Table of Contents

Figures xi

Tables xiii

Acknowledgements xx

0 EXECUTIVE SUMMARY AND CONCLUSIONS 1

0.1 Introduction 1

0.2 Metal Fluxes from Society to the Environment and between Environmental Media 3

0.2.1 The European Copper Cycle in the Mid-1990s 4

0.2.2 Metal Fluxes from Mining Waste - Falun Copper Mine 5

0.2.3 Urban Metal Flows - the Case of Stockholm 6

0.2.4 Critical Steps in Metal Fluxes from Cities to the

Environment 7

0.3 Speciation, Bioavailability and Effects of Trace Metals in the Environment 8

0.3.1 In the Water Column - BLM as a Tool for Prediction of

Toxicity 9

0.3.2 In Aquatic Sediments - AVS as a Tool for Prediction 10

0.3.3 In Soils - Laboratory versus Field Tests 11

0.4 General Conclusions 12

1 PURPOSE OF THIS REVIEW 15

1.1 Background and justification 15

1.2 The need and how to meet it 17

1.3 Target groups for the updated report 18

1.4 Implementation of the work 18

2 GLOBAL EXTRACTION, PRODUCTION AND CONSUMPTION 21

2.2 Nickel 22

2.3 Zinc 23

3 METAL CYCLES IN DEFINED GEOGRAPHICAL

AREAS: EUROPE, THE NETHERLANDS AND STOCKHOLM 25

3.1 Example 1: The European Copper Cycle 25

3.1.1 Introduction 26

3.1.2 Selection of boundaries of the system to be studied 28

3.1.3 Some definitions and characterisation of the technical components 29

3.1.3.1. Production (mining, milling, concentration, smelting, refining) 29

3.1.3.2. Fabrication, manufacturing and use 30

3.1.4 Waste management subsystem 33

3.1.5 Summary of stocks and flows of copper in European society, in 1994 37

3.2 Example 2: Dynamic Modelling of Metal Flows in the Netherlands; Cu and Zn 40

3.2.1 Models used 40

3.2.2 Summary of main results 42

3.2.3 Critical review of the Dutch calculations 46

3.3 Example 3: Urban Metal Flows - Stockholm;

3.3.1 New aspects of studies on urban metal flows 50

3.3.2 Stock of metals in Stockholm 51

3.3.3 Outflows of metals from existing stocks to the solid waste compartment 53

3.3.4 Outflows via other routes, e.g. diffuse emissions from goods 53

3.3.5 Metal fluxes to and from sewage treatment plants in Stockholm 55

3.3.6 Constraints in metal cycling to arable land with sewage sludge 59

3.3.7 Metal fluxes with groundwater in Stockholm 59

3.3.8 Metal accumulation and metal pools in urban soils in Stockholm 61

3.3.9 Metal fluxes to sediments of lakes and coastal areas in Stockholm 65

4 CRITICAL STEPS IN METAL FLUXES FROM SOCIETY TO THE ENVIRONMENT -SOME CASE STUDIES 71

4.1 Case Study 1: Corrosion and runoff of metals from roofing materials made of copper, galvanized steel or stainless steel (Cu, Zn, Cr and Ni) 72

4.1.1 Definitions, background and experimental approaches 73

4.1.2 Some principal results 75

4.1.3 Releases and fluxes of copper 76

4.1.4 Releases and flows of zinc 80

4.1.5 Releases and flows of chromium and nickel 84

4.2 Case Study 2: Relative importance of the traffic sector for metal fluxes from the urban environment to aquatic ecosystems 86

4.2.1 Difficulties to quantify the contribution of street traffic to trace metal fluxes 87

4.2.2 Bioavailability to aquatic organisms of traffic-emitted metals 88

4.2.3 Level of contamination with bioavailable trace metals in the waterways of central Stockholm, compared to other waters 92

4.2.4 Possible over-interpretation of bioaccumulation data -

a critical review 94

4.2.5 Which conclusions from the study are justified ? 96

4.3 Case Study 3: Metal fluxes from households to STPs, sludge and agricultural soils 98

4.3.1 Origin of trace metals in STPs and in sewage sludge 99

4.3.2 Assessment of the causes of copper release from tap water pipes 101

4.3.3 Use of sewage sludge as a fertiliser in agriculture 105

4.3.4 Permitted trace metal loads to agricultural soils 106

4.3.5 Sustainable trace metal loadings to agricultural soils 108

4.3.5.1 Trace metal deficiency symptoms and how to correct them 109

4.3.5.2 Application of sewage sludge to soils - risk of metal toxicity to soil ecosystems 110

4.3.5.3 Long-term field studies - effects of sewage sludge application to soils 110

4.3.5.4 Conclusions regarding sustainable trace metal loadings to agricultural soils 117

4.4 Case Study 4: Metal fluxes from mine waste to rivers -Falun Copper Mine 120

4.4.1 Background and definition of the case to be discussed 121

4.4.2 Brief description of the level of pollution with metals in water and sediments of receiving rivers and lakes 124

4.4.3 Biological responses to the enhanced metal concentrations 127

4.4.4 Some conclusions from the Falun studies 130

4.5 Summing up: Fluxes of Cr, Cu, Ni and Zn from

Society to the Environment 131

5 SPECIATION, MOBILITY AND

BIOAVAILABILITY OF METALS IN THE ENVIRONMENT 139

5. 1 Introduction 139

5.1.1 General considerations 139

5.1.2 Definitions 141

5.1.3 Fundamental properties of the selected metals 142

Chromium 144

Copper 145

Nickel 146

Zinc 147

5.2 In surface waters 149

5.2.1 Metal speciation in the aqueous (dissolved) phase 151

5.2.2 Adsorption versus bioavailability 156

5.2.3 Competition between aqueous and solid phases 158

5.3 In groundwaters 160

5.4 In aquatic sediments 163

5.4.1 Introduction 163

5.4.2 Today's knowledge on metal speciation in sediment/water systems 164

5.4.2.1 General overview 165

5.4.2.2 Total concentration approach 166

5.4.2.3 Partly theoretical approaches to metal speciation 167

5.4.2.4 More empirical approaches to metal speciation (chemical extraction) 168

5.4.3 The Acid-Volatile Sulphides (AVS) concept 170

5.4.3.1 Development and application 172

5.4.3.2 Refinement of the "AVS hypothesis" 181

5.4.3.3 Operational drawbacks of SEM/AVS-based approaches. 187

5.4.3.4 New empirical evidence 192

5.4.4 Chemical extraction and mobility 197

5.4.5 New spectroscopic approaches 201

5.4.6 Bioturbation, resuspension and bioirrigation 206

5.4.7 Metal-ligand interactions 214

5.4.7.1 Free ion activity model (FIAM) 215

5.4.7.2 Surface complexation 218

5.4.8 Speciation-bioavailability interactions in sediment-ingesting biota 222

5.4.8.1 Absorption efficiency (AE) 223

5.4.8.2 Gut juice extraction 227

5.4.9 Redox effects 230

5.5.1 Introduction 232

5.5.2 Metal adsorption and partitioning 233

5.5.3 Chemical extraction and plant uptake 237

5.5.4 Surface reactions 246

5.5.5 Redox effects 250

5.5.6 Aging and weathering 254

5.5.7 Sludge application and contaminated soils 258

5.6 In biota 265

5.7 A proposal for "natural" or "preindustrial" regional background levels of metals in the sediment in waters surrounding Stockholm 271

6 BIOTIC LIGAND MODELS 275

6.1 Need for improved models to assess bioavailable fraction of metals 276

6.2 Development of Biotic Ligand Models 279

6.3 Application of BLMs 284

7 TOXIC AND OTHER ADVERSE BIOLOGICAL EFFECTS OF TRACE METALS 289

7.1 Toxicity to aquatic organisms in the water column 290

7.1.1 Copper 292

7.1.1.1 Sensitivity to copper of different aquatic organisms 292

7.1.1.2 Toxicity of copper estimated by means of BLMs 297

7.1.2 Nickel 302

7.1.3 Zinc 303

7.1.3.1 Sensitivity to zinc of different aquatic organisms 303

7.1.3.2 Toxicity of zinc estimated by means of BLMs 304

7.2 Toxicity to sediment-dwelling organisms 307

7.2.1 Some general considerations 309

7.2.2 Field validation of the SEM/AVS model for zinc 311

7.2.3 Metal release and toxicity of sediments from the Stockholm area 314

7.2.3.1 Background and experimental design 314

7.2.3.2 Experimental results: transfer of metals from sediments to water and organisms 316

7.2.3.3 Experimental results: toxicity to amphipods 317

7.2.3.4 Interpretation of results 318

7.2.3.5 Some remarks on experimental design in sediment research 320

7.3 Toxicity to soil-dwelling organisms and to higher plants 321

7.3.1 Some general considerations 323

7.3.2 Summary of toxicity thresholds for soil organisms and plants 326

7.3.3 Toxicity of trace metals in contaminated urban soils 330

7.3.4 Systematic assessment of zinc toxicity in laboratory spiked soils and in gradually contaminated field soils 331

7.4 Essentiality, regulation and deficiency 333

7.4.1 Some useful definitions 334

7.4.2 Examples of copper essentiality and copper tolerance 336

7.4.3 Examples of zinc essentiality and zinc tolerance 338

REFERENCES 341

Abbreviations 379

Index 385

0 0

Post a comment