The Characterisation and Control of Ochre Deposits
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THE CHARACTERISATION AND CONTROL OF OCHRE DEPOSITS IN LAND DRAINAGE SYSTEMS A thesis for the Degree of PhD by I Ap Dewi BSc(Wales) February 1985 Acknowledgements It is with gratitude that I acknowledge the guidance and assistance given by my supervisors Mr W I Kelso and Dr D B Johnson. I am indebted to all the staff in the Biochemistry and Soil Science department at Bangor for their advice and help. I wish to thank the farmers and others who allowed access to ochre sites and helped to collect the deposits. I am grateful to Mrs M Pritchard for typing the untidily written drafts and to Mrs E Richter for translating some German and Dutch articles. My wife, Sian,A deserves all gratitude for her support, encouragement, and patience. This work was supported by a Ministry of Agriculture, Fisheries and Food Postgraduate Studentship. CONTENTS Page 1. Summary 7 2. Literature Review 2.1 Introduction 9 2.2 The nature of iron ochre 13 2.2.1 Types of ochre 14 2.2.2 The composition of ochre 15 203 The microbiology of filamentous ochre 16 2.3.1 The filamentous bacteria 2.3.1.1 Definition and history 17 2.3.1.2 Taxonomy 18 2.3.1.3 Sphaerotilus 22 2.3.1.4 Leptothrix app 25 2.3.1.5 Other sheathed filamentous bacteria 27 2.3.1.6 The relationship between filamentous bacteria and iron 29 2.3.2 Gallionella 32 2.3.3 Other microorganisms 33 2.4 The microbiology of pyritic ochre 2.4.1 The Thiobacilli 34 2.4.2 Acidophilic heterotrophs 37 2.4.3 The coexistence of microorganisms associated with pyritic and filamentous ochre 38 2.5 The formation of iron ochre 2.5.1 Factors influencing ochre formation 40 2.5.2 The mechanisms of ochre formation 41 2.5.2.1 Chemical oxidation 43 2.5.2.2 The action of autotrophic iron bacteria (pyritic ochre formation) 46 2.5.2.3 Decomposition of the organic component of soluble complexes by heterotrophic organisms 50 2.5.2.4 The action of microorganisms causing environmental changes. 51 2 2.6 Possible solutions to the iron ochre problem 2.6.1 Prediction 52 2.6.2 Prevention 2.6.2.1 Self-cleaning grades 54 2.6.2.2 Special drainage systems 54 2.6.2.3 Aerobic and anaerobic conditions 55 2.6.2.4 Lime 56 2.6.2.5 Filters 57 2.6.2.6 Bacteriocides 58 2.6.3 Cure 2.6.3.1 Mechanical methods 62 2.6.3.2 Chemical treatment 63 3. Sampling and chemical analysis of ochre samples 3.1 Sampling 65 3.2 Chemical analysis 74 3.2.1 Methods 3.2.1.1 pH 74 3.2.1.2 Loss on ignition 74 3.2.1.3 Total iron and manganese 74 3.2.1.4 Total organic carbon 77 3.2.1.5 Colour 78 3.2.1.6 Absolute sugar levels 79 3.2.1.7 Relative sugar levels 80 3.2.2 Results 3.2.2.1 pH 82 3.2.2.2 Loss on ignition 82 3.2.2.3 Total iron and manganese 82 3.2.2.4 Total organic carbon 83 3.2.2.5 Colours 91 3.2.2.6 Absolute sugar levels 91 3.2.2.7 Relative sugar levels 91 3 3.3 Discussion 105 4. The microbiology of ochre samples 4.1 Light and scanning electron microscopy 128 4.1.1 Light microscopy 128 4.1.2 Scanning electron microscopy 134 4.2 Autotrophic microbiology 142 4.3 Heterotrophic microbiology 145 4.3.1 Acidophilic heterotrophs' 145 4.3.2 Complex-degrading heterotrophs 157 4.4 Discussion 167 5. The culture of sheathed filamentous bacteria 5.1 Standard media 182 5.2 Model systems 200 5.2.1 Tank model 200 5.2.2 Open ditch model 203 5.3 Experimental media 5.3.1 Drainage water 204 5.3.2 Extracts and infusions 205 5.3.2.1 Hay infusions 205 5.3.2.2 Dried grass 206 5.3.2.3 Heather extracts 207 5.3.3 Organic acids 208 5.3.3.1 Ascorbic acid 208 5.3.3.2 Tannic, Citric and Latic acid 209 5.3.4 Glucose-iron media 210 5.3.4.1 Glucose at 10 pg/ml 213 5.3.4.2 Glucose at 50yeml and 100 yeml 216 5.4 Discussion 217 11 6. Chemical oxidation and the formation of ochre 6.1 Chemical oxidation of ferrous iron in drainage water 225 6.2 The effect of ochre on the rate of ferrous iron oxidation 230 6.2.1 The apparent growth of filamentous bacteria in hay extract media 230 6.2.1.1 Qualitative observations 230 6.2.1.2 Quantitative observations 231 6.2.1.3 The effect of sterilized ochre on the concentration of iron in hay extract medium and distilled water 23k 6.2.2 The effect of air dried ochre on the concentration of Fe(II) in a ferrous sulphate solution 237 6.2.2.1 The effect of air dried ochre on the rate of oxidation of Fe(II) in a ferrous sulphate solution 237 6.2.2.2 The effect of various weights of air dried ochre on the concentration of Fe(II) in ferrous sulphate solutions 238 6.2.2.3 The effect of air dried ochre on the Fe(II) concentration of ferrous sulphate solutions in a continuous flow apparatus 241 6.2.3 The effect of air dried ochre on the concentration of iron in a citric acid - ferrous sulphate solution 243 6.2.4 The effect of sterilized ochre on the concentration of iron in drainage water 244 6.3 Discussion 253 7. The control of microorganisms associated with ochre deposition 7.1 The effect of copper on sheathed filamentous bacteria 259 7.1.1 The effect of copper on sheathed filamentous bacteria in glucose-- iron medium 259 7.1.2 The effect of VC-17 antifouling on sheathed filamentous bacteria in drainage water 260 7.2 The effect of biocides on Thiobacillus ferrooxidans 262 7.3 The effect of antibacterial compounds on ferric citrate complex-degrading heterotrophic bacteria in ferric ammonium citrate medium 264 7.3.1 The effect of copper on complex-degrading heterotrophs in ferric ammonium citrate medium 264 7.3.2 The effect of acrolein and panacide on complex-degrading heterotrophs in ferric ammonium citrate medium 265 7.3.3 The effect of antifouling paints on complex-degrading heterotrophs 266 7.3.3.1 VC-17 7.3.3.2 U644, W492, W319 antifouling paints 267 7.4 The effect of antifouling paints on acidophilic heterotrophic bacteria 269 7.5 The release of copper from VC-17 antifouling 270 7.5.1 Release of copper from VC-17 in different volumes of distilled water 270 7.5.2 The effect of pH on the release of copper from VC-17 antifouling 271 7.6 Discussion 273 8. Discussion and Conclusion 8.1 Characteristics 278 8.2 Formation 281 8.3 Types of ochre 286 8.4 Control 287 9. References 291 6 1. SUMMARY Ochre deposits from sites in England and Wales varied widely in their composition, their appearance, their rate of formation and where they occurred. It was demonstrated that chemical oxidation could account for the precipitation of iron from drainage water. In sterile samples of drainage water from ochreous sites 80% of the total iron in solution was oxidized within 48 hours. It was also shown that autocatalysis of ferrous iron oxidation by ferric precipitates could occur in drainage water. Filamentous bacteria were observed by light microscopy in most samples and were assigned to the genus Leptothrix. Gallionella 'app were observed in some deposits but their distribution was not widespread. Shaerotilus slop_ were not found by light microscopy or isolated in artificial media. The chemolithotroph T.ferrooxidans was found in acidic ochre samples (pH44.0) and in samples from drainage water of near neutral pH suggesting that it can survive in microenvironments of low pH, contributing to ochre formation over a wide range of drainage water pH. Heterctrophic bacteria capable of growing in artificial media of low pH were isolated, primarily from acidic samples, and the results suggested that they were polysacchuride producing. Complex degrading heterotrophic bacteria were also isolated from ochre using a ferric ammonium citrate medium. Some deposits, on the basis of chemistry and microbiology, could be described as either pyritic or filamentous ochre. However, the majority of samples fell between these extremes and had various combinations of filamentous bacteria, Thiobacilli and heterotrophic organisms. 7 A marine antifouling paint containing copper was used to control the growth of sheathed filamentous bacteria in drainage water and other heterotrophic bacteria in artificial media. Since ochre results from the interaction of many factors, chemical and microbial, the use of copper applied as an antifouling paint or incorporated into drainage pipes, must be proved effective and economic in relation to ochre prevention in agricultural drainage systems. 2. LITERATURE REVIEW 2.1 INTRODUCTION Field drainage can be defined as the removal from agricultural land of surplus water which might otherwise restrict crop growth (Hudson, 1975). In 1977 the Ministry of Agriculture, Fisheries and Food (MAFF) estimated that for over a half of the agricultural land of England and Wales, field drainage was a fundamental necessity for efficient farming. A national survey by MAFF (1977) showed that agricultural production on approximately three million hectares of land was limited by the absence of efficient drainage, while almost another three million hectares depended upon the maintenance of existing drainage systems.