Heavy Metals in the Environment: Origin, Interaction and Remediation, Volume 6

Heavy Metals in the Environment

INTERFACE SCIENCE AND TECHNOLOGY

Series Editor: ARTHUR HUBBARD

In this series:

Vol. 1: Clay Surfaces: Fundamentals and Applications

Edited by F. Wypych and K.G. Satyanarayana

Vol. 2: Electrokinetics in Microfluidics

By Dongqing Li

Vol. 3: Radiotracer Studies of Interfaces

Edited by G. Horányi

Vol. 4: Emulsions: Structure Stability and Interactions

Edited by D.N. Petsev

Vol. 5: Inhaled Particles

By Chiu-sen Wang

Vol. 6: Heavy Metals in the Environment

Edited by H.B. Bradl

INTERFACE SCIENCE AND TECHNOLOGY - VOLUME 6

Heavy Metals in the Environment

Edited by

H.B. Bradl

University of Applied Sciences Trier

Neubrucke, Germany

2005

ELSEVIER

ACADEMIC

PRESS

Amsterdam - Boston - Heidelberg - London - New York - Oxford - Paris

San Diego - San Francisco - Singapore - Sydney - Tokyo

ELSEVIERB.V.

Radarweg 29

P.O. Box 211, 1000 AE Amsterdam

The Netherlands

ELSEVIER Inc.

525 B Street, Suite 1900

San Diego, CA 92101-4495

USA

ELSEVIER Ltd

The Boulevard, Langford Lane

Kidlington, Oxford OX5 1GB

UK

ELSEVIER Ltd

84 Theobalds Road

London WC1X 8RR

UK

© 2005 Elsevier Ltd. All rights reserved.

This work is protected under copyright by Elsevier Ltd., and the following terms and conditions apply to its use:

Photocopying

Single photocopies of single chapters may be made for personal use as allowed by national copyright laws. Permission of the

Publisher and payment of a fee is required for all other photocopying, including multiple or systematic copying, copying for

advertising or promotional purposes, resale, and all forms of document delivery. Special rates are available for educational

institutions that wish to make photocopies for non-profit educational classroom use.

Permissions may be sought directly from Elsevier's Rights Department in Oxford, UK: phone (+44) 1865 843830, fax (+44)

1865 853333, e-mail: [email protected]. Requests may also be completed on-line via the Elsevier homepage

(http://www.elsevier.com/locate/permissions).

In the USA, users may clear permissions and make payments through the Copyright Clearance Center, Inc., 222 Rosewood

Drive, Danvers, MA 01923, USA; phone: (+1) (978) 7508400, fax: (+1) (978) 7504744, and in the UK through the Copyright

Licensing Agency Rapid Clearance Service (CLARCS), 90 Tottenham Court Road, London W1P 0LP, UK; phone: (+44)

20 7631 5555; fax: (+44) 20 7631 5500. Other countries may have a local reprographic rights agency for payments.

Derivative Works

Tables of contents may be reproduced for internal circulation, but permission of the Publisher is required for external resale or

distribution of such material. Permission of the Publisher is required for all other derivative works, including compilations and

translations.

Electronic Storage or Usage

Permission of the Publisher is required to store or use electronically any material contained

or part of a chapter.

in this work, including any chapter

Except as outlined above, no part of this work may be reproduced, stored in a retrieval system or transmitted in any form or by

any means, electronic, mechanical, photocopying, recording or otherwise, without prior written permission of the Publisher.

Address permissions requests to: Elsevier's Rights Department, at the fax and e-mail addresses noted above.

Notice

No responsibility is assumed by the Publisher for any injury and/or damage to persons or property as a matter of products liability,

negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material

herein. Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages

should be made.

First edition 2005

Library of Congress Cataloging in Publication Data

A catalog record is available from the Library of Congress.

British Library Cataloguing in Publication Data

A catalogue record is available from the British Library.

ISBN: 0-12-088381-3

ISSN: 1573-4285 (Series)

@ The paper used in this publication meets the requirements of ANSI/NISO Z39.48-1992 (Permanence of Paper).

Printed in The Netherlands.

Preface

Heavy metals in the environment pose a variety of very interesting scientific

questions. The fields of work involved cover a wide range of disciplines. Thus,

heavy metals are a good example for an interdisciplinary field of work ranging

from geology, mineralogy, and geochemistry, if their origin and natural

occurrence is concerned, to analytical, physical, and colloid chemistry, when it

comes to detection of heavy metals and their interactions with environmental

media such as water, groundwater, soil, rock, and air, and biology, ecology,

ecotoxicology, and medicine, if one is concerned with their impact on global

ecosystems and their effects on human and animal health. Finally, the

remediation of heavy metals requires cooperation of several engineering

disciplines such as environmental, chemical, and civil engineering.

Of course it is not possible to cover this wide range in sufficient depth in

one single book alone. Nevertheless this book aims at giving an overview on the

most important topics for the reader interested in the subject. Although this book

is not meant to be an introductory textbook, pain was taken to keep the text to a

level, which allows graduate students to read and understand it. The first chapter

gives some ideas on both natural and anthropogenic sources of heavy metals in

the environment. The second chapter introduces analytical methods for their

detection, the most important biogeochemical processes regulating their

mobility, and their ecotoxicological effects on plants, animals, and humans. In

this chapter, detailed information over the behaviour of some selected heavy

metals is given as well. The third chapter gives an overview over different

strategies for the remediation of heavy metals. In this context, innovative new

strategies for the remediation of soil and groundwater contaminated with heavy

metals such as permeable reactive barriers are discussed along with approved

technologies such as encapsulation, soil washing, solidification, and

phytoremediation.

There have been many sources of support during the work on this book.

First I would like to thank my contributors, who took pain, work, and patience in

V

Preface

preparing their subchapters. Prof. Dr. Doris Stiiben, University of Karlsruhe,

Germany, gives an overview over Platinum Group Metals. Prof. Dr. Chris Kim,

Chapman University, Orange, CA, USA, prepared the subchapter on sorption of

heavy metals. Dr. Utz Kramar, University of Karlsruhe, Germany, introduces

analytical methods for their detection, and last but not least, Dr. Anthimos

Xenidis, National Technical University of Athens, Greece, wrote a subchapter

on stabilization and solidification. Their time and effort is greatly appreciated.

Parts of this book were prepared during a sabbatical leave at the Environmental

Research Centre, University of Karlsruhe, Germany. I would like to express my

thanks to all the colleagues there for never-ending support and a good time.

Finally, I would like to thank my colleagues and students at the Umwelt￾Campus, Birkenfeld, for their help and patience during the work on this book.

Heike B. Bradl

Birkenfeld

November, 2004

vi

Table of Contents

Preface V

CHAPTER 1: SOURCES AND ORIGINS OF HEAVY METALS

1. Introduction 1

2. Heavy Metals in Rocks and Soils 1

2.1. Magmatic Rocks 1

2.2. Sedimentary Rocks 4

2.3. Metamorphic Rocks 5

2.4. Soil Formation 6

2.4.1. Organic Material 7

2.4.2. Clay Minerals 8

2.4.3. Oxides and Hydroxides 11

3. Heavy Metals in Water and Groundwater 12

3.1. Surface Waters 12

3.2. Groundwater 12

4. Heavy Metals in the Atmosphere 15

5. Anthropogenic Sources of Heavy Metals 17

5.1. Agricultural Activities 18

5.1.1. Phosphatic Fertilizers 18

5.1.2. Pesticides 19

5.1.3. Sewage Effluents 19

5.1.4.Biosolids 21

5.2. Industrial Activities 22

5.2.1. Mining 22

5.2.2. Coal and Petroleum Combustion 23

5.2.3. Indoor and Urban Environments 23

5.2.4. Solid Waste Disposal 25

References 25

vii

viii Table of Contents

CHAPTER 2: INTERACTION OF HEAVY METALS

1. Analytical Procedures for the Detection of Heavy Metals (U. Kramar) 28

1.1. Sample Preparation 28

1.1.1. Soils and Sediments 29

1.1.2. Vegetation 29

1.1.3. Waters 29

1.2. Digestion Methods 30

1.2.1. Soils, Sediments, and Building Materials 30

1.2.2. Vegetation 32

1.3. Analytical Methods 32

1.3.1. Optical Spectroscopic Methods 32

1.3.2. Microanalytical Methods 45

2. Biogeochemical Processes regulating Heavy Metal Mobility 46

2.1. Sorption (C.Kim) 47

2.1.1. Introduction 47

2.1.2. Adsorption Mechanisms 48

2.1.3. Utility of X-Ray Absorption Spectroscopy in Determining Sorption

Mechanisms 56

2.1.4. Model Approaches for Heavy Metal Sorption (H.B. Bradl) 59

2.1.5. Geochemical Parameters influencing Adsorption 73

2.2. Redox Reactions 76

2.3. Weathering 77

2.4. Driving Factors 77

2.4.1. pH and Redox Potential 77

2.4.2. Complexing Agents 78

2.4.3. Type and Chemical Speciation of Metal 83

3. Ecotoxicological Effects of Heavy Metals 85

3.1. Pathways of Heavy Metal Access 85

3.1.1. Respiration 85

3.1.2. Water 86

3.1.3. Food 86

3.2. Bioavailability and Bioaccumulation 87

3.2.1. Definition 87

3.2.2. Bioavailability in the Soil-Plant System 90

3.2.3. Bioavailability in the Aquatic System 91

4. Individual Behaviour of Selected Heavy Metals 93

4.1. Arsenic 93

4.1.1. Chemical and Physical Character of Arsenic 93

4.1.2. Sources and Applications of Arsenic 94

4.1.3. Ecotoxicological Effects of Arsenic 96

Table of Contents ix

4.2. Cadmium 98

4.2.1. Chemical and Physical Character of Cadmium 98

4.2.2. Sources and Applications of Cadmium 101

4.2.3. Ecotoxicological Effects of Cadmium 103

4.3 Chromium 104

4.3.1. Chemical and Physical Character of Chromium 104

4.3.2. Sources and Applications of Chromium 106

4.3.3. Ecotoxicological Effects of Chromium 107

4.4. Copper 108

4.4.1. Chemical and Physical Character of Copper 108

4.4.2. Sources and Applications of Copper 110

4.4.3 Ecotoxicological Effects of Copper Il l

4.5. Lead Il l

4.5.1. Chemical and Physical Character of Lead Il l

4.5.2. Sources and Applications of Lead 114

4.5.3. Ecotoxicological Effects of Lead 115

4.6. Manganese 115

4.6.1. Chemical and Physical Character of Manganese 115

4.6.2. Sources and Applications of Manganese 117

4.6.3. Ecotoxicological Effects of Manganese 118

4.7. Mercury 119

4.7.1. Chemical and Physical Character of Mercury 119

4.7.2. Sources and Applications of Mercury 121

4.7.3. Ecotoxicological Effects of Mercury 122

4.8. Molybdenum 124

4.8.1. Chemical and Physical Character of Molybdenum 124

4.8.2. Sources and Applications of Molybdenum 125

4.8.3. Ecotoxicological Effects of Molybdenum 126

4.9. Nickel 126

4.9.1. Chemical and Physical Character of Nickel 126

4.9.2. Sources and Applications of Nickel 127

4.9.3. Ecotoxicological Effects of Nickel 128

4.10. Platinum Group Elements PGE (D. Stiiben) 128

4.10.1. Introduction 128

4.10.2. Chemical and Physical Character of PGE 129

4.10.3. Sources and Applications of PGE 131

4.10.4. PGE Emission by Car Catalytic Converters 134

4.10.5. PGE in Environmental Matrices 135

4.10.6. Transformation of PGE and Bioaccumulation

in the Environment 137

4.11. Zinc (RB.Bradl) 139

4.11.1. Chemical and Physical Character of Zinc 139

4.11.2. Sources and Applications of Zinc 141

4.11.3. Ecotoxicological Effects of Zinc 142

X Table of Contents

4.12. Other Heavy Metals 143

4.12.1. Cobalt 143

4.12.2. Silver 144

4.12.3. Thallium 146

4.12.4. Tin 147

References 148

CHAPTER 3: REMEDIATION TECHNIQUES

1. Introduction 165

2. Physical Remediation Techniques 165

2.1. Soil Washing 165

2.1.1. Particle-Size Dependent Distribution of Pollutants 167

2.1.2. Wet Liberation 168

2.1.3. Classification of Fine Particles 169

2.2. Encapsulation 170

2.2.1. Slurry Walls 170

2.2.2. Thin Walls 171

2.2.3. Sheet Pile Walls 172

2.2.4. Bored-pile Walls and Jet Grouting 172

2.2.5. Injection Walls 172

2.2.6. Artificial Ground Freezing and Frozen Walls 173

2.3. Vitrification 174

2.4. Electro kinetic Techniques 176

2.4.1. Principle Electrokinetic Transport Processes 177

2.4.2. Electrode Reactions 178

2.4.3. Applications 179

2.5. Permeable Reactive Barrier Systems 179

2.5.1. Permeable Walls 180

2.5.2. Funnel and Gate Systems 182

2.5.3. Reactor Technologies for Removal of Heavy Metals 183

2.5.4. Engineering Methods for Execution of

Permeable Reactive Barriers 186

3. Chemical Remediation Techniques 191

3.1. Precipitation 192

3.2. Ion Exchange 193

3.3.FloccuIation 194

3.3.1. Colloidal Systems 194

3.3.2. Flocculation Chemicals 197

3.4. Membrane Filter Processes 198

3.5. Solidification/Stabilization (A. Xenidis) 200

Table of Contents xi

3.5.1. Introduction 200

3.5.2. Solidification/Stabilisation Mechanisms 202

3.5.3. Evaluation of Solidification/Stabilisation Processes 209

3.5.4. Technology Description 216

3.5.5. Field Applications 230

4. Phytoremediation of Heavy Metals (H.B. Bradl) 235

4.1. Introduction 236

4.2. Basic Physiological Processes 236

4.2.1. Processes involving Microorganisms 237

4.2.2. Plant Processes 239

4.3. Mechanisms of Phytoremediation 241

4.3.1. Phytoextraction 241

4.3.2.Phytostabilization 245

4.3.3. Phytovolatilization 247

4.3.4. Phytofiltration 248

4.4. Advantages and Limitations of Phytoremediation 249

References 251

Index 263

This Page Intentionally Left Blank

Heavy Metals in the Environment

H.B. Bradl (editor)

© 2005 Elsevier Ltd. All rights reserved.

Chapter 1

Sources and Origins of Heavy Metals

H.B.Bradl3

"Department of Environmental Engineering, University of Applied Sci￾ences Trier, Umwelt-Campus Birkenfeld, P.O. Box 301380,55761 Birk￾enfeld, Germany

1. INTRODUCTION

There are different sources for heavy metals in the environment. These

sources can be both of natural or anthropogenic origin. This chapter gives a

general introduction into the different heavy metal sources such as mag￾matic, sedimentary, and metamorphic rocks, weathering and soil formation,

the rock cycle, the origin of heavy metals in surface and groundwater as

well as in the atmosphere, and anthropogenic sources stemming from hu￾man activities such as industrial production and agriculture [1,2].

2. HEAVY METALS IN ROCKS AND SOILS

2.1. Magmatic Rocks

Rocks and soils are the principal natural sources of heavy metals in

the environment. The primary rocks, which are called magmatic or igneous

rocks, crystallize from magma upon cooling down. Magma is defined as

molten rock material originating from the earth's mantle, which can be

transported to the surface by several geological processes such as volcan￾ism or plate tectonics [3]. Magma contains a large variety of different

chemical elements. Heavy metals are incorporated as trace elements into

the crystal lattice of the primary minerals, which form during the cooling of

the magma. This process is called isomorphic substitution, as the heavy

metals substitute other atoms during the crystallization. The amount of

isomorphic substitution is determined by the ion radius, the ion charge, and

the electronegativity of the main element and of the substituting element.

The trace elements occurring in the most common rock forming minerals

are given in Table 1.

2 H.B. Bradl

Table 1

Trace elements of the most common rock forming minerals

Mineral

Olivine

Hornblende

Augite

Biotite

Apatite

Anorthite

Andesine

Oligoclase

Albite

Garnet

Orthoclase

Muscovite

Titanite

Ilmenite

Magnetite

Turmaline

Zircon

Quartz

Trac

Ni, Co,

Ni, Co,

Ni, Co,

Rb,Ba,

e Eleme

Mn, Li,

Mn,Se,

Mn, Se,

. Ni. Co.

nt Re

Zn, Cu, Mo

Li, V, Zn, Cu, Ga

Li, V, Zn, Pb, Cu, Ga

Mn.Se.Li.V. Zn. Cu.

Rare earth elements, Pb, Sr

Sr, Cu,

Sr, Cu,

Cu, Ga

Cu, Ga

Mn, Cr

Rb,Ga

F,Rb,l

Ga, Mn

Ga, Mn

, Ga

, Sr, Cu, Ga

Ba, Sr, Cu, Ga, V

Rare earth elements, V, Sn

Co, Ni,

Zn, Co

Cr,V

, Ni, Cr,

Li, F, Ga

Hf,U

V

sistance to Weathering

weathers easily

Ga

intermediate stability

resistant

Modified after Ref. 4.

Magmatic rocks can be classified by their chemical composition on

the one hand and their crystal size and texture on the other hand. If magma

cools down slowly within the earth's crust, there is enough time for large

crystals to be formed, which can easily be recognized with the naked eye. If

magma is extruded rapidly onto the earth's surface (e.g. by volcanic activ￾ity), crystallization occurs quickly, and consequently, those magmatic rocks

are characterized by very fine crystals that can not be seen with the naked

eye. Magmatic rocks showing large crystals are called intrusive rocks or

intrusiva, while those with fine texture and small crystals are called effu￾sive rocks or effusiva. The principal effusive and intrusive magmatic rocks

and their mineral and chemical components are identified in Fig. 1. For

each individual intrusive rock, there is an equivalent effusive counterpart,

which is identical in chemical composition, yet shows different crystal size

and texture (e.g. granite and rhyolithe). During the crystallization phase of

a magma body, a process called chemical differentiation takes place. Min￾eral crystallization is a function of both temperature and pressure condi￾tions, which change constantly during cooling. Different minerals precipi￾tate according to their stability fields at limited ranges of temperature, pres￾sure, and chemical composition conditions.