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University of Southampton Research Repository Eprints Soton University of Southampton Research Repository ePrints Soton Copyright © and Moral Rights for this thesis are retained by the author and/or other copyright owners. A copy can be downloaded for personal non-commercial research or study, without prior permission or charge. This thesis cannot be reproduced or quoted extensively from without first obtaining permission in writing from the copyright holder/s. The content must not be changed in any way or sold commercially in any format or medium without the formal permission of the copyright holders. When referring to this work, full bibliographic details including the author, title, awarding institution and date of the thesis must be given e.g. AUTHOR (year of submission) "Full thesis title", University of Southampton, name of the University School or Department, PhD Thesis, pagination http://eprints.soton.ac.uk This thesis is dedicated to my parents, the people whom I love and who love me University of Southampton Phosphorus biogeochemistry and models in estuaries: Case study of the Southampton Water system By Jian XIONG Thesis submitted to the University of Southampton in partial fulfilment of the degree of Doctor of Philosophy. February 2000 School of Ocean and Earth Science University of Southampton United Kingdom UNIVERSITY OF SOUTHAMPTON ABSTRACT FACULTY OF SCIENCE SCHOOL OF OCEAN AND EARTH SCIENCE DOCTOR OF PHILOSOPHY Phosphorus biogeochemistry and models in estuaries: Case study of the Southampton Water system By Jian XIONG Various factors may increase the supply of organic matter content (eutrophication status) of estuarine and coastal systems. The most common cause of eutrophication is considered to be nutrient enrichment. In this study data has been collected in monthly surveys from January 1998 to April 1999 in the Southampton Water system, and the major features of nutrients (nitrogen, phosphorus and silicon) and suspended particulate matter (SPM) thus obtained. Additionally phosphorus in porewaters, and the solid phase in sediments were measured. The forms of phosphorus in the solid phase of sediment (deposited and suspended) were also measured using a modified sequential phosphorus extraction protocol (SPEPs) method. The ranges of the dissolved inorganic phosphorus (DIP) and other nutrients are similar to the data from the SONUS investigations. The overall distribution of DIP are strongly influenced by the sewage inputs to the system, with a peak in concentration in the River Itchen from the sewage works followed by apparently conservative behaviour. The concentration of dissolved organic phosphorus (DOP) were often low (rarely exceeded 5 |iM) and irregularly distributed in the system. The concentrations of particulate phosphorus in the water column and in the particles decreased seaward. The P:Fe ratio in the bicarbonate-dithionite released phase from particles implied that the phosphorus "saturated" particles near the sewage outfall are likely buried before they reach the high salinity waters and the particles in the high salinity waters are mainly from sediment resuspension, the detritus of phytoplankton or from offshore. The N/P ratios obtained implies that the system has potential phosphorus limitation of phytoplankton growth. The concentrations of the forms of inorganic phosphorus in the sediment generally decreased seaward. The Ca-bound phosphorus appears to be the dominant form of inorganic phosphorus (about 55%-85% of total inorganic phosphorus) in most of the sediments in the system. Benthic flux measurements revealed that the sediments in the system generally act as a sink of dissolved inorganic phosphorus and a source of dissolved organic phosphorus. This is in contrast to the fluxes of DIP predicted from the pore-water concentration gradients and implied the presence of a ferric iron-rich oxidising cap on the sediment surface. The results of a Kd model applied on the freshwater-sea boundary revealed that within the range of the riverine DIP concentration only a small amount of removal or addition of DIP is likely to occur. The Kd model is useful in predicting the influence of resuspended particles on DIP in the water column after resuspension "events" caused by storm and dredging activities. The total phosphorus input to the system is estimated as 144 ± 23.7 tonnes per year. The riverine input is the major source of phosphorus (about 69% of the total inputs). The direct sewage input (30% of the total phosphorus inputs) is also an important source of phosphorus in the system, especially in summer. The atmospheric input (1% of the total phosphorus inputs) is small. A considerable exchange flux with adjacent coastal waters (about 40% of total phosphorus inputs) reveals that the system is a phosphorus source to the English Channel and adjacent areas. The particle burial is an important process and retains about 60% of the phosphorus entering the system. However, significant removal of phosphorus from the water column was not obviously observed, suggesting that there are other sources of phosphorus in the system or the estimate of internal loss is overestimated. Further study is needed to reaffirm the behaviour of all forms of phosphorus in the system, and assess their yearly variation. An investigation of the forms of particulate phosphorus and phosphorus in surfacial sediments on better temporal and spatial resolution is also needed together with more geological information on the origin and sizes of particles. Contents CONTENTS Page Contents I Abbreviations VI List of Figures VIII List of Tables XI Acknowledgements XIII Chapter 1: General introduction 1.1 Phosphorus sources, sinks and global cycles 1 1.2 Phosphorus speciation in the marine environment 8 1.3 Phosphorus processes in the marine environment 11 1.4 Phosphorus budgets in coastal and shelf seas, and estuaries (LOICZ biogeochemical model) 16 1.5 The study area 18 1.6 Objectives 20 Chapter 2: Overview of analytical methods for the determinations of phosphorus in marine waters and sediments 2.1 Introduction 23 2.2 The determinations of Dissolved Inorganic Phosphorus (DIP) 24 2.3 The determinations of Total Dissolved Phosphorus (TDP) and Dissolved Organic Phosphorus (DOP) 25 2.4 The determinations of phosphorus in the bottom sediments and suspended sediments (PTP) 27 I Contents 2.5 Sequential Phosphorus Extraction Protocols (SPEPs) for different forms of solid phase phosphorus 30 Chapter 3: Study of water column phosphorus in the Southampton Water system: sampling, analysis and results 3.1 Introduction 32 3.2 Sampling and storage procedures 36 3.3 Methods 38 3.3.1 Dissolved inorganic phosphorus 38 3.3.2 Dissolved organic phosphorus and particulate total phosphorus 39 3.3.3 Chlorophyll a 40 3.4 Results 41 3.4.1 Salinity 41 3.4.2 Temperature 42 3.4.3 DIP N 44 3.4.4 DOP 45 3.4.5 DIN 46 3.4.6 Dissolved silicon 49 3.4.7 SPM 50 3.4.8 PTP 52 3.4.9 Chlorophyll a 55 Chapter 4: Study of water column phosphorus in the Southampton Water system: comparison with historical data and discussion n Contents 4.1 Summary of existing knowledge of nutrient behaviour in the Southampton Water system 58 4.2 Nutrient distributions and nutrient-salinity relationships 64 4.3 Transformation of particle-bound phosphorus in the Southampton Water system73 4.3.1 Introduction 73 4.3.2 Sampling and methods 75 4.3.3 Results and discussions 77 4.4 Dissolved inorganic phosphorus pattern in the Southampton Water system — application of the Kd model 82 4.4.1 Introduction 82 4.4.2 Dissolved inorganic phosphorus behaviour in the low salinity water in the Itchen Estuary — application (I) of the Kd model 87 4.4.3 Prediction of the influence of storm event and dredging activities on DIP concentration in the Southampton Water system — application (II) of the Kd model 92 4.4.4 Critique of application of the Kd model in the Southampton Water system 96 4.5 Summary 97 Chapter 5: Study of phosphorus in the sediments of Southampton Water and the Itchen Estuary 5.1 Introduction 99 5.2 Sampling and methods 107 5.2.1 Pore water chemistry investigation 107 ffl Contents 5.2.2 Direct measurement of phosphorus fluxes across the sediment-water interface 109 5.2.3 Inorganic and organic phosphorus distributions in the sediments 110 5.2.4 Forms of inorganic phosphorus in the sediments 112 5.3 Results and discussions 115 5.3.1 Porewater chemistry of phosphate in the sediments in the Itchen Estuary 115 5.3.2 Direct measurement of benthic fluxes of phosphorus by core incubation 118 5.3.3 Phosphorus distributions in the solid phases of sediments 119 5.3.4 Inorganic phosphorus speciations in the sediments 122 5.4 Summary 125 Chapter 6: The Phosphorus budget in the Southampton Water system 6.1 Introduction 127 6.2 Magnitude of phosphorus inputs to the Southampton Water system 130 6.2.1 Introduction 130 6.2.2 Phosphorus sources and inputs estimates 131 6.3 Internal losses of phosphorus 140 6.4 Exchange of phosphorus across seaward boundary 142 6.5 Reservoirs of phosphorus 142 6.6 Water column and sediment recycling rates 144 6.7 Budget summary and discussion 145 6.7.1 Summary of the phosphorus budget in the system 145 6.7.2 Comparison of phosphorus budget in the Southampton Water system with the budget in Chesapeake Bay 149 IV Contents 6.7.3 Application of LOICZ model in the Southampton Water system and the comparison 150 Chapter 7: Conclusions and further work 7.1 Phosphorus distribution in the Southampton Water system 154 7.1.1 Phosphorus in the water column 154 7.1.2 Phosphorus in the sediments 155 7.2 Application of the Kd model to the Southampton Water system
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