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As Yet There Was No Field Shrub on Earth and No Grass of The ... as yet there was no field shrub on earth and no grass of the field had sprouted, for the Lord God had sent no rain upon the earth and there was no man to till the soil, b u t a stream was welling u p out of the earth and was watering all the surface of the ground... ANALYSIS OF TRACE ELEMENTS IN IRISH FRESHWATERS BY ICP-MS Fionnuala O’Connor, B.Sc. A thesis submitted to Dublin City University for the award of Master of Science Supervisor: Professor Dermot Diamond School of Chemical Sciences Dublin City University Glasnevin Dublin 9 Ireland In collaboration with: Central Fisheries Board Mobhi Boreen Glasnevin Dublin 9 Ireland SEPTEMBER 2003 AUTHOR’S DECLARATION ! herby certify that this material, which 1 now submit for assessment on the programme of study leading to the award of Master of Science is entirely my own work and has not been taken from the work of others save and to the extent that such work has been cited and acknowledged within the text of my work. Signed: <-v Ay I.D.No.: Date: / c/* L' . 5 ^ ¿ e - 2 0 0 2 TABLE OF CONTENTS 1. INTRODUCTION..............................................................................1 1.1 Ireland’s Freshwater Resource............................................................................... 1 1.2 Water pollution and legislation..............................................................................3 1.3 Methods of analysis................................................................................................. 8 1.4 Development of freshwater quality measurement............................................. 10 1.5 Factors influencing element concentrations............................. 21 1.6 The role of the Fisheries Boards in Inland water management.......................25 1.7 Aims and Objectives.................................................. 27 2. INSTRUMENTATION AND METHODS...................................29 2.1 History o f ICP-MS................................................................................................. 29 2.2 Principles of ICP-MS.............................................................................................30 2.3 Applications of ICP-MS.......................................................................................36 2.4 Problems & Interferences.....................................................................................37 2.5 Materials and Methods.......................................................................................... 43 3. LAKE WATER ANALYSIS.......................................................... 49 3.1 Introduction.............................................................................................................49 3.2 Trace elements in lakes......................................................................................... 50 3.3 Sample collection...................................................................................................51 3.4 Results and Discussion......................................................................................... 55 3.5 Conclusions.............................................................................................................79 4. RIVER WATER ANALYSIS......................................................... 82 4.1 Introduction.............................................................................................................82 4.2 Trace element concentrations in rivers...............................................................83 4.3 Lough Corrib and its catchment area.................................................................. 85 4.4 Geology in the Lough Corrib Catchment...........................................................87 4.5 Sample Collection.................................................................................................91 4.6 Results and Discussion.........................................................................................91 4.7 Conclusions...........................................................................................................106 5. CANAL WATER ANALYSIS..................................................109 5.1 Introduction...........................................................................................................109 5.2 Sampling site locations....................................................................................... 111 5.3 Sample collection................................................................................................ 112 5.4 Sample analysis....................................................................................................113 5.5 Results and Discussion....................................................................................... 114 5.6 Conclusions.......................................................................................................... 127 6. CONCLUSIONS AND RECOMMENDATIONS.................. 129 7. REFERENCES............................................................................ 139 iv ABSTRACT Analysis of Trace Elements in Irish Freshwaters by ICP-MS Fionnuala O’Connor Ireland’s largely unpolluted surface waters are one of the most valuable natural resources of the island. Until the 1970’s there was very little information available on the quality of Irish water bodies. Since then, drinking water legislation has required the monitoring of certain specific parameters and the problem of eutrophication has resulted in extensive investigation of nutrient levels. In more recent years, however, the availability of modern analytical techniques has greatly assisted routine monitoring of waters for a wider range of chemical parameters. Over the period 1998-2001 thousands of samples from Irish rivers, lakes and canals were analysed by the Central Fisheries Board using Inductively Coupled Plasma - Mass Spectroscopy (ICP-MS), a method that allows for rapid and sensitive multi-element measurements. The purpose of the analyses was primarily to increase knowledge of Irish surface water chemistry. It was also hoped that the work would assist in the understanding of biological processes and begin the development of a database of chemical “signatures” for Irish waters. This thesis attempts to summarise and interpret a large quantity of analytical information obtained from about 230 sites chosen from the larger dataset of sampling locations on Irish lakes, rivers and canals. Sixteen elements were routinely analysed, resulting in approximately 100,000 individual measurements during this study. In Chapter 3 eighteen lakes of varying size and location are compared and contrasted. The distinctive characteristics of twenty-eight rivers to the east and west of Lough Corrib are studied in Chapter 4 and differences in the water chemistry of the four main canal systems are investigated in Chapter 5. In each of these specific areas, temporal and spatial variations in the concentrations of major and minor elements were studied. The effects of local geology was also considered and found to play a large part in the chemical composition of surface waters. It is anticipated that the knowledge gained from this preliminary investigation of trace elements in Irish waters will advance more in-depth future studies in this area. LIST OF TABLES Table 1.1: Irish standards for trace metals in waters........................................................... 7 Table 1.2: Criteria for Total Zinc from Directive 78/659/EEC............................................ 8 Table 1.3: Criteria for Dissolved Copper from Directive 78/659/EEC...............................8 Table 1.4: OECD Classification of Lake Waters...................................................................13 Table 1.5: Quality Rating Scale.............................................................................................. 14 Table 1.6: High metal concentrations reported in 1974 by An Foras Forbartha..............19 Table 1.7: Elements reported in EPA Dangerous Substances report 1999-2000............ 21 Table 1.8: Average composition of crustal rocks, in terms of elements........................... 21 Table 2.1: Analyte solution history from introduction to final ionisation .......................33 Table 2.2: Typical operating conditions for normal and cool plasma conditions........... 46 Table 3.1: Size, geology and samples taken from lakes studied ......................................53 Table 3.2: Mean element concentrations for each lake sample location........................... 54 Table 3.3: Summary of Cross-Validation Results................................................................73 Table 4.1: Lough Corrib Facts and Figures........................................................................... 87 Table 4.2: Sample sites in the Lough Corrib catchment......................................................89 Table 4.3: Mean values and %RSD’s for Corrib River sites...............................................90 Table 4.4: Summary of Cross-Validation Results.............................................................. 101 Table 5.1: Summary data for each canal system ................................................................ 115 Table 5.2: Summary of Cross-Validation Results.............................................................. 123 LIST OF FIGURES Figure 1.1: Surface drainage in Ireland.................................................................................3 Figure 1.2: Shoreline algal bloom as a result of nutrient enrichment.................................12
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