682 029 DECLARATION I, Sreeja A., hereby declare that this thesis entitled “Chromated Copper Arsenate (CCA) Treatment for Rubber Wood Preservation and its Impact on the Aquatic Biota”, is an authentic record of the research work carried out by me under the supervision and guidance of Dr. Leela Edwin, Principal Scientist, Fishing Technology Division, Central Institute of Fisheries Technology, Cochin, in partial fulfillment of the requirement for the Ph.D. degree in the Faculty of Marine Sciences and that no part thereof has previously formed the basis for the award of any degree, diploma, associateship, fellowship or any other similar title of any University or Institution. Cochin - 29 Sreeja A. August, 2008 Central Institute of Fisheries Technology (Indian Council of Agricultural Research) P.O. Matsyapuri, Cochin - 682 029 ACKNOWLEDGEMENT First and foremost I convey my reverential salutation to the Almighty, for enabling me to take up and complete this task. I would like to express my deep sense of profound gratitude and indebtness towards my guide, Dr.Leela Edwin, Principal Scientist, Fishing Technology Division, Central Institute of Fisheries Technology, Cochin, for her inspirational valuable guidance, sustained encouragement and critical assessment during the entire period of research I sincerely thank Dr. K. Devadasan, Director, for his invaluable guidance, encouragement, timely assessment of research work and also for extending all the facilities at the Central Institute of Fisheries Technology for my research work. My sincere thanks to Dr. B. Meenakumari, HOD, Fishing Technology Division, for worthful guidance throughout the work I sincerely thank Dr. A.V. Saramma HOD, for her wholehearted encouragement and for being a member of the Doctoral Committee. My sincere thanks are due to all Scientists of Fishing Technology Division of the Central Institute of Fisheries Technology for their fruitful comments and help during the work I am grateful to Dr. Geethalakshmi V., Dr. T. V. Sankar and Shri. P. Muhamed Ashraf (Scientists, CIFT) for their valuable suggestions and help during the work. I would like to thank Shri. P.T. Sebastian, Smt. K.G. Sasikala, Shri. N. Krishnan and Shri. P. Raghavan (Staff of Material Science and Marine Pollution Section) for the immense help. I am also indebted to the scientific, technical, administrative, supporting staff of the CIFT for their kind co-operation and goodwill. I sincerely thank all Senior Research Fellows of CIFT, especially in the Fishing Technology Division for their support, candid and critical comments and goodwill. I express my sincere gratitude to the Scientists and staff of Forest Research Institute, Dehra Dun; Institute of Wood Science and Technology, Bangalore and Marine Biodeterioration Division, IWST, Visakhapatnam, Rubber wood Testing Laboratory, Rubber Board, Kottayam for their help and providing me with library and testing facilities for the successful completion of work. I owe loving thanks my entire family and friends especially to my parents, sister and my fiancé for without their encouragement, understanding and prayers it would have been impossible for me to finish this work. CONTENTS Page No. 1. Introduction 1 1.1. Biodeterioration of wood 2 1.2. Agencies causing marine biodeterioration 4 1.3. Durability of rubber wood 7 1.4. Assessment of biodeterioration 9 1.5. Prevention of biodeterioration 12 1.6. Chromated Copper Arsenate (CCA) as wood preservative 13 1.7. Leaching of CCA 19 1.8. Impact of CCA components on non-target biofouling organisms 20 1.9. Alternatives to CCA 31 1.10. Scope of the study 33 1.11. Objectives of the study 34 2. Materials and Methods 36 2.1. Materials 36 2.1.1. Rubber wood 2.1.2. Marine plywood 2.1.3. Preservative solutions 2.1.4. Paint 2.1.5. Fibreglass Reinforced Plastic (FRP) 2.2. Methods 39 2.2.1. Preservative impregnation procedure 2.2.2. Field exposure of preservative treated panels 2.2.3. Hydrographical conditions of the test site 2.2.4. Arrangement of the panels and sampling strategy 2.2.4.1. Qualitative assessment 2.2.4.2. Quantitative assessment 3. Resistance of CCA Treated Rubber Wood to Marine Biodeterioration 49 3.1. Introduction 49 3.2. Materials and Methods 51 3.2.1. Examination and evaluation of the panels 3.2.1.1. Visual observations 3.2.1.2. X - ray radiographic analysis 3.3. Results and Discussion 54 3.3.1. Visual observation 3.3.2. X-ray radiographic studies 3.3.3. Reduction of Surface area and volume 3.4. Conclusion 63 4. Microstructural Changes in Untreated and Preservative Treated Rubber Wood on Estuarine Exposure 72 4.1. Introduction 72 4.2. Materials and methods 73 4.3. Results and discussion 74 4.4. Conclusion 79 5. Biodeteriorative Changes in the Physical Chemical and Mechanical Properties of Rubber Wood Due to Estuarine Exposure 84 5.1. Introduction 84 5.2. Materials and Methods 86 5.2.1. Specific gravity 5.2.2. Compressive strength 5.2.3. FTIR analysis 5.3. Results and Discussion 88 5.3.1. Changes in specific gravity 5.3.2. Effect of preservative treatment on mechanical strength 5.3.3. Effect of biodeterioration on mechanical strength 5.3.4. FTIR analysis 5.3.4.1. Spectra of preservative treated panels 5.3.4.2. Spectra of biodeteriorated panels 5.4. Conclusion 100 6. Acute Toxicity of CCA and its Constituents Copper, Chromium and Arsenic in Villorita cyprinoides 112 6.1. Introduction 112 6.2. Materials and Methods 115 6.2.1. LC50 values and BCF values 6.3. Results and Discussion 118 6.4. Conclusion 122 7. Bioaccumulation of Chromated Copper Arsenate Components in Oreochromis Mossambicus 127 7.1. Introduction 127 7.2. Materials and Methods 128 7.2.1. Fish 7.2.2. Experimental panels 7.2.3. Sampling procedure 7.2.4. Data analysis 7.3. Results and Discussion 130 7.3.1. Hydrographical parameters 7.3.2. Concentration of CCA components in fish tissues 7.2.3. Concentration of metals in the leachate 7.4. Conclusion 140 8. Bioaccumulation of CCA Components in Non-Target Organisms Growing on Rubber Wood Panels 156 8.1. Introduction 156 8.2. Materials and Methods 158 8.3. Results and Discussion 160 8.3.1. Metals in water 8.3.2. Metals in barnacle tissues 8.3.3. Metals in shells 8.4. Conclusion 169 9. Impact of Chromated Copper Arsenate on Non -Target Organisms 174 9.1. Introduction 174 9.2. Materials and Methods 175 9.3. Results and Discussion 178 9.3.1. Occurrence of wood boring organisms 9.3.2. Occurrence of fouling organisms 9.3.3. Changes in Percent coverage 9.3.4. Changes in the total biomass 9.4. Conclusion 189 10. Summary 200 11. Recommendations 205 LIST OF TABLES S. Page No. Table no. Table name No. 1. Table 2.1. Conditions of Vacuum - Pressure Impregnation 48 2. Table 3.1. Performance rating of panels for attack by 65 Teredinids, other molluscs and crustaceans after an exposure period of six months in the estuary 3. Table 3.2. Rating for attack by Teredinids, other molluscs 66 and crustaceans after an exposure period of twelve months in the estuary 4. Table 3.3. Rating system for attack by Teredinids, other 67 molluscs and crustaceans after an exposure period of eighteen months in the estuary 5. Table 3.4. Rating system for attack on panels (that are 68 scraped of monthly to remove fouling) by Teredinids, other molluscs and crustaceans after an exposure period of eighteen months in the estuary 6. Table 3.5. The percentage area and volume of the panels 69 deteriorated during 6, 12 and 18 months of immersion in the field 7. Table 5. 1. Tukey’s test results for the (a) Compression 101- Strength at Maximum Load of (1) untreated 102 rubber wood panels, CCA treated panels to retention of (2) 16 kg m-3 (3) 29 kg m-3 (4) 42 kg m-3 (5) dual treated panels 8. Table 5.2. Tukey’s test results for the Compression Strength 102- at Maximum Load of (a) untreated rubber wood 104 panels, CCA treated panels to retention of (b) 16 kg m-3 (c) 29 kg m-3 (d) 42 kg m-3 (e) dual treated panels; exposed in cochin estuary for durations (1) unexposed (2) 6months (3) 12 months (4) 18 months 9.