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A Thesis Submitted in Partial Fulfilment of the Requirements of the University Karst hydrogeology, hydrogeochemistry and processes of tufa deposition in Carboniferous Limestone springs of the Mells Valley, Somerset Lisa Thomas A thesis submitted in partialfulf ilment of the requirements of the University of the West of England, Bristol for the degree of Doctor of Philosophy at Bath Spa University School of Science and the Environment, Bath Spa University June 2007 ABSTRACT A number of karst springs rise in the Carboniferous strata of the Mells Valley, Somerset which is an area surrounded by many active and disused quarries. Some of these karst springs actively deposit tufa, a secondarypr ecipitate of calcium carbonate, and they have been identified by the Environment Agency as potentially vulnerable to the effects of local sub-water table quarrying. A comparative study of a tufa-depositing spring, Whitehole Farm Spring, and a non tufa-depositing spring, St. Dunstan's Well, was carried out in order to determine the influence of hydrogeology, hydrogeochemistryand environmental biology on the processes of tufa deposition. The two springs are approximately 2 km apartand located within the same outcrop of Carboniferous Limestone strata. A series of qualitative dye-tracing tests established a positive hydraulic connection between a feeder stream which rose in the Old Red Sandstone of the upper hydrological catchment, a sinkhole at the junction with the Lower Limestone Shales and Whitehole Farm Spring resurgence in the Carboniferous Limestone. The sinkhole was shown to have two separate channels to the water table. The tests demonstrated that structural geology and the water table had definable effects on the subterranean route and travel time of the allogenic recharge water. The recharge water to Whitehole Farm Spring was guided by the SE - NW Downhead Fault and did not follow the SW - NE course of the natural dryval ley. The water velocity was dependent on the height of the local water table at the time of the tests. Hydrograph analysis of flow data combined with the dye-tracing tests illustrated the rapid response of the springs to storm events (< 24 hrs). The results gave an indication of the shallow nature of the Carboniferous Limestone aquifer and the different stages of development of fissures and conduits in the twospr ing systems, St. Dunstan's Well being a more mature karst system than Whitehole Farm Spring. Analysis of 18 monthly water samples from both springs at their resurgences and 100 metres downstream revealed temporal and spatial differences in the 2 hydrogeochemistryof the springs and their streams. Ca + and HC03- were the dominant ions in both spring waters, however, neither of the spring resurgences were supersaturated with respect to calcite (Whitehole Farm ing, mean -0. 17 + 0.08 Sic ; St. Dunstan's Well, mean -0.33 + 0.08 Sic). Spr 2 The resurgence water at Whitehole Farm Spring was higher in Ca + (mean + 3.35 mg r1) than at St. Dunstan's Well and became supersaturated as it 112 2 flowed downstream (mean 0.43 ± 0.10 Sic). Lower Ca + levels at St. 1 Dunstan's Well (80 + 2. 7 mg r ) were influenced by the degassing of recharge water and the deposition of calcite as speleothem within the open system of caves behind the resurgence. Downstream supersaturation was also lower (-0.01 1 ± 0.079 Sic). There was a highly significant difference (p <0.001) 1 between mean daily flow at Whitehole Farm Spring (0.95 + 0.19 ML d- ) and 1 St. Dunstan's Well (11. 58 ± 1.93 ML d- ). Electrical conductivity, total dissolved solids, alkalinity, Na, K, and N03 were also higher at Whitehole Farm Spring, the differences being significant (p < 0.01 ). I There were major differences in the biodiversity and environment of the two sites. Petrographic examination of field-collected tufa samples from Whitehole Farm Spring demonstrated that the stream flora, in particular lower plants, and the surrounding riparian vegetation were a major influence on the formation and morphology of the tufa deposits. Newly accreted tufa which had formed on artificial substrates placed in the stream, revealed calcite crystals surrounding the empty moulds of filamentous cyanobacteria. Hydrological conditions within the stream also influenced the micromorphology of calcite crystals forming on twofi lamentous algal species, Vaucheria longata and Zygnema stellinum. Whitehole Farm Spring was also found to be the more stable environment where biodiversity was higher. The shaded conditions created by Whitehole Farm Spring's woodland environment were beneficial to the growth of filamentous algae, cyanobacteria and bryophytes. The dominant species upstream was a crustose epilithic red alga Hildenbrandia rivularis. Downstream, in and on the tufa deposits the dominant aquatic flora were a number of species of the filamentous yellow-green alga Vaucheria and the cyanobacterium Lyngbya and the moss species Palustriella ( Cratoneuron) commutatum. These species were either absent or growing under different ecological conditions at St. Dunstan's Well where there was sparse woodland. The dominant species at St. Dunstan's Well was the filamentous green alga Cladophora glomerata which was not present at Whitehole Farm Spring. Debris from the surrounding riparian vegetation at Whitehole Farm Spring acted as substrates for colonisation by microorganisms which enhanced the nucleation and growth of tufa in the stream. Hydrological and environmental conditions at St. Dunstan's Well prevented the accumulation of organic debris within the stream flow. The study highlighted the need for conservation of the natural environment and biota in order to maintain actively-depositing tufa spnngs. II ACKNOWLEDGEMENTS The funding for this project was provided by Hanson Quarry Products, Europe and the Environment Agency and I would like to express my gratitude to Malcolm Keeble (Hanson), MartinCr ow (Hanson), Pauline Johnstone (EA) and Paul Whittaker(EA). In particular, I would like to thank Roger Griffiths (Hanson) a valued friend and colleague, for his supportand patient understanding throughout the period of this study. I am also grateful to Prof. Alan House and Dr. Nick Rukin (Entec) for taking partin the Steering Group meetings. I would like to thank my supervisors Dr. Juliet Brodie (Natural History Museum) and Dr. Nigel Chaffey (Bath Spa University) for their help and advice on all sections of the text. I would also like to thank Dr. Ani I de Sequira (Bath Spa University), Mr. Allan Dyson (Bath Spa University), Dr. Gill Odolphie (Hanson) and Dr. Mary Holmes for their helpful advice and literary contributions. Many thanks to Mr. Hugh Prudden, Dr. Willie Stanton and Prof. Eric Robinson (Somerset Geology Group) for their encouragement and enthusiasm for the project (and inside information on the Mendip Hills!). I am grateful to Prof. Brian Whitton and Dr. David John for their assistance with species identification at the Freshwater Algal Identification workshop, University of Durham. A special mention must go to my brother Nick, for retrieving hundreds of lost files when my ancient computer suddenly and unexpectedly expired. How did he do it? I am indebted to Dr. Clem Maidment, also a valued friend and colleague, for all his help as my voluntary external supervisor, German translator and general sounding board. Finally, and most of all, I want to thank my partnerand uncomplaining field assistant, Alan, who has supported me in every way during my academic and scientific career. III CONTENTS ABSTRACT ACKNOWLEDGEMENTS Ill CONTENTS IV LIST OF FIGURES X LIST OF TA BLES XV CHAPTER 1 - GENERAL INTRODUCTION 1.1 BA CKGROUND TO THE STUD Y 1 1.2 RE ASONS FORTHE STUD Y 3 1.3 AIMS AND OBJECTI VE S 5 1.4 TUFA 7 1.4.1 Definition of terms 7 1.4.2 Processes of tufa deposition 7 1.4.3 Tufa morphology and geomorphology 9 1.4.4 Karst springs and tufa deposition 11 1.4.5 The decline in tufa deposition 11 1.5 QUARRYING AN D WATERAB STRACTION 12 1.6 THE STUD YAR EA AND FIELD SITES 15 1.6.1 Catchment land use 18 1.7 THE SPRINGS 20 1.7.1 St. Dunstan's Well 20 1.7.2 Whitehole Farm Spring 23 IV CHAPTER 2- GEOLOGY AND HYDROGEOLOGY 2.1 INTRODUCTION 25 2.2 GEOLOG YOF THE STUD YAR EA 27 2.2.1 The Lower Carboniferous Series 30 2.2.2 The Upper Carboniferous Series 31 2.3 STRUCTURAL GEOLOG Y 32 2.3.1 Faults, bedding planes and joints 32 2.4 HYDROLOG YAND HYDROGEOLOG YOF THE STUD YAR EA 35 2.4.1 The hydrodynamics of karst groundwater flow 37 2.4.2 The water table 37 2.4.3 Groundwater zones 39 2.4.4 Cave and karst development 40 2.4.5 Hydrographs and characteristics of karst drainage 43 2.5 RE VI EW OF MENDIP KA RS T HYDROGEOLOG YRE SEARCH 45 2.6 RA TIONALE FOR DYE TRACING TESTS 50 2.7 GROUNDWATERTR ACING 52 2.7.1 Dye tracing techniques 52 2.8 AIMS 53 2.9 MATERIALS 54 2.10 METHODS 55 2.11 RE SULTS 60 2.1 1.1 Hydrograph analysis 63 2.12 DISCUSSION 66 v CHAPTER 3 - HYDROGEOCHEMISTRY 3.1 HYDROGEOCHEMICAL PROCESSES 71 3.2 THE SYSTEM CONCEPT 72 3.3 EQUILI BRI UM 73 3.4 CALCITE 75 3.5 SATURATION STATES AND THE LANGELIERIN DE X 77 3.6 CARBONATE CHEMISTRYAND KI NETICS 80 3.7 GROUNDWATERCH EMISTRY 82 3. 7.1 Limestone weathering, solution and precipitation 82 3.7.2 Carbon dioxide 83 3.8 THE HYDROGEOCHEMISTRYOF TUFA DEPOSITION 84 3.9 AIM 91 3.10 MATERIALS AND METHODS 92 3.1 0.1 Field methods 92 3.1 0.2 Water sampling procedure 93 3.1 0.3 Laboratory methods 94 3.1 0.4. Data analysis and statistics 95 3.11 RE SULTS 96 3.11.1 Precipitation and flow rates 96 3.1 1.2 Hydrogeochemical data 99 3.11.3 Physical parameters 104 3.
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