Dioxin and Furan Extraction and Trace Metal Leaching From Selected Building Materials For Housing

DIOXIN AND FURAN EXTRACTION, AND TRACE METAL LEACHING
FROM SELECTED BUILDING MATERIALS FOR HOUSING

A thesis submitted in fulfilment of the requirements of the Doctor of Philosophy, at the
University of Dundee, 2007

Malcolm Alexander Sutherland

2
DECLARATION

The author hereby declares that this thesis has been entirely composed by himself and that
none of its contents has either been submitted for any other university degree, or has been
published elsewhere.

Malcolm Alexander Sutherland

3
CERTIFICATE

This is to certify that Malcolm Alexander Sutherland has conducted his work under our
supervision, and that he has fulfilled the requirements of Ordinance 14 of the University of
Dundee, so that he is qualified to submit the following thesis in application for the degree of
Doctor of Philosophy.

T. D. Dyer
Lecturer
Concrete Technology Unit
The University of Dundee

J. E. Halliday
Post-doctoral Researcher

R. K. Dhir
Director

4
ACKNOWLEDGEMENTS

I presume that there are few other PhD projects, which have required the involvement of more
people than this one, or which required the student to travel to every region of the UK (!)

First and foremost, I wish to thank Dr J. Halliday for working closely with me on this project,
especially during the many months in 2004 which were spent developing successful dioxin
and furan extraction and analysis methods. I am particularly grateful to Dr T. Dyer for
devoting his time and effort to reading and commenting on my thesis.

I am greatly indebted to Richard and Frank Morrison (managers of RUM Consultancy), who
allowed access to their GC-MS/MS facilities, and who worked closely and patiently with Dr
J. Halliday and I over many months. I also thank Prof. A. Mehlert and Dr L. Morris for their
patience and advice when I initially tried (unsuccessfully) to develop a dioxin and furan
analysis method at the university.

I extend my thanks to Dr J. Brindle and Dr. L. Csetenyi for their advice and assistance with
operating the voltammetry machine. I also thank the department technicians for their
involvement alongside my laboratory work.

Conducting this PhD project would have been impossible were it not for the assistance and
co-operation I received from so many people I contacted for my UK-wide survey of building
materials and soil samples. There is simply not enough room on this page to list the names of
all the tradesmen, construction site managers, housing association managers and engineers
who allowed me to access all the sites where I collected my samples.

I am very grateful to Euan Ferguson who lent me his laptop for a generous five months during
the difficult weeks when I was revising for my PhD viva, and later when I was making all the
corrections to my thesis mostly at Dundee or on night shift at work! There is no way I
could have submitted my final bound theses by May 2008 without his laptop.

Finally, I am grateful to Professor R. K. Dhir, for offering me the opportunity to pursue a
PhD, and for his guidance throughout the project.

5
ABSTRACT

Dioxins and furans are two families of organic compounds, 17 of which are considered to be
highly toxic. They are products of incomplete combustion (PIC), and may therefore be
enriched in ashes (namely from MSW incinerators). The use of secondary materials in
building materials (including ashes such as PFA) is increasing in the UK, and public concern
was raised in 2001 when incinerator ash was used in concrete. In spite of this, there is very
limited information on the concentration of dioxins and furans in building materials. In
addition, there is also very limited information in the literature on the leaching of cadmium,
copper, lead or zinc from standard building materials. Furthermore, the standard monolith
leaching test (which lasts 64 days) is impractical for general use in industry.

Samples of non-organic, no-metallic construction materials were therefore collected from new
housing construction sites and existing housing throughout the UK. In addition, samples of
demolition materials, as well as concrete containing secondary and waste materials, were also
investigated. Selected samples were subjected to (1) processing and analysis for dioxins and
furans using Soxtherm extraction and GC-MS/MS; (2) leaching of cadmium, copper, lead and
zinc using the NEN7345 method for monolithic samples, and (3) accelerated leaching of these
elements by altering the leaching time, and the leachant temperature and pH. For the leaching
tests, analyses of extracts were conducted using voltammetry and atomic absorption
spectroscopy (AAS).

169 building material samples, 13 demolition waste samples, 8 PFA samples and 22 soil
samples were successfully processed and analysed for dioxins and furans. No dioxins and
furans were detected in any of the samples, possibly with the exception of some minor (albeit
questionable) furan peaks in two soil sample extract chromatographs. Overall, the
concentration of these compounds in concrete, clay bricks, calcium silicate, demolition waste
and aircrete was determined to be below 47.5ng ITEQ / kg.

A selection of clay brick, concrete, calcium silicate and aircrete samples collected from new
housing construction sites were subjected to leaching using the NEN7345 standard, and
extracts were analysed using voltammetry. Cadmium was undetected, and lead was rarely
detected in the extracts. Copper and zinc were detected in all extracts, although the
concentrations in tap-water extracts were lower in comparison with those in tap-water blank
extracts. In general, it was determined that the leaching of cadmium, copper, lead and zinc
from these samples were insignificant.

A range of concrete samples (some containing GGBS, SSA, PFA or silica fume) plus some
clay brick samples were subjected to accelerated leaching tests, all of which lasted 7 days.
These samples were leached using phosphate buffer (set to pH6) and dilute nitric acid (set to
pH4). Samples were treated at room temperature, 60C, or at 100C. Cadmium and lead
were generally undetected in the extracts produced. Copper and zinc were usually detected
using both voltammetry and AAS, although the quantities leached were minor (usually less
than 10mg.m
-2
over 7 days). Furthermore, the rate of leaching did not appear to be affected
by pH control or by temperature increase.

In conclusion, it was determined that the concentration of dioxins and furans in building non-
metallic, inorganic building materials for housing in the UK are generally negligible, and that
the leaching of cadmium, copper, lead and zinc from these materials (including those
containing certain secondary or waste materials) is also insignificant. Further investigation is
needed, in order to clarify the relationship between the leaching rate of trace metals from
building materials with leachant temperature and pH alteration, before a standard shortened
leaching test can be developed.
0
CONTENTS

DECLARATION
CERTIFICATE
ACKNOWLEDGEMENTS
ABSTRACT
TABLE OF CONTENTS
LIST OF TABLES
LIST OF FIGURES
LIST OF SYMBOLS AND ACRONYMS

1 INTRODUCTION
1.1 Background
1.1.1 Secondary and waste materials for construction products
1.1.2 Dioxins and furans
1.1.3 Leaching of Cadmium, Copper, Lead and Zinc
1.2 Aims and objectives of the Project
1.3 Scope of the project
1.4 Layout of thesis

2 LITERATURE REVIEW
2.1 Introduction and objectives
2.2 Materials and products used for modern British housing
2.2.1 Materials used in concrete and mortar
2.2.1.1 Overview of materials
2.2.1.2 Production of concrete
2.2.1.3 Production of mortar
2.2.1.4 Portland cement
2.2.1.5 Natural aggregate
2.2.1.6 Lime
2.2.1.7 Water
2.2.1.8 Admixtures and synthetic additives
2.2.1.9 Secondary materials used in concrete
2.2.1.10 Waste materials considered for concrete
2.2.2 Clay brick production
2.2.3 Calcium silicate bricks
1
2.2.4 Plasterboard and flue gas desulphurisation (FGD) gypsum
2.2.5 External rendering
2.3 Dioxins (PCDDs) and furans (PCDFs)
2.3.1 Chemical and physical data
2.3.2 Sources of dioxins and furans to the environment
2.3.3 Formation and destruction
2.3.4 The mechanisms of PCDD/F formation
2.3.5 Control of dioxin and furan emissions
2.3.6 Health effects of exposure to dioxins and furans
2.3.6.1 Background
2.3.6.2 Toxicity of PCDD/F congeners
2.3.7 Levels of environmental and anthropogenic materials
2.3.7.1 Introduction
2.3.7.2 Regulations and recommended concentrations of PCDD/Fs in solids
2.3.7.3 Reported concentrations of PCDD/Fs in the environment (soil,
sediment) 34
2.3.7.4 Reported concentrations of PCDD/Fs in construction materials/
/products 34
2.3.7.5 Reported concentrations of PCDD/Fs in secondary and waste
materials
2.4 Cadmium, Copper, Lead and Zinc (Cd, Cu, Pb, Zn)
2.4.1 Introduction
2.4.2 The chemical properties of Cd, Cu, Pb and Zn
2.4.3 Applications and use of Cd, Cu, Pb and Zn
2.4.4 Health/environmental effects of exposure to Cd, Cu, Pb and Zn
2.4.4.1 Cadmium intoxication
2.4.4.2 Copper intoxication
2.4.4.3 Lead intoxication
2.4.4.4 Zinc intoxication
2.4.5 Occurrence of Cd, Cu, Pb and Zn in environment and construction
materials
2.4.6 Concentrations of Cd, Cu, Pb and Zn in construction materials
2.4.6.1 Summary of literature search
2.4.6.2 Legislation and regulation
2.4.6.3 Levels of Cd, Cu, Pb and Zn in materials associated with cement kilns
2.4.6.4 Levels in clay bricks
2.4.6.5 Levels of concrete
2
2.4.7 Leaching studies: method design and quantities obtained
2.4.7.1 Leaching of monolithic construction materials: basic principles
2.4.7.2 Quantities of Cd, Cu, Pb with Zn leached from construction materials
2.5 Conclusions

3 MATERIALS AND METHODS 63 96
3.1 Introduction 63
3.2 The UK survey: collection of samples 64
3.2.1 Sampling strategy 64
3.2.2 New housing construction sites 65
3.2.3 Existing housing 65
3.2.4 Demolition waste 65
3.2.5 Collection and storage of samples 65
3.3 Extraction and analysis of dioxins and furans 66
3.3.1 Introduction 66
3.3.2 Health and safety 67
3.3.3 Sample extraction 67
3.3.4 Clean-up filtration 72
3.3.4.1 Introduction 72
3.3.4.2 EPA method 1613 cleanup procedure 73
3.3.4.2 Altered cleanup procedure 73
3.3.5 Evaporation of extracts to 20l 75
3.3.6 GC-MS/MS 77
3.3.6.1 Introduction to GCMS 77
3.3.6.2 Suitable GCMS techniques for dioxin and furan analysis 78
3.4 Laboratory methods used for trace metal analysis 81
3.4.1 Total trace metal analysis in samples using XRF 81
3.4.1.1 Introduction to XRF 81
3.4.1.2 Preparation (of XRF samples) 82
3.4.2 Analysis of metals at trace levels using voltammetry 83
3.4.3 Atomic Absorption Spectrometry (AAS) 85
3.5 Leaching of Cadmium, Copper, Lead and Zinc from monolithic
samples 86
3.5.1 Preparation and testing of monolithic samples using the NEN7345
method 87
3.5.2 Leaching of UK survey samples under the NEN7345 test 88
3.5.3 Samples A to J and the CB and CN samples 89
3
3.5.4 Leaching of Samples A to J under NEN7345 test 89
3.5.5 Accelerated leaching using heating of pH4-acidified distilled water 93
3.5.6 Tests on CB and CN samples 93
3.5.7 Tests on department samples (samples A to J) using pH4-
-acidified water 94
3.5.8 Leaching of department samples using pH6 phosphate buffer 94

4 GC-MS.MS: CONFIGURATION AND CALIBRATION 97 117
4.1 GC temperature programme 97
4.2 Obtaining the Dioxin and Furan signals 98
4.3 Calibration 102
4.3.1 Calibration solutions 102
4.3.2 Calibration results: discussion 103
4.3.3 Correlation between
12
C-congener peak areas and theoretical
concentrations 104
4.4 GC-MS/MS: limit of detection and peak resolution 110
4.4.1 Visual determination of peaks 110
4.4.2 Solutions used for determining the limit of detection 111
4.4.3 Limits of detection: chromatographic data 112
4.4.4 Determining the limit of detection 112
4.5 PAR extracts and blanks 114
4.6 The internal standard 115

5 DIOXINS AND FURANS IN UK SURVEY SAMPLES 118 142
5.1 Introduction 118
5.2 Analysis of GC-MS/MS data 118
5.2.1 Calculating the concentration in solid samples 118
5.2.2 Results for dioxins and furans in samples 118
5.2.2.1 Results for samples analysed in December 2004 (EPA Method 1613) 119
5.2.2.1 Results for samples analysed in February 2005 (Altered Method) 119
5.3 Recovery of Dioxins and Furans 123
5.3.1 Recovery of congeners in samples processed in December 2004 126
5.3.2 Recovery of congeners in samples processed in February 2005 129
5.4 Conclusions and recommendations 131

4
6 LEACHING OF Cd, Cu, Pb AND Zn FROM SELECTED
UK SURVEY SAMPLES 143 171
6.2 Dates and times of sample processing and analysis 143
6.3 pH of sample leachates 144
6.4 Leaching of UK Survey samples: results and discussion 145
6.5 Discussion 153
6.6 Conclusions 156

7 LEACHING OF CADMIUM, COPPER, LEAD AND ZINC USING
ACCELERATED LEACHING METHODS 172 218
7.2 Standard leaching test (NEN7345) using tapwater leachant 172
7.2.1 Details of samples used 172
7.2.2 Results of standard leaching tests 173
7.3 Treatment of clay brick and PFA-laden concrete samples (CB,
CN) using pH4-acidified distilled water and raised temperature 180
7.3.1 pH data 180
7.3.2 Cumulative release data 181
7.3.3 Comparison with XRF data 184
7.4 Investigation into the influence of temperature on leaching of
metals from Samples A-J using distilled water acidified to pH4 184
7.4.1 Materials and methods 185
7.4.2 Proportions of dissolved and precipitated metals 185
7.4.3 Cumulative release of copper, lead and zinc 186
7.5 Treatment of Samples A to J using pH6 Phosphate Buffer 189
7.5.1 AAS results 189
7.5.2 Voltammetry results 189
7.5.3 XRF analysis of results 198
7.6 Oven heating of samples at 60C 199
7.7 Collation of results from different leaching methods 201
7.7.1 Influence of altered parameters on leaching 202
7.7.2 Correlation between cumulative release and XRF data 212
7.8 Discussion 214
7.9 Conclusions 217

5
8 CONCLUSIONS AND RECOMMENDATIONS 219 - 224
8.1 Literature Review 219
8.2 Collection of Samples 220
8.3 Extraction and analysis of Dioxins and Furans 221
8.4 Leaching of Cadmium, Copper, Lead and Zinc from a selection of
Building materials using the 64-day test 222
8.5 Accelerated leaching of Cadmium, Copper, Lead and Zinc 223

REFERENCES 225 236

APPENDIX 1: Referenced Dioxin and Furan concentrations 237 248
APPENDIX 2: Referenced trace metal content in construction materials 249 251
APPENDIX 3: Samples collected for the UK Survey 252 261
APPENDIX 4: Chromatographs of PCDD/F calibration
(Front page) 262
(Chromatograph print-outs)

6
INDEX OF TABLES

Table 2.1: Composition of concrete conforming to BS standards 7
Table 2.2: Mass ratios of materials in mortar 10
Table 2.3: Fuels used in UK cement kilns 12
Table 2.4: Aggregates for concrete 13
Table 2.5: Classification and purpose of admixtures 15
Table 2.6: Recognised secondary materials 16
Table 2.7: Possible uses of C&DW in construction materials 22
Table 2.8: Plastering varieties 26
Table 2.9: Dioxin and Furan homologues 28
Table 2.10: Air pollution control devices for PCDD/F emissions control 31
Table 2.11: The six recognised TEF systems 32
Table 2.12: Health effects of exposure to Dioxins (PCDDs) and Furans (PCDDFs) 33
Table 2.13: Uses of Cd, Cu, Pb and Zn in industry 37
Table 2.14: Monolithic Sample leaching methods reported in literature 47 to 48
Table 2.15: NEN7345 guideline leaching limits for Cd, Cu, Pb and Zn 50

Table 3.1: Solutions used to investigate loss of congeners during experiment 69
Table 3.2: Details of concrete and Calcium Silicate samples used for
64-day tests 90
Table 3.3: Details of clay bricks used for the 64-day tests 91
Table 3.4: Samples subjected to accelerated leaching tests 92
Table 3.5: Accelerated leaching tests conducted on Samples A to J 92
Table 3.6: Dimensions of department sample monoliths leached using the 64-day test 92
Table 3.7: CB and CN test samples 93
Table 3.8: Details of samples tested using pH4-acidified distilled water 94
Table 3.9: Samples treated at 60C in Soxtherm units using pH6 Phosphate buffer 96
Table 3.10: Samples treated at room temperature using pH6 Phosphate buffer 96
Table 3.11: Samples treated at 60C in oven using pH6 Phosphate buffer 96
Table 4.1: Gas Chromatography settings 97
Table 4.2: Mass Spectrometric criteria for the PCDD/F congeners 102
Table 4.3: Congener concentrations in calibration solutions 103
Table 4.4: Statistical data regarding
13
C-congeners in calibration solutions 103
Table 4.5: Preparation of diluted calibration solutions for determining LOD 111
Table 4.6: Results of the limit of detection tests 112
Table 4.7: Internal standard peak areas 115
7

Table 5.1: Samples analysed in December 2004 119
Table 5.2: Toxicity levels in samples collected in East Anglia 120
Table 5.3: Toxicity levels in samples collected in East Midlands 120
Table 5.4: Toxicity levels in samples collected in London 120
Table 5.5: Toxicity levels in samples collected in Northeast England 120
Table 5.6: Toxicity levels in samples collected in Northwest England 121
Table 5.7: Toxicity levels in samples collected in the English south coast 121
Table 5.8: Toxicity levels in samples collected in southwest England 121
Table 5.9: Toxicity levels in samples collected in the West Midlands 121
Table 5.10: Toxicity levels in samples collected in Yorkshire 122
Table 5.11: Toxicity levels in samples collected in Northern Ireland 122
Table 5.12: Toxicity levels in samples collected in Scotland 122
Table 5.13: Toxicity levels in samples collected in Wales 122
Table 5.14: Toxicity levels in samples collected in existing housing 123
Table 5.15: Toxicity levels in demolition samples 123
Table 5.16: Toxicity levels in soil and PFA samples 123
Table 5.17: Minimum prescribed recoveries of dioxins and furans 126
Table 5.18 (a, b): Recovery of
13
C-based congeners in samples (December
2004) 127 to 128
Tables 5.19 5.29: recoveries of spiked dioxin and furan congeners
(February analyses) 132 to 142

Table 6.1: Cumulative release regulatory limits 143
Table 6.2: Processing of UK Survey samples: dates of analysis 144
Table 6.3: Raw voltammetric analyses of cadmium in leachates first replicates 157
Table 6.4: Raw voltammetric analyses of cadmium in leachates second
Replicates 158
Table 6.5: Raw voltammetric analyses of copper in leachates first replicates 159
Table 6.6: Raw voltammetric analyses of copper in leachates second
Replicates 160
Table 6.7: raw voltammetric analyses of lead in leachates first replicates 161
Table 6.8: raw voltammetric analyses of lead in leachates second replicates 162
Table 6.9: raw voltammetric analyses of copper in leachates first replicates 163
Table 6.10: raw voltammetric analyses of copper in leachates second replicates 164

Table 7.1: details of Samples A J tested using NEN7345 method 173
8
Table 7.2: AAS analyses of Copper in leachates raw data (ug/l) 174
Table 7.3: AAS analyses of Lead in leachates raw data (ug/l) 174
Table 7.4: voltammetric analyses of Cadmium in leachates raw data (ug/l) 175
Table 7.5: voltammetric analyses of Copper in leachates raw data (ug/l) 176
Table 7.6: voltammetric analyses of lead in leachates raw data (ug/l) 177
Table 7.7: voltammetric analyses of zinc in leachates raw data (ug/l) 178
Table 7.8: raw leachate data (voltammetry analyses) (ug/l): cadmium 181
Table 7.9: raw leachate data (voltammetry analyses) (ug/l): copper 181
Table 7.10: raw leachate data (voltammetry analyses) (ug/l): lead 182
Table 7.11: raw leachate data (voltammetry analyses) (ug/l): zinc 182
Table 7.12: copper in sample leachates (pH4-acidified distilled water
at room temperature) 187
Table 7.13: copper in sample leachates (pH4-acidified distilled water at 60C) 187
Table 7.14: copper in sample leachates (pH4-acidified distilled water at 100C) 187
Table 7.15: lead in sample leachates (pH4-acidified distilled water at room 187
temperature)
Table 7.16: lead in sample leachates (pH4-acidified distilled water at 60C) 188
Table 7.17: lead in sample leachates (pH4-acidified distilled water at 100C) 188
Table 7.18: zinc in sample leachates (pH4-acidified distilled water at room
temperature) 188
Table 7.19: zinc in sample leachates (pH4-acidified distilled water at 60C) 188
Table 7.20: zinc in sample leachates (pH4-acidified distilled water at 100C) 189
Table 7.21: leaching of copper (pH6 buffer, 60C using Soxtherm heating) 190
Table 7.22: leaching of zinc (pH6 buffer, 60C using Soxtherm heating) 190
Table 7.23: raw voltammetric data of extracts of samples leached at room
temperature using pH6 buffer (Cadmium) 192
temperature using pH6 buffer (Copper) 192
temperature using pH6 buffer (Lead) 193
temperature using pH6 buffer (Zinc) 193
Table 7.27: raw voltammetric data of extracts of samples leached at 60C
using pH6 buffer (Cadmium) 194

9
using pH6 buffer (Copper) 194
using pH6 buffer (Lead) 194
Table 7.30: raw voltammetric data of extracts of samples leached 60C using
pH6 buffer (Zinc) 195
Table 7.31: cumulative release of cadmium from samples oven-heated to 60C 199
Table 7.32: cumulative release of copper from samples oven-heated to 60C 200
Table 7.33: cumulative release of lead from samples oven-heated to 60C 200
Table 7.34: cumulative release of zinc from samples oven-heated to 60C 200
Table 7.35: XRF analyses of copper 213
Table 7.36: XRF analyses of lead 213
Table 7.37: XRF analyses of zinc 213
Table 7.38: Averaged concentrations of copper 214
Table 7.39: Averaged concentrations of zinc 214

10
INDEX OF FIGURES

Figure 1.1: Methodology of aims and activities of project (insert follows page 5)

Figure 2.1: Materials and products (potentially) available for UK housing 8
Figure 2.2: Dense aggregate concrete production 9
Figure 2.3: The Portland cement production process 11
Figure 2.4: Main lime kiln designs in the EU 14
Figure 2.5: The Blast furnace slag production process 17
Figure 2.6: A pulverised coal-fired power plant 18
Figure 2.7: PFA utilisation in the UK 19
Figure 2.8: The Silica Fume production process 20
Figure 2.9: Fluidised Bed SS (Sewage Sludge) Incineration 23
Figure 2.10: Clay brick production processes 24
Figure 2.11: Dioxin and furan molecular structures and Cl atom positions 27
Figure 2.12: Sources of dioxin and furan emissions to air in the UK in 1999 28
Figure 2.13: The three main PCDD/F formation routes 30
Figure 2.14: Concentrations of PCDD/Fs in solid materials: main categories 35
Figure 2.15: Environmental cycling of Cd, Cu, Pb and Zn 39
Figure 2.16: Concentrations of Cd, Cu, Pb and Zn in construction materials 42
Figure 2.17: Diffusion-controlled leaching of Trace Metals: release rate 46
Figure 2.18: Determining factors affecting metal leaching from monoliths 49
Figure 2.19: Cadmium leaching (reported in literature) 53
Figure 2.20: Cadmium leaching (reported in literature logarithmic projection) 54
Figure 2.21: Release of Cu from mortar, brick, etc. 55
Figure 2.22: Copper leaching (reported in literature) 56
Figure 2.23: Copper leaching (reported in literature logarithmic projection) 57
Figure 2.24: Leaching of lead (reported in literature) 58
Figure 2.25: Leaching of lead (reported in literature logarithmic projection) 59
Figure 2.26: Release of Zn from cement mortars containing IFA 60
Figure 2.27: Leaching of Zinc (reported in literature) 61
Figure 2.28: Leaching of Zinc (reported in literature logarithmic projection) 62

Figure 3.1: Programme of experimental work of the PhD project 63
Figure 3.2: The Twelve UK regions and British population density 64
Figure 3.3: Locations of existing housing (UK Survey) 66
Figure 3.4: The experimental procedure for Dioxin and Furan extraction/analysis 68
11
Figure 3.5: The Soxtherm unit 70
Figure 3.6: Extraction of dioxin and furan homologues 71
Figure 3.7: Extraction of individual dioxin and furan congeners 72
Figure 3.8: The EPA 1613 clean-up filter column 74
Figure 3.9: Simplified clean-up filter column 75
Figure 3.10: Acceptable level of residual extract 76
Figure 3.11: Evaporation of extracts from 200l to 20l 77
Figure 3.12: The gas chromatogram 78
Figure 3.13: Fragmentation of TCDD under MS/MS Conditions 79
Figure 3.14: Fragmentation of TCDF under MS/MS Conditions 80
Figure 3.15: The MS/MS Chamber 81
Figure 3.16: The excitation of electrons by X-rays 82
Figure 3.17: XRF instrumentation 82
Figure 3.18: The three stages in voltammetric determination (hanging mercury drop) 84
Figure 3.19: conversion of the voltage sweep signal into metal concentration peaks 84
Figure 3.20: AAS instrumentation 86

Figure 4.1: Raw chromatographic analysis of calibration solution 97
Figure 4.2: Full chromatogram, showing the Dioxin-Furan Window 99
Figure 4.3: Program used to identify individual congener peaks 100
Figure 4.4: Chromatographs of each tetra-chlorinated congener (TCDF, TCDD) 101
Figure 4.5: Peak Areas (counts) for
13
C Congeners in Calibration Solutions 105
Figures 4.6 (a, b): Calibration data for
12
C-2378-TCDF 106
12
C-2378-TCDD 106
Figure 4.8 (a, b): Calibration data for
12
C-12378-PeCDF 106
12
C-23478-PeCDF 107
12
C-12378-PeCDD 107
12
C-123478-HxCDF 107
12
C-123678-HxCDF 108
12
C-234678-HxCDF 108
12
C-123478-HxCDD 108
12
C-123678-HxCDD 108
12
C-123789-HxCDD 109
12
C-123789-HxCDD 109
12
C-1234678-HpCDF 109
12
C-1234678-HpCDD 110
12
C-1234789-HpCDF 110
12
Figure 4.21: Possible interpretations of the Limit of Detection 110
Figure 4.22: Decision and detection limits 113
Figure 4.23: Line-fit plot of linear regression analysis of limit of detection data 113
Figure 4.24: Tetra-chlorinated congener chromatographs, with internal standard peak 116
Figure 4.25: Histogram of internal standard peak areas 117
Figure 4.26: Correlation between internal standard and
13
C-2378 TCDD peak areas 117

Figure 5.1: Possible Detection of 1234678-HpCDF and 1234678-HpCDD in Soil
Sample N200 124
Figure 5.2: Possible Detection of 1234678-HpCDF and 1234678-HpCDD in soil
sample N201 125
Figure 5.3: Proportion of tetra-chlorinated congeners retained throughout experiment 129
Figure 5.4: Proportion of penta-chlorinated congeners retained throughout experiment 130
Figure 5.5: Proportion of hexa-chlorinated congeners retained throughout experiment 130
Figure 5.6: Proportion of hepta-chlorinated congeners retained throughout experiment 130

Figure 6.1: containers used for UK Survey samples for leaching 145
Figure 6.2: pH of Samples 1 10 leachates 146
Figure 6.6: Influence of sample containers on pH 150
Figure 6.7: blank leachate concentrations (copper) 152
Figure 6.8: blank leachate concentrations (zinc) 152
Figure 6.9: concentrations of metals in tapwater 154
Figure 6.10: leaching of copper from UK survey samples: cementitious samples 165
Figure 6.11: leaching of copper from UK survey samples: clay bricks 166
Figure 6.12: leaching of zinc from UK survey samples: cementitious samples 167
Figure 6.13: leaching of zinc from UK survey samples: clay bricks 168
Figure 6.14: leaching of copper from cementitious samples (Samples 31 - 40 group) 169
Figure 6.15: leaching of copper from clay brick samples (Samples 31 - 40 group) 169
Figure 6.16: leaching of zinc from cementitious samples (Samples 31 - 40 group) 170
Figure 6.17: leaching of zinc from clay brick samples (Samples 31 40 group) 170

Figure 7.1: pH of sample leachates under standard NEN7345 test 177
Figure 7.2: leaching of copper from department samples under NEN7345 test 178
Figure 7.3: leaching of zinc from department samples under NEN7345 test 179
13
Figure 7.4: pH data for the clay brick (CB) leachates 180
Figure 7.5: pH data for the concrete (CN) leachates 180
Figure 7.6: CB/CN tests: cumulative release data (copper) 183
Figure 7.7: CB CN Tests: cumulative release data (zinc) 183
Figure 7.8: XRF analysis of CB and CN replicates 184
Figure 7.9: Proportions of leached and re-precipitated Zn 185
Figure 7.10: Proportions of leached and re-precipitated Cu 186
Figure 7.11: cumulative release of copper from department samples (treated at pH4) 186
Figure 7.12: leaching of copper from samples treated with phosphate buffer at 60C
(AAS results) 190
Figure 7.13: leaching of zinc from samples treated with phosphate buffer at 60C
(AAS results) 191
Figure 7.14: cumulative release of cadmium from samples leached with pH6 buffer at
room temperature and at 60C 195
Figure 7.15: leaching of copper from samples treated with pH6 buffer at room
temperature, and at 60C 196
Figure 7.16: leaching of zinc from samples treated with pH6 buffer at room temperature,
and at 60C 197
Figure 7.17: Copper content of samples leached with pH6 buffer 198
Figure 7.18: Lead content of samples leached with pH6 buffer 198
Figure 7.19: Zinc content of samples leached with pH6 buffer 199
Figure 7.20: cumulative release of copper from samples oven-heated to 60C 201
Figure 7.21: cumulative release of copper from samples oven-heated to 60C 201
Figure 7.22: cumulative release of copper from sample A under different leaching
conditions 202
Figure 7.23: cumulative release of zinc from sample A under different leaching
conditions 203
Figure 7.24: cumulative release of copper from sample B under different leaching
conditions 203
Figure 7.25: cumulative release of zinc from sample B under different leaching
conditions 204
Figure 7.26: cumulative release of copper from sample C under different leaching
conditions 204
Figure 7.27: cumulative release of zinc from sample C under different leaching
conditions 205

Figure 7.28: cumulative release of copper from sample D under different leaching
14
conditions 205
Figure 7.29: cumulative release of zinc from sample D under different leaching
conditions 206
Figure 7.30: cumulative release of copper from sample E under different leaching
conditions 206
Figure 7.31: cumulative release of zinc from sample E under different leaching
conditions 207
Figure 7.32: cumulative release of copper from sample F under different leaching
conditions 207
Figure 7.33: cumulative release of zinc from sample F under different leaching
conditions 208
Figure 7.34: cumulative release of copper from sample G under different leaching
conditions 208
Figure 7.35: cumulative release of zinc from sample G under different leaching
conditions 209
Figure 7.36: cumulative release of copper from sample H under different leaching
conditions 209
Figure 7.37: cumulative release of zinc from sample H under different leaching
conditions 210
Figure 7.38: cumulative release of copper from sample I under different leaching
conditions 210
Figure 7.39: cumulative release of zinc from sample I under different leaching
conditions 211
Figure 7.40: cumulative release of copper from sample J under different leaching
conditions 211
Figure 7.41: cumulative release of zinc from sample J under different leaching
conditions 212
Figure 7.42: correlation between averaged XRF and cumulative release data: Copper 215
Figure 7.43: correlation between averaged XRF and cumulative release data: Zinc 215

15
LIST OF SYMBOLS AND ACRONYMS

AAS Atomic Absorption Spectrometry
C&DW Construction & Demolition Waste
Cd Cadmium
Cu Copper
GGBS Ground-granulated Blast-furnace Slag
HxCDD/HxCDF Dioxins and furans containing 6 chlorine (Cl) atoms
HpCDD/HxCDF Dioxins and furans containing 7 chlorine (Cl) atoms
IFA Incinerator Fly Ash
IBA Incinerator Bottom Ash
NEN 7345 The standard leaching test for monolithic samples
OCDD/OCDF Dioxins and furans containing 8 chlorine (Cl) atoms
PCDD/Fs Dioxins and furans (initials represent their full chemical names)*
*PCDDs Poly-chlorinated dibenzo-para-dioxins (Dioxins)
*PCDFs Poly-chlorinated dibenzofurans (Furans)
PeCDD/PeCDF Dioxins and furans containing 5 chlorine (Cl) atoms
PFA Pulverised Fuel Ash
Pb Lead
Samples A-J A set of samples used mainly for accelerated leaching tests (some
containing secondary materials)
SF Silica Fume
SS Sewage Sludge
SSA Sewage Sludge Ash
TCDD/TCDF Dioxins and furans containing 4 chlorine (Cl) atoms
(I)-TEF Toxic Equivalence Factor (i.e. the measure of toxicity of a dioxin or
furan molecule, compared with 2378-TCDD (a decimal value)
(I)-TEQ Toxic Equivalence Quotient (the net toxicity posed by the 7 toxic
dioxins and 10 toxic furans, expressed as concentration (e.g. ng/kg)
as if it was all 2378-TCDD)
UK Survey Samples A group of cementitious and clay brick samples collected throughout
the UK and subjected to leaching tests
VA Voltammetry analysis
Zn Zinc

16
1 INTRODUCTION

1.1 BACKGROUND
1.1.1 Secondary and Waste Materials for Construction Products

There is an unprecedented demand for new housing construction in Britain today. Both social
and economic trends favour the rapid expansion of British residential estates: the average
number of occupants per household has decreased markedly during the past few decades, as a
result of an aging population (elderly couples or widows living alone), divorce, and personal
demand for single occupancy. Other factors include immigration, and economic growth in
southeast England (The Guardian, 2001). Nevertheless, demand for new housing is offset by
limited supply. In addition, the transportation and manufacturing costs of construction
products is steadily rising as a result of environmental tax levies, including landfill tax,
aggregate levies, as well as taxes on emissions (namely carbon dioxide), and on fuel.

One solution which partly addresses these environmental and financial issues is to increase, or
develop the means, of using secondary or waste materials in construction products. This was
promoted under the 6
th
Environmental Action Programme by the European Union, and
industrial by-products such as PFA are already being used to partly replace cement or natural
aggregate (in this thesis, these are referred to as secondary materials). There are other by-
products (referred to as waste materials, e.g. sewage sludge ash) which could be used in
construction products, although this is not practised commercially in the UK.

The use of waste materials may provoke public anxiety and opposition. Essentially, waste
production is the enrichment of unwanted chemical or physical content. With incinerator ash,
this has proved true regarding pollutants such as dioxins, furans and trace toxic metals (e.g.
cadmium). However, some industrial by-products previously discarded as waste were
discovered to possess physical or chemical properties which improved those of building
products (e.g. PFA, or GGBS). These have proved to be commercially viable secondary
materials, which generally do not present any immediate health hazards to the public, and
which have been used for many years in the UK. However, not all industrial by-products
with potential use in building materials have been endorsed. For example, attempts were
made to use incinerator fly ash (IFA) as a pozzolan in concrete, but this was abandoned after
the Edmonton incinerator ash scandal, which arose in July 2000, mainly because of concerns
regarding the dioxin and furan content of incinerator ash (Environment Agency, 2002).

17
1.1.2 Dioxins and Furans

Dioxins and furans are a large family of organic compounds, each of which comprise 2
benzene rings with oxygen, hydrogen and chlorine atoms attached. Dioxins are compounds
with 2 benzene rings linked by 2 oxygen atoms, whilst furan compounds are characterised by
2 benzene rings linked by one oxygen atom, and also by a direct link between 2 carbon atoms
within the benzene rings. Dioxin and furan compounds contain between 0 and 8 chlorine
atoms bonded to the benzene rings. 17 of these compounds are considered to be dangerous to
health, although the precise reasons for this have not been fully deduced. The potential health
risks of dioxins and furans were vividly brought to peoples attention following the usage of
Agent Orange during the Vietnam War, and a large explosion at a chemical plant in Seveso
(Italy) in 1978. These events produced contamination of local biota and soil with dioxin and
furan compounds. Affected residents reported a wide range of debilitating symptoms,
including retardation amongst children born to exposed parents, cancer, lung disease and skin
lesions. Nevertheless, to this day there remains a limited understanding of the relationship
between reported health symptoms, and exposure to individual dioxin/furan molecules
(IARC, 1997; Bates, 2001).

During the Edmonton incinerator ash scandal, information on IFA used for concrete blocks
(possibly for new housing) was released to the press, and the resulting media attention
focussed on the possible health risks posed by their dioxin and furan content. It was neither
known how many houses were constructed using the ash-laden concrete blocks, nor if dioxins
and furans existed in the construction materials of houses in general. The only detailed study
of dioxins and furans in construction materials for housing found in the literature was
published by the Environment Agency, in response to the Edmonton scandal. Ash-laden
concrete blocks contained measurable quantities of these toxins, whereas ordinary clay brick
and concrete samples contained negligible quantities (Environment Agency, 2002).

1.1.3 Leaching of Cadmium, Copper, Lead and Zinc (Cd, Cu, Pb, Zn)

All four metals generally occur at trace quantities in environmental media, although all serve
some important functions in mechanical, electronic and/or domestic appliances. Cadmium
and lead are dangerous to human health, causing blood poisoning and possible mental
retardation upon exposure via contaminated water. Although copper and zinc present a much
lower risk to human health, they can become eco-toxic at highly enriched levels, particularly
in soil. Building materials, landfills and surface waste tips may release these metals into
surrounding water, especially when the water is acidic.
18
There have been several studies into the leaching of trace metals into water from cementitious
materials. Again, the prime focus has been on products (namely concrete) containing MSW
incinerator ash, with relatively few studies into leaching from commercial, ordinary concrete
and clay bricks. From those studies, it has generally been concluded that the release of the
above metals via leaching rarely presents an environmental problem, mainly due to the
alkalinity of the cementitious matrix retaining the metals.

The standard leaching tests for monoliths (sample blocks) are time-consuming. Standard
leaching tests (namely the NEN7345 test, now succeeded by the NEN7375 test) specifies an
experimental duration of 64 days. Some researchers have conducted shortened tests, or have
altered other parameters (including temperature) in order to accelerate the leaching process.
However, few studies using shortened leaching methods were found in the literature.

1.2 AIMS AND OBJECTIVES OF THE PROJECT

Dioxin and furan studies have mainly focussed on the concentrations in MSW incinerator ash,
or in biota. Almost no studies have been conducted on materials worthy of use in housing
construction. Likewise, limited data on the leaching of trace metals from ordinary
construction materials exists in the literature. This PhD project aimed to address this shortage
of data, and therefore contribute to these limited bodies of knowledge.

Additionally, having recognised the lengthy periods of time required to conduct monolithic
leaching tests employed in the UK, the PhD also aimed to establish whether accelerated tests
could be applied to construction materials.

The objectives of the PhD project were as follows:

1 to conduct a review of the literature concerning building products for housing,
and the occurrence of dioxins and furans and selected trace metals in such
products and related materials;
2 to collect representative building product and soil samples from new-build and
existing housing throughout the UK, plus samples of demolition materials and
concrete containing secondary and waste materials;
3 to develop a method for the extraction and analysis of dioxins and furans from the
materials collected, using GC-MS/MS techniques;
4 to study the leaching of cadmium, copper, lead and zinc from selected samples
using a standard monolith leaching test; and,
19
5 to assess the suitability of modifying leach test conditions to achieve accelerated
leaching.

1.3 SCOPE OF THE PhD PROJECT

The thesis addresses two different categories of trace chemicals organic dioxins and furans,
and four inorganic transition metals. Almost no published papers or reports concerning these
chemicals in housing materials were identified during the literature review. In addition, some
laboratory methods used for this project were unique. This project is therefore an exploratory
investigation, and the data generated during the project needs to be supported by further
research.

Building product samples collected were limited to inorganic, non-metallic materials, partly
as these materials are predominant in a housing structure (accounting for approximately 80%
of the structure) (European Commission, 2000). Concrete, calcium silicate, clay brick,
cement, mortar, and plasterboard samples were collected. In addition, soil samples were
collected on-site, as these contained background concentrations of dioxins and furans.
Samples were collected from new-build and existing house-construction sites throughout the
UK. In addition, a selection of demolition waste samples, and test concrete samples
containing secondary/waste materials were provided from other research projects.

1.4 LAYOUT OF THESIS

A full methodology of the PhD project is illustrated in Figure 1.1. Chapters 2 to 6 focus on
the information and outcomes of the aims detailed in section 1.2:

Chapter 2 comprises a literature review, which focussed on the following subjects:
- conventional, secondary and potential waste materials which are/could be used in
British housing;
- the properties, sources, environmental occurrence, and possible health risks of dioxins
and furans, as well as their analysis, and reported concentrations of dioxins and furans
in a range of materials;
- the properties, applications, environmental occurrence and leaching behaviour of Cd,
Cu, Pb and Zn are detailed, as well as a review of the leaching methods found in the
literature.

20
Chapter 3 describes the materials and methods used throughout the PhD project. (A full list
of all samples collected throughout the UK is given in Appendix 4 at the end of the thesis.)

Chapter 4 is a continuation of the description of dioxin and furan analysis in Chapter 3.
Special coverage is given to the development and calibration of the GC-MS/MS, and on the
meaning of the data generated.

Chapter 5 describes the dioxin and furan results generated for the survey samples, as well as
detailing the reference standard solutions used alongside sample analysis, in order to
accurately quantify and identify the dioxin and furan congeners.

Chapter 6 addresses the leaching of Cd, Cu, Pb and Zn from a selection of UK survey
samples, and also from Samples 1-10 provided within the department. All samples listed in
this chapter were treated according to the NEN7375 test for 64 days without pH control.

Chapter 7 addresses the leaching experiments using significantly altered parameters,
including raised temperature, pH alteration (using nitric acid or phosphate buffer solution),
and reduced leaching time (7 days).

Chapter 8 concludes on the overall findings from the PhD project, and provides
recommendations for further work in the field.

21

22
2 LITERATURE REVIEW

2.1 INTRODUCTION

The use of waste materials and fuels for the British construction industry has become a
necessity during the past decade, when tightening EU environmental legislation has imposed
increasing financial penalties for conventional practices. Fossil fuel and raw aggregate
consumption, plus the emission of greenhouse and acid rain gases, are subject to taxation and
scrutiny under legislation such as the Aggregates Levy, the Landfill Directive, and Integrated
Pollution Prevention & Control (IPPC). In addition, the inclusion of certain industrial by-
products such as PFA (Pulverised Fuel Ash) can impart improved physical or chemical
properties to concrete, thus enabling contractors to make financial savings (Harrex, 2003).

Nevertheless, it is known that certain by-products which could be used in construction
products may also contain pollutants, namely dioxins, furans, and trace metals such as
cadmium and lead (Dawy, 2004). The occurrence of potentially hazardous chemicals in
houses is a particularly sensitive issue. In 2000, it was revealed that MSW incinerator fly ash
from Edmonton had been used in housing concrete blocks. The revelation was reported both
by the press and the BBC, since the blocks contained dioxins and furans (BBC, 2000).
Dioxins, furans, cadmium, lead, copper and zinc are trace chemicals which may be enriched
in residues such as incinerator ash. All except copper and zinc are considered to be toxic,
although a high consumption of copper can also be damaging to health (Porteous, 1996).

In order to evaluate the potential for enriched levels of these chemicals and their release from
materials used for housing, a literature review was conducted into three main topics:

1 A survey of inorganic, non-metallic materials and products which are (potentially)
used for British housing
2 The chemistry, formation, environmental occurrence and health risks of dioxins and
furans
3 The chemistry, environmental occurrence, plus leaching and health risks posed by
cadmium, copper, lead and zinc

The following sections focus on these topics in the above order.

23
2.2 MATERIALS AND PRODUCTS USED FOR BRITISH HOUSING

The composition of new housing in the UK is dominated by inorganic, non-metallic materials
including concrete, mortar, clay bricks and plasterboard. These materials are therefore the
focus of the PhD project. Clay bricks are also widely used, and gypsum-based plasterboard is
used for almost all new properties. Figure 2.1 summarises both active and potential
manufacturing and usage of construction materials and products. It is not known to what
extent secondary materials such as ash or slag are being incorporated into building materials,
since such information is usually kept confidential. A broad range of waste materials and
other industrial by-products have been (successfully) tested in construction products, although
only PFA (in concrete) and FGD gypsum (in plasterboard) are knowingly used in housing.

2.2.1 Materials Used in Concrete and Mortar
2.2.1.1 Overview of Materials

The production and usage of Portland cement-based concrete and mortar has proliferated in
the UK during the last century; in 2000, over 170 million tonnes of concrete were produced;
in 2002, around 31% of concrete was used for housing projects (Concrete Society, 2001).
Concrete is a ceramic composite product, composed of coarse aggregate and sand, entrapped
within a matrix of hydrated cement (typically Portland cement). Ordinary concrete varies in
composition, usually containing 7-15% Portland cement, 14-21% water, <1-8% air, 24-30%
sand, and 31-51% coarse aggregate, by volume (Smith, 1993).

The exact composition is dictated by a broad range of physical, chemical and environmental
factors, as defined under documents such as BS 8500:2 (2002), and Design of Normal
Concrete Mixes (Teychenne et al, 1988) (Table 2.1). These documents also address concrete
which accommodates a broad range of waste/secondary aggregates and pozzolans.

Table 2.1: Composition of concrete conforming to specified standards
Component British Standard/Guideline Content (kg/m
-3
)
Cement BS 8500: 2 (2002) Tables 7, 8 120 550 max
BS 8500: 2 (2002) Table 10 1705 1990
(Containing 25 40% mass
of fine aggregate)
Aggregate
(BRE, 1988)
Design of Normal Concrete Mixes
Figs 5, 6
2180 2700 (wet density)
(Comprising 13 78% of
<5mm diameter particles)

24

Figure 2.1: Materials/Products (potentially) used in UK housing (except admixtures)

Bold arrows indicate known processes which are commercially active; they do not indicate the exact
composition of the final product. Dashed arrows indicate potential processes being researched.
(Collated from the following references: Brick Development Association, 1994; Day, 1995; Marshall
and Worthing, 1995; Nawy, 1995; Neville, 1995; Thomas, 1996; Chandra, 1997; Joshi and Lohtia,
1997; Hewitt, 1998;CIRIA, 1999; Beall, 2001; European Commission, 2001
1, 2
; Sear, 2001; Anderson,
2002; Environment Agency, 2002; Halliday, 2002; Malhotra and Mehta, 2002; Ashurst, 2003)
Coarse
Aggregate
Igneous/metamorphic
rock
Sandstone/quartzite
Iron ore
Limestone
Gypsum ore
Crushing of
ore*
(Batching and steam-
compression of mix)*
(*Pre-cast)
Concrete
Demolition and
re-processing
Fine aggregate
Clay
Portland
Cement
Roasting in
cement kiln
CKD
Particulate
collection
Coal/Petcoke Power
generation PFA
FBA
FGD Gypsum
Sewage Sludge Incineration
SSA
Municipal
Solid Waste
Waste Tyres
Hazardous /
chemical waste
(oils, solvents,
pesticides etc.)
Water
Crushing
Incineration
Particulate
collection
IBA
IFA
Batching and steam-
compression of mix
Plasterboard
Brick-Earth
clay
Roasting in
brick kiln
Iron smelting BFS GGBS
SF
Electric arc
furnace
silica dust
collection
Silica ore
Masonry
Mortar
Pressurised
steam treatmnt
Calcium
Silicate brick
Clay Brick
Lime
Roasting in
lime kiln
25
2.2.1.2 Production of Concrete Blocks

Types of concrete block include dense aggregate, lightweight aggregate, re-constructed stone
masonry (or cast stone) and autoclaved aerated concrete (Thomas, 1996). Dense aggregate
concrete is the most abundant in residential projects, comprising crushed stone and gravel
(Brick Development Association, 1994; Thomas, 1996). Dense aggregate concrete is
manufactured at dedicated batching plants, and blocks/bricks are then distributed (Figure 2.2).
Cement, coarse aggregate, sand, water, and admixtures are mixed and autoclaved at around
100C under high-pressure steam injection; temperatures as high as 180C may be used to
obtain higher early strength. Hydraulic and mechanical concrete compression techniques are
used widely in the UK (Marshall and Worthing, 1995).

Figure 2.2: Dense aggregate concrete production (Marshall and Worthing, 1995)

Lightweight concrete blocks incorporate low-density aggregates (e.g. pumice), and are
prepared in a similar manner to dense aggregate concrete. Re-constructed stone masonry
units are composed of fine aggregate and a cementing binder, which are mixed and strongly
compressed to produce a product, which resembles sandstone, and can be used for
architectural design. Autoclaved aerated concrete contains Portland cement, lime, and PFA
(which partly replaces the cement); Al powder is included in the mix, and then the solid
materials are mixed with hot water. The aluminium powder reacts vigorously with the lime
(producing hydrogen bubbles), and the PFA undergoes a pozzolanic reaction with the
Portland cement hydration products (Marshall and Worthing, 1995; Thomas, 1996).

26
2.2.1.3 Production of Mortar

Mortar is used for all block-work applications, and is chiefly produced on-site. Although this
is not a structural unit, mortar comprises over 16% of a clay brick wall and around 7% of a
concrete block wall by volume - and its composition will determine the stability of the wall.
Mortars include (1) masonry mortar: (Portland cement + lime + sand), (2) masonry cement
mortar (cement + lime), and (3) cement mortar (cement + sand + air-entraining admixture)
(Powell, 1979; Beall, 2001). Early mortars comprised lime and sand, but these set very
slowly, and so are rarely used. Masonry mortar is used for mortar in brickwork, and may also
contain GGBS, PFA or inert filler. Masonry mortar is comparatively weak, and cannot be
used with concrete blocks (Marshall and Worthing, 1995; Neville, 1995). The proportions of
sand, lime, Portland cement and/or other constituents also vary, depending on the nature of
the structure; ranges are listed in Table 2.2.

Table 2.2: Mass ratios of materials in mortar

Standard/Guideline

Portland Cement

Sand

Lime
Powell (1979) (<75% volume)
BS 4721

3 12 1
BS 8103: 2 (2005) Table 4 1 5 6 1
BS 998:2 (2003) (Example) 10 75 15

2.2.1.4 Portland Cement

Portland cement is an invaluable binding material, which has been used in the UK since its
invention in the 1820s. Its inclusion in mortar and concrete is essential, and approximately 13
million tonnes are produced by 20 plants in Britain. For centuries, lime mortars had been
used extensively. However, Portland cement mortars set more rapidly, allowing construction
or concrete production to proceed more economically (Nawy, 1995; Dept. of Statistics, 2002).

Production of Cement

The cement production process (in its simplest depiction) is illustrated in Figure 2.4. The
production of cement is only possible through the fusion of iron, aluminium, silicon and
calcium oxides. These four elements are traditionally provided by shale, clay, iron ore,
sandstone and limestone. Apportioned batches of these raw materials are initially crushed
and batched together in blending silos to produce raw meal (European Commission, 2001
1
).
27
The raw meal may either be injected as a dry powder (Dry Process, which accounts for
around 80% of European cement); it may be wetted into pellets (Semi-dry process, which
accounts for around 15% of European cement), or it may be immersed in water to produce a
slurry (Wet Process). The raw meal is passed through a series of pre-heating chambers,
wherein the temperature is raised to over 900C, thereby decomposing the limestone (CaCO
3
)
to yield lime (CaO) and CO
2
; emission gases from the rotary kiln are transferred to the pre-
heaters. Within the rotary kiln, a temperature exceeding 1400C is required, which forces the
lime to react with the Si, Al and Fe oxides to produce the calcium phases present in Portland
cement clinker. In order to prevent flash-setting of the clinker, gypsum is inter-ground with
the product (Neville, 1995; European Commission, 2001
1
).

Figure 2.3: The Portland cement production process (European Commission, 2001
1
)

Despite its indispensability and comparative cheapness, Portland cement manufacture
requires rapid fuel and raw material consumption, and results in copious emissions, especially
CO
2
. Approximately 40 60% of the price of cement is attributed to the heating required for
production, and approximately a tenth of the price attributes to purchasing and processing of
raw materials. These disincentives alone have encouraged the cement industry to consider
substituting expensive raw aggregates and fossil fuels with alternative feeds and fuels
(Livesey, 1994; Neville, 1995; British Cement Association, 2002).

Blending
silos
Rotary Kiln

Clinker
cooler
Pre-calciner
CKD collection

Blending
silos
Raw feed
CKD
Shale/clay
Sand Iron ore
Limestone
Gypsum
PORTLAND
CEMENT
Clinker
Waste heat recycled
FUEL
28
Waste co-incineration was explored in the 1980s, and was adopted in the early 1990s in the
UK. Under EU legislation, waste co-disposal has been further encouraged, since the cement
industry can secure an 80% rebate on the Climate Change Levy. Secondly, tyre incineration
in kilns has proliferated since the disposal of waste tyres to landfill was prohibited in 2003
(British Cement Association, 2002
1, 2
; ENDS Report, 2002). Table 2.3 shows the broad range
of waste and secondary materials that have been tested in this role. One concern associated
with the inclusion of waste feedstocks and fuels is the possibility of increased dioxin and
furan emissions, especially when organic substances (namely those composed of chlorine-
bearing compounds) are fed into the kiln (Eduljee, 1999).

Table 2.3: Fuels and alternative feedstock used in UK cement kilns
Fuels used/tested in UK kilns References
Cemfuel*, RLF**, tyre (chips), carpets, plastics,
waste paper and paper sludge, waste oils/solvents,
wood, sewage sludge, animal wastes
FoE, 1997; Environment Agency,
1998; BCA, 2002
1, 2
Castle Cement,
2003
1, 2
; La Farge (Blue Circle), 2003
Secondary/waste raw meal materials used/tested References
Tyres (reduces raw iron oxide feed)
PFA, GGBS (substitutes for shale and clay)
CKD (cement kiln dust)
Environment Agency, 1998
BCA, 2002
RMC, 2003

* Cemfuel is composed of methanol, ethanol and acetone, and is derived from paint fillers, cosmetics, antiseptics and
carwash chemicals (Castle Cement, 2003
2
)
** RLF (Recycled Liquid Fuel) is produced from wastes of inks, paint and brush-cleaning agents; this is being used at the
Dunbar LaFarge works (Blue Circle/LaFarge, 2003)

2.2.1.5 Natural Aggregate

Aggregates typically comprise three-quarters of the volume of concrete, and they also form
the prime component in mortar. It is therefore essential that they are physically and
chemically stable. Aggregates are either quarried, or dredged; they are classified either as
dense or lightweight. They must not contain deleterious substances, nor should they
absorb large quantities of water. Table 2.5 details suitable aggregates, and deleterious
substances. Raw aggregates are extracted and processed at hundreds of sites throughout the
UK, since transportation is expensive and must be minimised. However, the progression of
environmental legislation has encouraged companies to utilise recycled and secondary
aggregates (Day, 1995; Nawy, 1995; Neville, 1995; Concrete Society, 2001).

2.2.1.6 Lime

29
76 million tonnes of limestone and 8 million tonnes of chalk were extracted in the UK in
2002. The prime recipient was the construction industry, which utilised 77% and 10% of
limestone and chalk, respectively.

Table 2.4: Aggregates for concrete
Suitable Aggregates References
Dense Igneous Basalt, Granite, Gabbro, Porphyry Neville, 1995
Metamorphic Schist, Quartzite, Hornfels Neville, 1995
Sedimentary Gritstone, Limestone, Neville, 1995
Lightweight Pumice, scoria, vermiculite
(Not relevant in the UK)
Day, 1995
Nawy, 1997
Concrete Society leaflet (2001)
Deleterious substances
(must either be absent, or present at minor/trace
quantities)
References

Organic impurities (vegetable matter, humus, soil) Neville, 1995
Clay, silt, crusher dust Powell, 1979
Neville, 1995
(BS 1199: Building Sands from
Natural Sources)
Salt (and other chloride/alkali salts)
(Salt must be washed from sea-dredged sediment)
Powell, 1979
Neville, 1995
Nat Sources)
(BS 8500: 2 (2005))
Unsound particles (coal, shale, mica flakes, gypsum and
other sulphates, iron pyrites, marcasite, shell fragments)
Powell, 1979
Neville, 1995
Thomas, 1996
Natural Sources)

The use of (hydraulic) lime alone as a binder has been almost exclusively replaced with
Portland cement-based mortars. Nevertheless, hydraulic lime may be used for special or
conservational projects, and it is used in mortar, external rendering, and occasionally in
gypsum plaster (Thomas, 1996; Ashurst, 2003; British Geological Survey, 2004).

Lime (or quick-lime) (CaO) is manufactured via the calcination of the limestone (CaCO
3
),
yielding CO
2
- this reaction proceeds at 825C. As much as half the cost of the product can
be attributed to fuel consumption in lime kilns. Coal has been substituted with a variety of
gaseous, liquid and/or waste fuels - used tyres, wastepaper, biomass, plastics, and other waste
residues may be co-incinerated (Landesumweltamt Nordrhein-Westfalen, 1997; European
Commission, 2001
1
).

30
There is a variety of lime kilns in existence in the EU; Figure 2.5 illustrates three of the most
common types. In general, highly pure limestone is fed from above, and passes through a
combustion chamber. As the material reacts and descends, it passes towards colder regions,
until the quicklime is discharged. Fuel burners and air injectors are inserted either through
opposite ends of the kiln, or throughout the kiln (European Commission, 2001
1
).

Figure 2.4: Main lime kiln designs in the EU (European Commission, 2001
1
)

2.2.1.7 Water

In addition to its vital role of reacting hydraulically with cement, the water within concrete
and mortar influences the fluidity of the final product. Only approximately half of the water
will react with the cement, whereas the residual water will be trapped within pores. In
general, water suitable for concrete and mortar is pure enough for drinking; seawater is never
used (Powell, 1979; Thomas, 1996; Concrete Society, 2001).

2.2.1.8 Admixtures and Synthetic Additives

Admixtures have been used in a variety of forms for concrete throughout the last century.
Although they comprise less than 0.1% of the volume and around 0.04% of the mass of
concrete, they are necessary to adjust the physical nature of the product. They may also alter
the rate of cement hydration. Although they have proved popular abroad, their value has only
recently been acknowledged in the UK, particularly after British standards were drafted
during the 1980s to control the ambiguous quality of admixtures on the market (Powell, 1979;
Doran, 1992; Concrete Society, 2001). Concrete typically contains one type of admixture
31
(Simmons and Olin, 2001). Two or more are only used in special applications. The most
abundantly used admixtures for mortar are air-entraining agents; other commonly used
admixtures include water-reducers, retarders (for cold climates) or accelerators (also used for
mortar). Table 2.6 details the varieties and purposes of admixtures and other minor
substances.

Table 2.5: Classification and purpose of admixtures
Category Purpose Chemicals References
Admixtures
Accelerating Increases initial pozzolanic
reaction between cement and
water. May be used in masonry.
Useful for colder climates.
Sodium thiocyanate used
extensively in the UK (Doran,
1992)
Calcium formate
Calcium chloride
Calcium nitrate
Triethanolamine
(Other inorganic chlorides,
salt, carbonates, aluminates,
borates, formates,
thiosulphates, etc. etc.)
Sodium thiocyanate
Powell (1979)
Concrete Society
(1980)
Doran (1992)
Dodson (1990)
Paillere (1995)
Air-entraining Introduces microscopic air
globules into the concrete. This
reduces water expulsion
(bleeding), and increases frost
resistance and impermeability.
Salts of wood resins most
commonly used (Doran, 1992).
Abietic, primeric and fatty
acids(and their salts)
Alkyl sulphonates
Aryl sulphonates
Phenol ethoxylates
Ethylene oxide polymers
Salts of wood resins (sodium
abietate), and proteins
Synthetic detergents
(Animal tallow, bitumen,
waste oil or grease used in
older sites)

Powell (1979)
Concrete Society
(1980)
Dodson (1990)
Doran (1992)
Paillere (1995)
Bonding Organic polymer emulsions used
to toughen the link between
concrete and mortar units.
PVA (poly-vinyl acetate)
SBR (styrene butadiene)
Acrylic
Concrete Society
(1980)

Corrosion-
inhibit.
This is particularly important
with steel-reinforced concrete
Sodium salts
(nitrate/benzoate/chromate)
Concrete Society
(1980)
Damp-proofing Repulsion of water from surfaces Stearates, oleates, other oil
waste
Concrete Society
(1980)
Expanding Used to control concrete
shrinkage (also see Gas-
forming)
Granulated iron
Powdered aluminium
Activated carbon
Concrete Society
(1980)
Gas-forming (See Expanding) Zinc, magnesium filings
Hydrogen peroxide
Nitrogen/ammonium/hiadrazin
compounds
Paillere (1995)
Retarding
(Water-reducing)
(Plasticizing)
Disciplines the reaction between
water and cement; this is
necessary if the concrete is being
transported over long distances.
Must be used with caution.
Salts of boric/phosphoric acid
Salts of lignosulphonic or
carboxylic acids
Ethanoamines, naphthalenes
Glucose
Zn salts
Melamine derivatives
Powell (1979)
Concrete Society
(1980)
Dodson (1990)
Paillere (1995)
Thomas (1996)
Super-
plasticizing
Usage restricted to specialist
applications (irrelevant)
Doran (1992)

32
2.2.1.9 Secondary Materials used in Concrete

The capital and operational costs involved in producing and purchasing construction materials
have made the use of secondary (industrial by-product) materials increasingly favourable.
The inclusion of secondary and waste materials in concrete has been practised for several
decades. BS 8500: 2 (2002) specifies the maximum content of secondary materials in
cement, as summarised in Table 2.6.

Table 2.6: Recognised secondary materials in BS 8500:2 (2002)
Secondary
material
Classification Content (mass)*
Silica Fume CEM II/A D (BS-EN 197-1: 2000) 6%-10% of cement
CIIA S 6% - 20% of CEM I cement replaced by GGBS
CIIB S 21% - 35% of CEM I cement replaced by
GGBS
CIIIA 36% - 65% of CEM I cement replaced by
GGBS
CIIIB 66% - 90% of CEM I cement replaced by
GGBS
BIIIA 36% - 65% of cement replaced by GGBS
(BS 146: Specification for Blastfurnace
Cements)
Slag
BIIIB 66% - 80% of cement replaced by GGBS
(BS 146: Specification for Blastfurnace
Cements)
CIIA V 6% - 20% of CEM I cement replaced by fly
ash (conforming to BS EN 450) or PFA (BS
3892-1)
CIIB V 21% - 35% of CEM I cement replaced by fly
3892-1)
Fly Ash**
CIVB V 36% - 55% of CEM I cement replaced by fly
3892-1)
* CEM I cement is Portland cement designated under BS EN 197-1
** Fly ashes must be derived from ESPs or mechanical collectors of pulverised coal ashes

In addition, the document recognises the use of furnace bottom ash (FBA), blastfurnace slag
(BFS) and recycled (demolition-derived) aggregates. The maximum proportion of secondary
aggregates in concrete is determined by their chemical composition and physical stability, as
defined under the British standards. Secondary materials relevant to this project are
addressed in the following sub-sections.

33
Blastfurnace Slag (BFS) and Ground-Granulated BFS (GGBS)

Approximately 4 million tonnes of BFS are produced annually in the UK (Dunster, 2001).
Both BFS and GGBS are highly valued industrial by-products, and have been used since the
early 20
th
century. Nearly all British-produced BFS is used: approximately 40% is water-
quenched to produce GGBS. Approximately half of BFS is used as aggregate for transport
and construction, and of this, approximately a fifth is used in masonry and structural concrete.
GGBS is chemically similar to Portland cement. It contains the necessary aluminium,
calcium and silicon oxides - albeit in different proportions and, therefore can be used in
masonry mortar. BFS can also be used as a feedstock in cement kilns, since it is rich in
calcium oxide, and its use in kilns reduces the energy requirement for calcination (Neville,
1995; CIRIA, 1999; Appleby Group Ltd, 2003). BFS is the solid furnace residue produced
from the smelting of iron (Figure 2.5). Iron extraction is conducted in two stages:
(1) Sintering the heating of iron ore mixed with coke, coal, lime, oil,
recycled sinter, olivine and/or other recycled dust to produce a pre-
designed intermediate product;
(2) Blastfurnace extraction the mixture is heated to 2000C, at which
elemental iron is obtained, and the slag floats on the molten iron
collecting at the base of the furnace. The BFS forms from the fusion of
limestone, dolomite, ash and other aluminous/siliceous fluxes (Chandra,
1997; Dunster, 2001)

Figure 2.5: The blastfurnace slag production process (European Commission, 2001
2
)

COKE/COAL
IRON ORE
LIMESTONE
Sintering Blast furnace
BLAST
FURNACE
SLAG
Collected Dust
Recycled
sinter
MOLTEN IRON
Aggregate
Immediate immersion
in water
GGBS
Product granulised
34
Furnace Bottom Ash (FBA)

Furnace Bottom Ash is one of two important by-products from coal combustion in power
plants (PFA is discussed later). Pulverised coal combustion produces approximately a third
of British electricity. The process involves granulating the coal into a fine dust, which is
sprayed into a boiler heated to over 1400C. Such temperatures convert water into steam in
pipes above the flame, which are linked to electricity-generating turbines. FBA is the coarser
derivative which collects at the base of a pulverised coal furnace; it contains important
compounds such as silica, alumina and iron oxide (Figure 2.6) (Joshi and Lohtia, 1997; Sear,
2001; Department of Trade & Industry, 2002).

Figure 2.6: A pulverised coal-fired power plant (Department of Trade & Industry, 2002)

FBA is almost entirely used in the UK as a coarse aggregate, primarily for road-base, bulk
fill, and also in block manufacture. Approximately 15% of FBA is currently as a lightweight
aggregate in concrete, although no reports of its use in housing were found in the literature
(CIRIA, 1999; Sear, 2001; UKQAA, 2002).

Incinerator Bottom Ash (IBA)

At present, there are 18 municipal solid waste (MSW) incinerators in the UK: 16 in England,
and 2 in Scotland (Environment Agency, 2006; SEPA, 2008). The 11 English incinerators
disposed of approximately 10% of English municipal waste per annum between the years
1999 and 2001. Likewise with coal-fired power plants, MSW incinerators also produce a
light particulate residue (incinerator fly ash (IFA)), and a heavier residue (incinerator bottom
ash (IBA)) (Environment Agency, 2002).
35
As with FBA, IBA can be used as an aggregate, and is heavily used in continental Europe to
this end. MSW incineration in the UK produces around 0.6 million tonnes of IBA and around
70,000 tonnes of IFA. In the UK, approximately half of IBA is sent to landfill. The
remainder is used as bulk fill aggregate in road-base and asphalt, and may be used in low-
strength concrete blocks (up to 25% by mass). It is not known if any IBA has been used in
housing (Anderson, 2002; Environment Agency, 2002; Dhir et al, 2005).

Pulverised Fuel Ash (PFA)

The value of PFA as a pozzolanic material in concrete has been recognised for nearly a
century, and it has been used worldwide since the 1950s (Nawy, 1997). Neville (1995)
reported that PFA became the most popular pozzolana on the market. In 1997, 56% of British
PFA was used in construction; in 2002, that figure rose to over 60%. During these years, the
uses and destinations of PFA in the UK were recorded (Figure 2.7) (UKQAA, 2002).
0% 20% 40% 60% 80% 100%
1997
2002
Disposal
Aerated concrete
Bulk fill
Concrete addition
Stockpiling
Grouting
Cement kilns
Blended cement
Miscell
Cenospheres

Figure 2.7: PFA utilisation in the UK (Sear, 2001; UKQAA, 2002)

In addition to partly replacing Portland cement, the benefits of using PFA include reduced
water requirement and bleeding, improved cohesion and plasticity, and reduced slump loss.
Other benefits include greater resistance of the concrete to heat. PFA may also be converted
into Lytag, which is used as aggregate for concrete. PFA particles are pelletised, and heated
until the pellets fuse together; any unburned carbon from the process is used as fuel. Damp
PFA is placed on a belt conveyor via inclined, rotating pan pelletisers, and further water
spraying converts them into pellets. The pellets are transferred onto a sinter stand, and
ignition is conducted at 1000-1200C. The Lytag aggregates are used for concrete blocks
which are designed to a high insulation standard (Sear, 2001; Malhotra and Mehta, 2002).
36
Silica Fume (SF)

In contrast to previously mentioned secondary materials, silica fume is neither produced in
the UK, nor is it extensively used. The UK imports modest quantities, which are used to
partially replace cement. SF imparts greater concrete durability, impermeability and
cohesion. It also reduces concrete bleeding and improves setting. It is not known whether or
not SF has been used in any housing projects in the UK. Silica fume is produced exclusively
by the electronic materials industry during the manufacture of silicon. High-purity quartzite
(and possibly some iron ore) is combined with coal, and heated in an electric arc furnace at
2000C (Figure 2.8). Within this environment, silicon is separated from oxygen, although
some silicon rises through the flue gases, and reacts with oxygen to form microscopic
spherules of amorphous silica (0.1 0.5m diameter). SF is typically light to dark grey,
comprising >85% silica; it may be supplied in powder form, or may be treated with water to
produce a slurry (Day, 1995; Neville, 1995; Chandra, 1997; Hewitt, 1998; Silica Fume
Association, 2005).

Figure 2.8: The silica fume production process (Silica Fume Association, 2005)

Construction and Demolition Waste (C&DW)

Clay bricks and concrete material from demolished structures are increasingly being utilised
in new buildings in the UK. Clay bricks from older structures (wherein the clay bricks are
mechanically stronger than the supporting mortar) are routinely dislodged and retrieved
during demolition for re-use in new structures (Gregory et al, 2004).

37
BS 8500-2 (2006) provides specifications regarding the use of both coarse recycled concrete
aggregate (RCA) and recycled aggregate (RA) from demolished structures. RCA comprises
at least 83.5% concrete, and is produced from demolished concrete structures, and from
discarded or unused pre-cast concrete units. The composition of RA is less specific
(containing concrete, masonry and/or natural stone), and RA material must be assessed on a
case-per-case basis prior to use. In addition, a note is provided under the standard on the use
of clean fine RCA and RA under the BS 8500-2 (2006) standard. Under the standard, RCA or
RA materials must meet strict standards prior to their use in concrete, with limits specified for
masonry, fines, asphalt, foreign materials (e.g. glass, plastics, metals), chloride and sulphate
content in the material. As a result, their usage in the construction industry is currently
restricted (Dhir et al, 2006).

2.2.1.10 Waste Materials Considered for Use in Concrete

Several other industrial by-products possess properties that make them potentially suitable for
use as aggregate or as pozzolanic materials, and have either been studied as part of research
projects, or used abroad. However, they have not yet been endorsed by the UK construction
industry, either because utilisation may be technically complicated, or due to environmental
concerns. Four main waste materials are examined in this sub-section.

Cement Kiln Dust (CKD)

Cement Kiln Dust is the particulate matter which ascends from the clinker in the cooling
chamber downstream from the rotary kiln in a cement kiln (Figure 2.3). CKD contains
cement clinker, condensed inorganic volatiles and some partially calcined raw materials. The
CKD is normally recycled back into the pre-heaters and the rotary kiln. The residue is
presently disposed of to landfill, or used as an alkaline treatment at sewage treatment works.
It may also be used as an agricultural fertiliser for acidic soils, and tests have been conducted
on using CKD as a filler in concrete. CKD has been used in construction for example, the
embankments along the M180. Nevertheless, it is neither generally used for housing building
blocks, nor is it recognised in any British Standards (Halliday, 2002).

Construction and Demolition Waste (C&DW)

Between 70 and 90 million tonnes of C&DW is produced in the UK each year. However,
only about a tenth of aggregate used in British housing is secondary or reclaimed (Entec,
2004). Only around 4% of C&DW is processed to a grade worthy of usage as aggregate in
38
building projects; recycled concrete waste is generally used as bulk fill (e.g. sub-base for new
roads). C&DW also has potential applications as a substitute for cement or for fine aggregate
(Table 2.7). Utilising C&DW for building projects can incur logistical and environmental
problems - it would rely on an adequate and consistent provision of locally sourced waste
material, which was processed to a high grade (CIRIA, 1999). A list of C&DW materials is
provided in Table 2.7 (Samarin, 1999).

Table 2.7: Possible uses of C&DW in construction materials

C&DW Material

Details

Potential Re-use
Rejuvenated cement Fine fraction of concrete rubble,
enriched in disaggregated
mortar and cement grains
Secondary binders, cement
extenders?
Crushed (clay)
bricks
Recycled clay bricks crushed or
fragmented
May be used as aggregate; some
projects undertaken
Crushed glass Retrieved glass from
demolished premises sieved and
crushed
May be used as fine aggregate
Retrieved clay
bricks*
Clay bricks (usually from pre-
1940 buildings) dislodged and
re-used
~150M bricks reclaimed in 2003,
substituting for ~6% of annual new
clay brick production. Lime
mortar-fixed (pre-1950s) bricks
easier to dislodge and re-use, in
contrast with Portland cement-
based mortar-fixed bricks.
* Buildings Research Establishment, 2003
Incinerator Fly Ash (IFA)

IFA is one of the most contentious, but potentially useable, by-products. IFA is a grey/white,
pozzolanic activating powder, which has been successfully tested as an addition to Portland
cement (meeting the BS EN 450 requirements). Nevertheless, the usage of IFA is beset by its
chloride content (making it unsuitable for pre-stressed/re-enforced concrete), and its potential
toxicity (especially its dioxin, furan and heavy metal content). If IFA was to be used, each
batch of ash would need to be rigorously examined. Furthermore, there are no BS standards
addressing the use of IFA. Consequently, IFA is disposed of to landfill (Environment
Agency, 2001; Dhir et al, 2005).

Sewage Sludge (SS) and Sewage Sludge Ash (SSA)

The annual quantity of sewage sludge (SS) produced by wastewater treatment plants in the
UK increased markedly during the last decade, when the EU Urban Waste-Water Treatment
Directive (WWTD) was implemented in Britain in 1998. Under this legislation, the marine
39
dumping of SS (the semi-solid residue separated from purified effluent), and untreated
sewage in rural regions, were both made illegal. An alternative option is incineration, which
is used to treat approximately one quarter of British SS, and which produces sewage sludge
ash (SSA) (Anderson and Skerratt, 2003).

Until the late 1990s, two types of incinerator were used: the multiple-hearth, and the fluidised
bed models. The multiple hearth model is no longer used (Anderson, 2003). Fluidised bed
incineration is conducted at 9 plants in England (Environment Agency, 2006). A typical plant
layout (based on four plants controlled by Yorkshire Water plc) is provided in Figure 2.9.
The SS is fed through a belt compressor to remove excess water, and injected into the steel
and refractory furnace chamber above the sand inlet (Cheremisnoff, 1992; Halliday, 2002).

Air is injected through the foundations, agitating the sand particles, and evenly distributing
heat and ignition of the SS. This also prevents dust depositing within the chamber there is
no bottom ash. Temperatures of 750 925C are maintained, and large quantities of excess
air are injected, in order to minimise incomplete combustion and the formation of unburned
hydrocarbons and carbon monoxide. The particulate (or SSA) is collected by electrostatic
precipitators (ESPs), fabric filters and scrubbers, all of which separate the particles out from
the flue gas (Cheremisnoff, 1992; Halliday, 2002).

Figure 2.9: Fluidised bed SS incineration (Cheremisnoff, 1992; Halliday, 2002)

Another option being tested is to co-incinerate SS in cement kilns, power plants and other
industrial furnaces. A third disposal option is to use SS as a feedstock for construction
materials, including concrete. SSA may also be incorporated into clay bricks or concrete
(Anderson and Skerratt (2003), and Halliday (2002)).
40
2.2.2 Clay Brick Production

The manufacture of clay bricks has been practised in the UK for centuries, and the material is
still used extensively in housing construction. Around the turn of the 1990s, 91% of bricks
(i.e. <10cm height, <30cm length (BS 6073-2: 1981)) produced in Britain were clay bricks
(2% were calcium silicate, and 7% were concrete). More recently (1997 2000), around 3.0
3.3 billion clay bricks were produced and sold in the UK per annum. In spite of popular
demand, the clay brick market is highly competitive, and clay bricks (per sq. metre of wall)
are generally more expensive than concrete (Brick Development Association, 1994; Everett,
1994; Dept. of Statistics, 2002). The clay brick production process is illustrated in Figure
2.10 (Brick Development Association, 1994).

Figure 2.10: Clay Brick Production Processes (Brick Development Association, 1994)
41
Traditionally, clay bricks are produced from a single input - brick-earth - which exists in
clays, marls, shales and alluvial strata mainly in northern England. The composition and
manufacturing process of clay bricks varies considerably. Three common brick varieties
include red brick, the Staffordshire blue brick and the pale brown lime brick. In general, clay
bricks are manufactured by firing bricks of brick-earth clay to temperatures exceeding
1000C. The most common kiln system in the UK is the continuous kiln, wherein a trolley
containing a batch of clay bricks is heated individually, before the next batch is heated. 90%
of clay bricks were manufactured using this method in the early 1990s (Brick Development
Association, 1994; Everett, 1994; Reid, 2000). Some bricks have been commercially
manufactured in the UK with addition of PFA, blast furnace slag, sewage sludge or sewage
sludge ash (CIRIA, 1999; CERAM, 2005), although no information on the use of such bricks
in housing was found in the literature.

2.2.3 Calcium Silicate Bricks

The composition and production of calcium silicate bricks is uncomplicated - yet this product
does not feature prominently in the housing construction market. Calcium silicate bricks are
formed from the hydraulic fusion of silica and lime, which is conducted using high-pressure
steam treatment. 90% of the product comprises siliceous aggregates, which are encapsulated
in a hydrated quick-lime matrix. Calcium silicate bricks, once compressed into bricks, are
placed in hardening chambers, before being sold to market. They are characterised by a
whitish-grey colour, and are resistant to frost and sulphate attack (Powell, 1979; Brick
Development Association, 1994; Marshall and Worthing, 1995).

2.2.4 Plaster, plasterboard and Flue Gas Desulphurisation (FGD) Gypsum

Plastering has been applied to internal walls for centuries, in order to prevent water intrusion,
and improve the aesthetic appearance. Table 2.8 details a few different plasters and
plasterboard materials which have been used during the last century in the UK.

FGD Gypsum

The use of natural gypsum for plasterboard has recently been substituted for an equally pure
gypsum ingredient, which is produced from flue gas desulphurisation units in power plants,
incinerators and other industrial plants. FGD is the product of processes used to treat acid
rain-producing emissions, namely oxides of sulphur.

42
Table 2.8: Plastering varieties
Category Composition Purpose/usage
Carlite Lightweight
Plasterboard
Gypsum + lightweight
expanded sand particles
Possesses all standard
properties of modern
plasterboards (thermal
insulation, water + fire
resistance, low mass).
Dominates the plaster
market.
Thistle Plaster (similar to Carlite
plasterboard)
Used in post-war years; no
longer available.
Gypsum Plaster class A Plaster of Paris; used rarely
for architectural restoration.
Gypsum Plaster class B
Gypsum (mixed with water)
Harder surface than Plaster
of Paris; more controlled
setting.
Lime plaster Lime putty Popular before 1950s. Now
rarely used due to low
strength mixed with water
and sand, the putty takes
several weeks to dry and
harden.
Perlite plaster Portland cement + lime +
Perlite lightweight
aggregates
For enhanced thermal
insulation.
Masonry Plaster Portland cement + lime +
sand
Suitable as an undercoat in
most masonry backgrounds.

This is achieved using lime powder or slurry, which is injected into an atmosphere heated to
130C, and reacts to produce gypsum (Joshi and Lohtia, 1997):

Ca(O
x
(H)
y
)
(x+y)
+ SO
2-3
CaSO
4
.H
2
O

If the FGD is collected downstream from particulate filters, the gypsum formed is pure
enough to be sold commercially. In addition, FGD can potentially be combined with ash,
lime and cement, and used in concrete (Chandra, 1997; Joshi and Lohtia, 1997).

2.2.5 External Rendering

As with plastering, external rendering and masonry have also featured on properties for
centuries. Today, rendering is a standard application on new housing, in order to improve
water resistance, thermal insulation, and the appearance of the house. It is usually composed
of mortar with medium-sized aggregates (namely quartz chips). Masonry and external
rendering have proved increasingly popular with home-owners both in the UK and abroad.
External rendering may comprise natural stone, clay brick, concrete, calcium silicate, cast
43
stone, structural clay, terra cotta, adobe or even glass ornamental or architectural blocks.
Additionally, external rendering may contain air-entraining or accelerating admixtures
(especially metal stearate water-repellants); pigments may also be added (Marshall and
Worthing, 1995; Beall, 2001; Hendry, 2001; Simmons and Olin, 2001).

2.3 DIOXINS (PCDDs) AND FURANS (PCDFs)
2.3.1 Chemical and Physical Data

The term dioxin is used to refer to two families of 210 structurally similar organic
molecules (which are referred to throughout this thesis as PCDDs and PCDFs). 75 types are
classed as dioxins (full name: polychlorinated dibenzo-para-dioxins, PCDDs, or CDDs);
135 are classed as Furans (full name: polychlorinated dibenzofurans, PCDFs, or CDFs)
(ATSDR, 1998; 1994).

Dioxin and furan molecules are composed of two benzene molecules linked, either by one or
two oxygen atoms (Figure 2.11). They contain a varying number of chlorine (Cl) atoms.
Each different type of molecule (or congener) is labelled according to the number and
positioning of its chlorine atoms. Thus 2,3,7,8-TCDD (the most toxic and famous dioxin)
contains Cl atoms located on the 2, 3, 7 and 8 positions (Figure 2.11) (McKay, 2002):

Figure 2.11: Dioxin and furan molecular structures and Cl atom positions

The 210 congeners are categorised into homologues, each representing congeners with a
certain number of Cl atoms on each molecule (Table 2.9). Congeners containing Cl atoms in
the 2, 3, 7 and 8 positions are believed to be toxic to humans and biota, possibly due to
greater reactivity of the molecules. PCDD/Fs are characterised by moderately high boiling
points, low vapour pressure (i.e. they will not quickly evaporate), and their strong affinity for
non-polar substances such as oils, organic matter and carbohydrates. They are therefore
hydrophobic, and they bind strongly to biological tissue, and thus are bio-accumulative.
PCDD/Fs are strongly attached to solid surfaces and do not easily leach from soil or sediment,
unless exposed to high temperatures (above 200C) (Agency of Toxic Substances & Disease
Registry, 1998; 1994).
44
Table 2.9: Dioxin and furan homologues

Cl atoms

Title and synonym

Cl atoms

Title and synonym
Dioxins Furans
0 Dibenzodioxin (DD) 0 Dibenzofuran (DF)
1 Monochlorodibenzodioxin (MCDD) 1 Monochlorodibenzofuran (MCDF)
2 Dichlorodibenzodioxin (DCDD) 2 Dichlorodibenzofuran (DCDF)
3 Trichlorodibenzodioxin (TrCDD) 3 Trichlorodibenzofuran (TrCDF)
4 Tetrachlorodibenzodioxin (TCDD) 4 Tetrachlorodibenzofuran (TCDF)
5 Pentachlorodibenzodioxin (PeCDD) 5 Pentachlorodibenzofuran (PeCDF)
6 Hexachlorodibenzodioxin (HxCDD) 6 Hexachlorodibenzofuran (HxCDF)
7 Heptachlorodibenzodioxin (HpCDD) 7 Heptachlorodibenzofuran (HpCDF)
8 Octachlorodibenzodioxin (OCDD) 8 Octachlorodibenzofuran (OCDF)

2.3.2 Sources of Dioxins and Furans to the Environment

Dioxins and furans occur at trace levels in the environment; they are produced both naturally,
and artificially. Emission sources are dominated by combustion processes (Kjeller and
Rappe, 1995; Dept of Environment, Fisheries & Rural Affairs, 2000). Dioxins and furans are
also formed within some chemical industry processes such as pesticide manufacturing.
Figure 2.12 illustrates the sources and proportions of PCDD/Fs released to the air in Britain in
1999. The management of dioxin and furan emissions has been the subject of widening EU
and British legislation during the 1990s. Total emissions of dioxins and furans into the
British atmosphere were reduced by over 80% between 1990 and 1999, and industrial
emissions were reduced by over 90% during that period. This was mainly achieved by
closure of several inefficient incinerators (Dept of Environment, Fisheries & Rural Affairs,
2000).
0 5 10 15 20 25
Miscellaneous
Accidental / open fires
Iron/steel production
Other industrial combustion
Hazardous incineration
Non-ferrous metal smelting
Power stations
Domestic energy use
Road transport
MSW incineration

Figure 2.12: Sources of dioxin and furan emissions to air in the UK in 1999 (%)
45
2.3.3 Formation and Destruction

Olie et al were the first researchers to identify the occurrence and formation of PCDD/Fs in
incineration, in 1977 (Addink et al, 1998). Since then, an overwhelming majority of research
into the formation and suppression of PCDD/F emissions has focussed on MSW incineration,
alongside limited interest in iron ore sintering, and scant investigation into other forms of
combustion. Existing theories on the formation of PCDD/Fs are therefore only relevant to
incineration; at best they are uncertain, and several reactions or catalysts proposed by some
researchers have been disproved or disputed of by others. To date, the exact mechanism of
PCDD/Fs remains unclear, although means of suppressing emissions into the environment
have been developed successfully (McKay, 2002).

2.3.4 The Mechanisms of PCDD/F Formation

The formation routes and chemical reactions producing PCDD/Fs have been continuously
debated during the last 25 years. It is generally agreed that in order to produce PCDD/Fs,
there must be (1) an adequate supply of appropriate quantities of carbon, oxygen, hydrogen
and chlorine atoms, and (2) certain combustion conditions, which produce products of
incomplete combustion (PICs), which consist of the necessary aromatic (benzene ring-based)
compounds, which in turn can react to form dioxins and furans (Stanmore, 2004). These
assumptions (in that order) support two main theories of formation:

(1) De novo formation - the assembly of C, Cl, H and O atoms in the correct
proportions to yield PCDD/Fs
(2) Pre-cursor formation whereby PCDD/Fs are produced from similar
compounds containing benzene rings. This may occur with particulate
matter catalysing the reactions.

Some researchers have presumed that certain products of incomplete combustion (PICs,
especially organic molecules, e.g. benzene) may react with one another to form dioxins and
furans in gas-phase formation reactions. This theory is strongly doubted by most researchers,
although it has not been conclusively disproved (Cains and Dyke, 1993; Eduljee, 1999;
Stanmore, 2004). The three dioxin/furan formation routes are illustrated in Figure 2.13. It
has also been speculated in the past that pre-existing PCDD/Fs contained in fuel and waste
feed entering an incinerator may pass through the furnace and into the flue gas emissions.
However, most combustion-based processes employ furnace conditions capable of destroying
dioxins and furans upon entry (McKay, 2002).
46

Figure 2.13: The three main PCDD/F formation routes (Environment Australia, 2003)

2.3.5 Control of Dioxin and Furan Emissions

Dioxin and furan formation will occur when particulate matter is retained by air pollution
control devices (e.g. fabric filters), within temperatures of between 200C and 800C, over
prolonged periods of time (i.e. a few hours). The maximum rate of formation is said to occur
between 300C and 400C (Tupperainen et al, 2998; McKay, 2002). Formation within a
furnace is unlikely, since temperatures in incinerators, power plants and kilns are in excess of
850C, as required under EU legislation. During the 1990s, the elimination of PCDD/F
emissions to air was prioritised under the EU Waste Incineration Directive, and as a result,
PCDD/Fs have been increasingly concentrated in fly ash (Landesumweltamt Nordrhein-
Westfalen, 1997). In cement kilns, coal-fired power plants, MSW and sewage sludge
incinerators, air pollution control devices (APCDs) can include electrostatic precipitators
(ESPs), bag filters, cyclone filters, scrubbers and activated carbon injectors. Table 2.10
describes the purpose and efficiency of the main filters used in the UK.

2.3.6 Health Effects of Exposure to Dioxins and Furans
2.3.6.1 Background

Dioxins are regarded by regulators and the media to be some of the most toxic chemicals in
existence (BBC, 2001). In reality, such a claim has been both inaccurate and difficult to
prove. However, during the 1970s and 1980s, public fears over PCDD/Fs were ignited by a
Pre-cursor
molecule I
Pre-cursor
molecule II
GAS PHASE FORMATION
(Chemical reaction)
Dioxins and
Furans

Particulate Matter
HETEROGENEOUS
FORMATION
(Chemical interaction with
particulate matter)
Carbon Metal
chlorides
DE NOVO
FORMATION
Hydrogen
Oxygen
47
number of poisoning incidents whereby people were heavily exposed to 2378-TCDD - the
Vietnam War, and the Seveso pesticide factory accident in northern Italy were the worst
cases. People exposed during these events experienced severe deformities, skin lesions and
several other symptoms, which prompted scientists to investigate if PCDD/F exposure was
the cause (Bates, 1999).

Table 2.10: Air Pollution Control Devices for PCDD/F emissions control

APCD

Description

Efficiency
Activated carbon
(Buekens and Huang,
1998; Environment
Agency, 2002; McKay,
2002)
Injection of carbon powder into the flue gas
can significantly adsorb and remove dioxin,
furan, mercury and other heavy metal
emissions. Used in UK MSW incinerators.
Removal efficiencies
exceed 95% of PCDD/Fs
from flue gas; satisfies EU
regulation
Electrostatic
precipitator
(Environment Agency,
2002; McKay, 2002)
An ESP employs an electrical field, which
charges and retains particulate matter.
ESPs in incinerators widely
replaced by activated
carbon and scrubber
facilities during 1990s, due
to weak PCDD/F control.
Fabric Filter
(Fell, 1998; McKay,
2002)
6-8 inch diameter fabric barriers composed
of woven fibre-glass material, usually
arranged in series retrain particulate matter
Traps particle-bound
dioxins and furans only
Scrubber
(McKay, 2002;
Stanmore, 2004)
Scrubbers are primarily designed to remove
acidic (acid rain) gases, namely nitrous and
sulphurous dioxides. These incorporate
lime, which can be sprayed as a powder or
as a slurry.
Lime (CaO) injection
suppresses PCDD/F
emissions, although CaCO
3
is less successful.
Selective Catalytic
Reduction (SCR)
(Buekens and Huang,
1998; McKay, 2002)
Used to treat nitrous gases. The catalysts
used in SCR devices (e.g. titanium,
vanadium, tungsten) also decompose
organohalogens (e.g. PCDD/Fs).
Temperatures exceeding
200C must be contained,
thus PCDD/F emissions
may increase

2.3.6.2 Toxicity of PCDD/F Congeners

Human data on exposure to dioxins and furans is both limited and inconclusive (International
Agency on Research into Cancer, 1997). Laboratory animal experiments conducted since the
1950s have produced evidence on the toxicity of some dioxin and furan congeners to some
species. Of the 210 congeners, 17 congeners (7 dioxins, 10 furans) are known to be toxic, and
of those toxic congeners, only the properties of 2378-TCDD have been extensively studied
(International Agency on Research into Cancer, 1997). Test animals exposed to 2378-TCDD
have exhibited skin lesions, cancerous, mutagenic and neurological disorders. However, the
toxicity of 2378-TCDD varies widely between species, and it is difficult to prove if symptoms
experienced by one or more species can be experienced in humans, since the adsorption and
metabolism of PCDD/Fs vary between species (Ahlborg et al, 1992; Bates, 1999).
48
Nevertheless, the degree of toxicity of 17 dioxin and furan molecules (Table 2.11) within
guinea pigs is used as a guideline for environmental and biological data analysis (Bates,
1999). The danger presented by the dioxin and furan mixture is presumed to be additive,
although the toxicity of each molecule varies. A Toxic Equivalency calculation is therefore
performed. It is generally agreed that 2378-TCDD is the most toxic congener therefore it is
ascribed with an I-TEF (Toxicity Equivalent Factor) value of 1.0. The other 16 congeners are
ascribed with TEF values, which reflect their toxicity in comparison with 2378-TCDD; their
TEF values are therefore smaller. The additive effects of the 17 toxic congeners are assessed
by multiplying the concentration of each congener by their TEF value, and then totalling the
values to produce a concentration of total PCDD/Fs (known as the Toxic Equivalent (I-
TEQ)), as if they were all 2378-TCDD (McKay, 2002). This is illustrated in Equation 2.1:
2.1
=
=
n
i
i i
C TEF TEQ
1
) (
Whereby C = concentration of each congener (e.g. ng/kg), and (n) = 17 (toxic congeners)

Six TEF tables are used internationally (Danish EPA, 1997) (Table 2.11). I-TEF values are
approximate, and are derived from toxicological and biological studies. The actual toxicity of
each congener relative to one another has been debated for many years (USEPA, 2001). The
most common table is the I-TEF system, which was produced by NATO during the late
1980s. Five other tables are also used in some countries.

Table 2.11: The six recognised TEF systems (Danish EPA, 1997; McKay, 2002)

Congener

I-TEF
(NATO)

WHO-TEF

N-TEF
(Norway)

BGA-TEF
(Germany)

EPA-TEF
(USA)

Eadon-TEF
(USA)

Dioxins
2378-TCDD 1 1 1 1 1 1
12378-PeCDD 0.5 1 0.5 0.1 0.5 1
123478-HxCDD 0.1 0.1 0.1 0.1 0.04 0.03
123678-HxCDD 0.1 0.1 0.1 0.1 0.04 0.03
123789-HxCDD 0.1 0.1 0.1 0.1 0.04 0.03
1234678HpCDD 0.01 0.01 0.01 0.01 0.001 0
OCDD 0.001 0.0001 0.001 0.001 0 0
Furans
2378-TCDF 0.1 0.1 0.1 0.1 0.1 0.1
12378-PeCDF 0.05 0.05 0.01 0.1 0.1 0.33
23478-PeCDF 0.5 0.5 0.5 0.1 0.1 0.33
123478-HxCDF 0.1 0.1 0.1 0.01 0.01 0.01
123678-HxCDF 0.1 0.1 0.1 0.01 0.01 0.01
123789-HxCDF 0.1 0.1 0.1 0.01 0.01 0.01
234789-HxCDF 0.1 0.1 0.1 0.01 0.01 0.01
1234678HpCDF 0.01 0.01 0.01 0.01 0.001 0
1234789HpCDF 0.01 0.01 0.01 0.01 0.001 0
OCDF 0.001 0.0001 0.001 0.001 0 0

49
The Agency for Toxic Substances and Disease Registry (1994; 1998) summarised the
reported symptoms, and commented on the certainty of their occurrence with exposure to
dioxins and furans. This was collated into two tables, which are reproduced and combined in
Table 2.12.

Table 2.12: Health Effects of Exposure to Dioxins (PCDDs) and Furans (PCDFs)

Symptoms (category)

Link with dioxin exposure

Link with furan exposure
Cancer (in general) Yes Probable
Cardiovascular diseases Probable (no data)
Chloracne Yes (no data)
Developmental effects in
children of exposed mothers
Yes Probable
Diabetes Uncertain (no data)
Immunodeficiency Uncertain Probable
Liver disease Probable (no data)
Mortality increase Probable Probable
Neurological effects Uncertain Probable
Reproductive disorders Uncertain Probable
Respiratory effects Uncertain (no data)
Thyroid gland effects Uncertain (no data)
Urinary (and kidney) disease No evidence (no data)

2.3.7 Levels in Environmental and Anthropogenic Materials

Dioxins and furans occur at trace concentrations in the environment. Each type of congener
may occur at a few tens to 100s of nanograms (ng, billionths of grams) in soil, plants and
animals. The concentrations in air are usually several orders of magnitude smaller (usually
below 1 10
-12
grams / m
-3
), and occurrence in water is negligible. Concentrations of dioxins
and furans (measured in terms of toxicity, i.e. TEQ) occurring at hundreds of ng I-TEQ/kg
and above are therefore viewed with concern. Figure 2.14 illustrates the concentrations of
dioxins and furans recorded in the literature for environmental materials (e.g. soil), industrial
wastes and by-products (e.g. PFA), and construction materials and products.

2.3.7.2 Regulations and Recommended Concentrations of PCDD/Fs in Solids

Regulations on dioxin and furan emissions have focussed on addressing their sources, such as
incineration and pesticide production. Regulations in the EU and in the UK have therefore
imposed limits on emissions to air, and imposed restrictions on processes. There are no
EU/UK guidelines or laws, which address the concentrations of PCDD/Fs in products such as
50
construction blocks. However, in Germany the Chem-Verbots V rule details maximum
permissible concentrations of the 17 toxic congeners for commercial products although not
in TEQ units. In the UK, the aggregates industry is considering a 50ng ITEQ / kg limit on
PCDD/Fs in their products (Dawy, 2004). This is similar to the ATSDR guideline in the
United States for soil remediation, whereby a soil containing above 50ng ITEQ / kg of
PCDD/Fs may need to be assessed before it can be used for further development (Halliday,
2002).

2.3.7.3 Reported Concentrations of PCDD/Fs in the Environment (Soil, Sediment)

The concentration of PCDD/Fs in the environment occurs across a wide spectrum, from a few
trillionths of grams per kg, to nearly 0.1grams per kg. Typical soils and sediments are usually
characterised by ITEQ concentrations of a few (tens of) ng PCDD/Fs per kg (Rose et al, 1997;
Bates, 1999; European Commission, 2003). Heavily polluted soils and sediments (especially
near (former) incinerators or organochemical plants) may be enriched with PCDD/Fs, with
concentrations which are several orders of magnitude more (Lorber et al, 1998; Watson,
1998; Krauss et al, 1999; Environment Agency, 2002). The most extreme concentrations of
PCDD/Fs tended to occur in soils outside major organo-chemical plants, or where waste oils
and/or sludge were dumped (e.g. Times Beach, Mississippi) (ATSDR, 1994; 1998).

2.3.7.4 Reported Concentrations of PCDD/Fs in Construction Materials/Products

Information regarding PCDD/F concentrations in construction materials and products is
scarce. Almost all data was obtained from the Environment Agency (2002), resulting from
analyses conducted in the aftermath of the Edmonton incinerator ash scandal. Cement kilns
are also a source of PCDD/F emissions, although cement itself has been found to contain
negligible quantities (Krauss et al, 1999; Hsu and Ling, 2000; Environment Agency, 2002).
When MSW incinerator ash was added to concrete, the concentration in the product exceeded
the 50ng ITEQ / kg limit proposed by the aggregates industry (Dawy, 2004).

2.3.7.5 Reported Concentrations of PCDD/Fs in Secondary and Waste Materials

The concentrations reported cover a wider spectrum than the values reported for primary
materials and construction products in the previous section. Incinerator bottom ash (IBA) and
Pulverised Fuel Ash (PFA) may contain PCDD/F concentrations exceeding 50ng ITEQ / kg,
and which can approach several thousand ng ITEQ / kg or above. However, such values have
been reported outside the UK, and these may owe to the way in
51
0.001
0.01
0.1
1
10
100
1000
10000
100000
1000000
10000000
Building materials
Secondary mat +
CKD Incineration ash Smelter dust Other ash Municipal waste Soil & sediment
C
o
n
c
e
n
t
r
a
t
i
o
n

(
n
g

I
-
T
E
Q
/
k
g
)
References: Sewert et al, 1995; Swithenbank et al, 1996; Danish Environment
Protection Agency, 1997; Dyke et al, 1997; Eduljee et al, 1997; Friends of the Earth,
1997; LUA-NRW, 1997; Rose et al, 1997; Lorber et al, 1998; Watson, 1998; Krauss
et al, 1999; Dionex, 1999; Bates, 1999; Hsu & Ling, 2000; Wunderli et al, 2000;
Nishida et al, 2001; Environment Agency, 2002; Halliday, 2002; Hunsinger &
Vehlow, 2002; McKay, 2002; UKQAA, 2002; Abad et al, 2003; Dyke et al, 2003;
Environment Australia, 2003; European Commission, 2003; Gan et al, 2003; Dawy,
2004

Figure 2.14: Dioxins and Furans in Solid Materials: Main Categories
52
which PFA and IBA are processed or produced abroad (Danish EPA, 1997; Abad et al, 2000;
McKay, 2002; Gan et al, 2003; Dawy, 2004).

Dioxins and Furans in Raw Waste Materials and CKD

CKD (cement kiln dust) contains PCDD/Fs below 50ng (I-TEQ)/kg, usually at negligible
levels. Since input materials entering cement kilns are mostly inorganic, and flue gases are
strongly alkaline, dioxins and furans are not expected to form on trapped particulate matter
(Sidhu et al, 2001). Municipal solid waste materials were reported to contain moderate to low
levels, occasionally above 50ng ITEQ / kg (Danish EPA, 1997; Dyke et al, 1997; Eduljee et
al, 1997; Abad et al, 2000; McKay, 2002; European Commission, 2003). A sole value for
PCDD/F content in waste tyres reveals a low level of 8.91ng ITEQ / kg (Hsu and Ling, 2000).

Dioxins and Furans in Sewage Sludge

Sewage sludge can contain a wide spectrum of concentrations, from below 50ng ITEQ / kg to
over 1000ng ITEQ / kg, depending on the source of the effluent. Sewage sludge from
treatment plants processing urban and/or industrial effluent can be more enriched in dioxins
and furans (Sewert et al, 1995; Danish EPA, 1997; Dyke et al, 1997; LUA NRA, 1997;
European Commission, 2003). One contributing factor to the varying dioxin (PCDDs)
content in sewage sludge is wash-off from urban roads, as particulate matter originating from
diesel and petrol tanks contains PCDDs (ATSDR, 1998). Particulate matter from vehicles or
deposited from the atmosphere is a prime source of PCDD/Fs in effluent (Sewert et al, 1995).

Dioxins and Furans in Sewage Sludge Ash and Industrial Ashes

Incinerator fly ashes of all types may contain concentrations which are consistently above
50ng ITEQ / kg. Some types of ash may be suitable; for example sewage sludge ash samples
(SSA) analysed by Halliday (2002) contained negligible concentrations. However, data for
other SSA samples was not found, so no further conclusions can be drawn. In contrast,
Likewise, foundry/smelter dust and wood incineration ash may contain highly variable
concentrations, although the data supporting this is limited (Danish EPA, 1997; Dyke et al,
1997; Wunderli et al, 2000; McKay, 2002).

53
2.4 CADMIUM, COPPER, LEAD AND ZINC (Cd, Cu, Pb, Zn)
2.4.1 Introduction

Cadmium, copper, lead and zinc occur ubiquitously in the environment at minor (typically
mg/kg) levels in soil, air and water, except in or near enriched mineral ores. All four elements
are transition metals, which have their applications in industry, and which can be toxic either
to humans or to biota, when ingested or absorbed. These elements are found at trace levels in
cement, clay bricks, and in concrete. The potential leaching of heavy metals from secondary
materials and concrete-encapsulated toxic wastes has been of major interest to engineers and
scientists during the past two decades.

2.4.2 The Chemical Properties of Cd, Cu, Pb and Zn

As with almost all metals, Cd, Cu, Pb and Zn occur as mineral compounds in the lithosphere,
and either as compounds, or complex mixtures in soil and biota (Harrison, 1999). They occur
in the solid phase, although they can dissolve into solution when exposed to water of a
moderate acidity (e.g. at <pH5, lead can dissolve). At a neutral or alkaline pH, these metals
are typically insoluble (Van der Sloot and Dijkstra, 2004). As a result, leaching of these
metals from soil, exposed rock or buildings into water is rare, although acid rain and acid
mine drainage may enable dissolution and transport (Markiewicz-Patkowska et al, 2005).

2.4.3 Application and Use of Cd, Cu, Pb and Zn

All four metals are commercially useful in their elemental form; nevertheless, neither these
metals nor their compounds serve any direct purpose for use in concrete, clay bricks or
cement. Their applications are summarised in Table 2.13 (Porteous, 1996).

Table 2.13: Uses of Cd, Cu, Pb and Zn in Industry

Element

Applications
Cadmium
Used in semi-conductors, electroplating bases, PVC manufacture and batteries. No reported
uses in the construction industry.
Copper
Widely used for electrical wires and appliances; also used for piping and various heat-transfer
applications. Also used in some fungicides.
Lead
Used in lead-acid batteries, old water pipes, printers metal, glazes. Lead piping now replaced
by copper piping; no other reported uses in the construction industry (except as shielding in
nuclear facilities). Used as flashings (covering) on buildings.
Zinc
Widely used for electronic components, and as an alloy element for a wide range of metallic
products and fittings (e.g. brass, bronze); also used in dry-cell batteries. Zn compounds used
for paint, rubber, dyes, wood preservatives and ointments. Zn galvinising and flashings used
on buildings.
54
2.4.4 Health / Environmental Effects of Exposure to Cd, Cu, Pb and Zn

Cadmium and lead are toxic to humans when ingested at trace levels, whilst copper and zinc
exhibit comparatively lower toxicity. Cadmium and lead serve no biological function, and are
therefore highly toxic to almost all organisms. Copper and zinc intake is essential only at
trace quantities.

2.4.4.1 Cadmium Toxicity

Cadmium intoxication in humans is exhibited by vomiting, diarrhoea, pneumonia, and colitis.
Even people exposed to atmospheric levels of Cd below recommended doses have
experienced Cd-poisoning symptoms, including hypertension and altered heart beat rates.
One notable cadmium-poisoning incident occurred in Japan in the early 20
th
century, when
local residents exposed to lead and zinc-mining (who drank contaminated water) suffered
from Itai-Itai disease, characterised by severe joint pain, and eventual immobility due to
gradual bone dissolution. Drinking water contaminated with >0.5mg/l of cadmium often
precludes cadmium poisoning for most biota (Porteous, 1996).

2.4.4.2 Copper Toxicity

Copper is an essential trace nutrient. However, a high ingestion rate may render symptoms
including nasal and throat irritation, nausea, and even vomiting or diarrhoea. Very high doses
of copper being ingested (or inhaled as dust) can lead to kidney and liver damage (Agency of
Toxic Substances & Disease Registry, 2004). Copper intoxication can also occur in biota.
Levels of a few mg/l in water can kill algae and fish. Brain-damage often results from high
exposure among higher animal species (Porteous, 1996).

2.4.4.3 Lead Toxicity

The health effects from exposure to lead have been known for decades. Consequently,
several governments worldwide have regulated and reduced the applications of lead, namely
by removing and banning the use of lead water-pipes, or illegalising lead-based petrol
combustion. Lead can penetrate into every organ in the body, especially the nervous system.
Infants drinking water from lead pipes are particularly at risk; high exposure has been
correlated with memory loss, weakened limbs and reflexes, retardation and hyperactivity.
Other symptoms include anaemia, kidney damage and reproductive disorders (Porteous,
1996).
55
2.4.4.4 Zinc Intoxication

As with copper, zinc is also an essential trace nutrient. If quantities more than 10-15 times
above the daily recommended amount are ingested, symptoms (such as stomach cramp,
nausea, anaemia and decreased cholesterol) may develop. It is known that laboratory rats
exposed to high doses became infertile, but similar symptoms have not been observed in
humans (Agency of Toxic Substances & Disease Registry, 2003).

2.4.5 Occurrence of Cd, Cu, Pb and Zn in Environment and Construction Materials

Cadmium, copper, lead and zinc occur in every environmental compartment, and all four
elements often occur in the same mineral deposits. Zinc and cadmium always occur together
in zinc mineral deposits, and lead deposits are also associated with zinc ores. Both natural
and anthropogenic processes have resulted in all four elements being present at elevated
concentrations in both aquatic zones (runoff, rivers, ocean) and in the atmosphere. As a
result, increased quantities of metals are deposited onto land. Figure 2.15 illustrates the
global fluxes of these four metals throughout the environment (units in thousands of tonnes
per annum).

Figure 2.15: Environmental Cycling of Cd, Cu, Pb and Zn (data extracted from ONiell,
1996)

56
All four elements occur in almost all geological strata, and they are therefore present in raw
materials being fed into cement kilns, brick kilns, and exist in aggregates being used in
concrete (Achternbosch et al, 2003; Gossman et al, 1990). In both construction products and
soils, all four elements may exist in the lower parts per million (ppm, mg/kg) range, although
cadmium usually occurs at trace levels (parts per billion, ppb, or g/kg). In comparison,
Radojevic and Bashkin (1998) reported typical soil levels of <0.018mg/kg Cd, <1-390mg/kg
Cu, <1-890mg/kg Pb and 1.5-2000mg/kg Zn.

2.4.6 Concentrations of Cd, Cu, Pb and Zn in Construction Materials

2.4.6.1 Summary of Literature Search

A literature search was conducted into the reported concentrations of total Cd, Cu, Pb and Zn
in construction materials; all data is recorded in Appendix 2. In contrast to dioxins and
furans, metals are never destroyed under intense heat or pressure, and are therefore transferred
from raw materials to cement, concrete and clay bricks, with some loss via flue gas emissions.
Figure 2.16 graphically summarises the data found. In general, the levels of Cu, Pb and Zn
occur between approximately 10mg/kg and 500mg/kg, with Zn concentrations on average
being slightly above the concentrations of Cu and Pb. Cd concentrations are consistently
smaller by around 1-2 orders of magnitude (typically occurring below 10mg/kg).

2.4.6.2 Legislation and Regulation

No prescribed levels of Cu or Zn in cement or concrete (of relevance in the UK) were found
in the literature. In Denmark, recycled materials for construction must satisfy Statutory Order
No. 655 (2000). Materials containing >0.5mg/kg Cd, >500mg/kg Cu, >40mg/kg Pb and/or
>500mg/kg Zn, must be assessed before being used. The health risks posed by these metals
relate to how easily they can be transferred from the product to the user or into the
environment. Leaching is one important pathway for pollutant transfer (Van der Sloot, 2003).

2.4.6.3 Levels of Cd, Cu, Pb and Zn in Materials Associated with Cement Kilns

In cement kilns, metals originate from both the raw feed and the fuel, and the inclusion of
wastes either as a fuel or as raw solid material tends not to exacerbate the levels found in the
clinker or in the final cement product (Achternbosch et al, 2003).

57
Raw Meal

The manufacture of cement has seen an increasing range of secondary materials (e.g.
blastfurnace slag) and alternative fuels (e.g. sewage sludge, petroleum residues) successfully
tested or used in cement kilns in the UK. Introduction of these materials can consequently
introduce trace metals, including Cd, Cu, Pb and Zn (Tanna and Shipholt, 2004).

Gossman et al (1990) analysed samples of coal and hazardous waste fuels. The range of Cd,
Pb and Zn levels reported for coal are comparable with the levels reported for clinker in
Figure 2.16, with Cd being undetected, and Pb and Zn ranging between <10mg/kg and
slightly above 200mg/kg. In contrast, the levels of Pb and Zn in the hazardous waste fuels
were several hundred mg/kg, whilst Cd levels could exceed 70mg/kg.

Achternbosch et al (2003) and Vite-Torres et al (2003) analysed the levels of trace metals in
raw materials being fed into cement kilns. Ordinary raw meal derived from mineral
resources contained comparatively low quantities: Cd levels occurred at trace levels (below
1mg/kg), whilst Pb, Cu and Zn levels were a few tens of mg/kg. Basalt aggregate contained
slightly elevated levels of Cd, Cu and Zn, compared with ordinary aggregate and raw meal.
The authors also investigated the levels of trace metals in blast furnace slag (BFS) and waste
foundry sand. In BFS, moderately elevated levels of Cu and Zn were identified. With
foundry sand, only Pb was analysed; the level was comparatively low. Chandra (1997)
reported minor levels of all four metals in natural and FGD gypsum. Cd levels occurred
below 1 mg/kg, Cu and Pb levels occurred below 10 mg/kg, and Zn levels occurred between
10 and 20mg/kg.

Clinker

The reported levels of Cd, Cu, Pb and Zn in clinker are not dissimilar to the levels reported
for raw meal materials. Cd concentrations occur at slightly higher levels (approaching
5mg/kg). Cu and Pb concentrations range from below 10mg/kg to nearly 50mg/kg, whilst Zn
concentrations are distinctly higher, ranging from 10 mg/kg to almost 200mg/kg. Based on
the findings by Mokrzycki et al (2001), the levels of all four metals do not appear to be
affected by waste co-incineration.

58
0.01
0.1
1
10
100
1000
10000
R
a
w

m
e
a
l

(
9
)
A
g
g
r
e
g
a
t
e

(
9
)
B
a
s
a
l
t

(
9
)
b
l
a
s
t
f
u
r
n
a
c
e

s
l
a
g

(
9
)
F
o
u
n
d
r
y

s
a
n
d

(
1
0
)
G
y
p
s
u
m

(
3
)
F
G
D

G
y
p
s
u
m

(
3
)
C
l
i
n
k
e
r

(
1
,

7
,

9
)
C
E
M

I

C
e
m
e
n
t

(
1
1
)
C
E
M

I
I
I

C
e
m
e
n
t

(
1
1
)
C
E
M

I

c
e
m
e
n
t

(
1
2
)
7
6
%
-
G
G
B
S

c
e
m
e
n
t

(
9
)
3
0
%
-
G
G
B
S

c
e
m
e
n
t

(
9
)
P
o
z
z
o
l
a
n
i
c

c
e
m
e
n
t

(
9
)
S
h
a
l
e

c
e
m
e
n
t

(
9
)
L
i
m
e
s
t
o
n
e

c
e
m
e
n
t

(
9
)
C
e
m
e
n
t

K
i
l
n

D
u
s
t

(
2
,

8
)
C
l
a
y

B
r
i
c
k

(
6
)
C
E
M

I

C
o
n
c
r
e
t
e

(
1
1
)
C
E
M

I
I
I

C
o
n
c
r
e
t
e

(
1
1
)
C
E
M

I

C
o
n
c
r
e
t
e

(
5
,

9
)
O
t
h
e
r

c
o
n
c
r
e
t
e

(
5
,

9
)
(Construction products) (Conventional and potential materials for construction)

Figure 2.16: Levels of Cd ( ), Cu ( ), Pb ( ) and Zn ( ) in construction materials (mg/kg)
(Gossman et al, 1990
1
; USEPA, 1995
2
; Chandra, 1997
3
; Hillier et al, 1999
4
; Hohberg et al, 2000
5
; Karius and Hamer, 2001
6
; Mokrzycki et al, 2001
7
; Halliday,
2002
8
; Achternbosch et al, 2003
9
; Vite-Torres et al, 2003
10
; Marion et al, 2004
11
; Seclerat et al, 2004
12
)
59
Cement and Cement Kiln Dust

The concentrations of Cd, Cu, Pb and Zn are not heavily influenced by the inclusion of
secondary materials in the cement. The concentrations of these metals in CEM I, CEM III
and Portland Cement are comparable with alternative cement types (Figure 2.16). With the
exception of levels reported by Chandra (1997), the range of values reported by Achternbosch
et al (2003) and Halliday (2002) are fairly typical: Cd concentrations barely stray above or
below 1 mg/kg; Cu and Pb concentrations occur in the lower tens of mg/kg, and Zn
concentrations mostly occur within the 50-150mg/kg band. Hillier et al (1999) did not detect
Cd in their Portland cement samples. In contrast, Chandra (1997) reported higher levels of all
four elements in Portland cement samples, with Cu concentrations exceeding 100mg/kg, and
Zn concentrations occurring near and above 500mg/kg.

Limited data exists for concentrations found in cement kiln dust. Only Cd and Pb values were
found. Halliday (2003) reported fairly low levels of Cd and Pb, whereas USEPA reported
much higher average levels (Appendix 2); USEPA also reported minimum and maximum
values of 0.065-44.9mg/kg Cd, and 3.1-2620mg/kg Pb, in CKD (USEPA, 1995).

2.4.6.4 Levels in Clay Bricks

No data was found regarding the levels of Cd, Cu, Pb or Zn in commercial clay bricks.
Karius et al (2000) examined test clay bricks produced using dredged harbour sand. Cd
concentrations were very low, ranging from trace (g/kg) up to 0.7mg/kg; Zn concentrations
were comparable with levels found in most other materials (Figure 2.16). However, whilst
most of the reported Pb concentrations were around 25mg/kg, one outlier value of 6400mg/kg
stands out.

2.4.6.5 Levels in Concrete

Data regarding the concentrations of Cd, Cu, Pb and Zn in concrete (with or without
secondary or waste materials) was reported by Marion et al (2004), Achternbosch et al (2003)
and Hohberg et al (2003). Overall, the inclusion of incinerator ash in concrete can result in
elevated concentrations of heavy metals. The use of secondary materials (namely blast
furnace slag) tends not to significantly raise metal concentrations in concrete.

Hohberg et al (2000) analysed ordinary concrete, and concrete containing incinerator fly ash:
noticeably higher concentrations of Cu and Pb existed in both samples of the latter material.
60
Cd and Zn levels in ash-containing blocks were either similar or much higher than levels
found in ordinary concrete. The levels of Cd, Cu and Pb in ordinary concrete are comparable
to the values produced by Marion et al (2004), except for the markedly higher concentration
of 311mg/kg Zn.

Achternbosch et al (2003) studied concrete samples produced using Portland cement, natural
aggregate, blastfurnace cement or blastfurnace slag. None of these materials strongly
influenced the levels of Cd, Cu or Pb, which existed at typical levels (between 0.1 and
1.0mg/kg Cd; between 10 and 100mg/kg Cu or Pb). In contrast, Zn levels were
approximately four times higher in samples containing blastfurnace slag.

2.4.7 Leaching Studies: Method Design and Quantities Obtained
2.4.7.1 Leaching from Monolithic Construction Materials: Basic Principles and Tests

Under natural environmental conditions, Cd, Cu, Pb and Zn are generally immobilised as
solid compounds or mixtures, with only very minor quantities being leached into water or
transcribed into biota. One prime influencing factor behind leaching is pH. In general,
transition metals are soluble under acidic or highly alkaline conditions; under neutral or
mildly alkaline conditions, they precipitate as compounds or are strongly attached to organic
or inorganic complexes. The release of cations (including Cd, Cu, Pb and Zn) from
construction materials into water is minimal at around pH8 - 9 (Van der Sloot et al, 2004; Van
der Sloot et al, 2001).

There are a wide variety of leaching tests devised for the analysis of both monolithic and
granular materials. With regards to concrete blocks, clay bricks and mortar, only tests for
monolithic samples apply. Table 2.14 summarises the methods detailed in literature. In the
next sub-section, diagrams illustrating reported leaching of metals are based on references
with specific symbols given in this table.

The NEN 7345 Tank Test

This 64-day leaching test using pH4- (nitric acid) - acidified distilled water has been used by
researchers worldwide throughout the last decade. As detailed in Table 2.14, other
researchers have used a variety of leaching test conditions and sample processing techniques.
However, the results from different leaching methods cannot be compared, and a harmonised
standard leaching test method has therefore been designed. This is based on the Dutch
61
NEN7345 test method, which in turn has been endorsed by the Environment Agency (2005)
(with the NEN7375: 2004 standard). It is acknowledged that immersing a monolithic cube in
a tank of distilled water under aerobic conditions over a period of 64 days does not imitate the
interaction of construction materials with soil, groundwater or surface biota. However only a
small number of parameters influencing the leaching of metals from a solid sample into water
can be accurately investigated (Van der Sloot, 2004). The test method is designed to subject
an intact sample to leaching via diffusion control. This is important since the release of
metals from a monolith sample is significantly lower, compared with leaching from a crushed
sample (Van der Sloot et al, 2001).

Where the material undergoing leaching is present as a monolith, metals pass from the
material into the leachant via diffusion. They can be dissolved inside saturated pores in a
sample, and diffuse into the surrounding solution. According to diffusion theory (expressed
using Ficks 1
st
Law of Diffusion), the rate of release of metals from an intact monolith into
solution decreases exponentially over time (Van der Sloot et al, 2004).

The nature and processes affecting metal leaching from buried materials into water can be
highly complex, and analysing them all at once would be impractical. Instead, researchers
have often resorted to using simpler models and tests for monitoring leaching, namely based
on diffusion of metals from impermeable structures (i.e. monoliths). A common theory of
diffusion of metals from monoliths into water derives from Ficks 1
st
Law of Diffusion. This
is a simplified view which only considers metals existing across one spatial dimension (i.e.
the transport of metals between the solid sample and the solution in contact metals from
outside this area entering and leaving the vicinity are not considered).

Ficks 1
st
Law of Diffusion (Equation 2.2) postulates that the Diffusion Flux (J) (i.e. quantity
of metals crossing a certain length in a given period of time) is directly proportional to the
difference in concentration of metals at either end (i.e. in the sample vs the leachant), and
inversely proportional to the distance travelled by the metals:

2.2 |
.
|
\
|
=
x
D J

J: Diffusion flux [(quantity).length
-2
.time
-1
]
D: Diffusion Coefficient [length
2
.time
-1
]
: Differences in Concentration of substance at each end of distance (x) [(quantity).length
-3
]
x: Distance [length]

62
The 1
st
Law of Diffusion also postulates that J is directly proportional to the Diffusion
Coefficient (D also known as KD), which in turn is proportional to temperature, as indicated
in Equation 2.3 (which relates to Gibbs Free Energy theory, whereby increased temperature
leads to faster chemical reactions) (Gutierrez et al, 1996):

2.3
|
.
|
\
|
|
.
|
\
|
=
x RT
Dc
J

J: Diffusion flux
D: Diffusion Coefficient
c: Concentration of species
R: Universal gas constant
T: Temperature (degrees Kelvin)
: Chemical potential
x: Distance [length]

When the log value of total quantity of metal released, is plotted against the log value of time,
the resulting line should have a gradient of approximately 0.5 (Figure 2.17) (Van der Sloot et
al, 2004). Results for monoliths are reported as the cumulative release over time (typically
over 64 days of continual submergence in water). Commonly used units include mg (metal)
released per m
-2
of sample, which are used throughout this report.

Figure 2.17: Diffusion-controlled Leaching of Trace Metals: Release Rate

The rate of diffusion of metals from building blocks is determined by several factors, mainly
acidity, exposure to the atmosphere, and physical changes such as frost intrusion. The release
of metals from a sample can be raised by as much as a few orders of magnitude if the sample
is pulverised, or even if cracks are widespread within a monolithic sample (due to additional
Log cumulative
(mg/m
-2
) metal
release
Log (time)
63
Table 2.14: Monolithic Sample Leaching Methods (taken from references listing results for Cd, Cu, Pb and/or Zn) (continues over-page)
* Symbols are used for plotted / quoted results on Figures 2.18 2.25

Reference*

Method

Material

Dimensions (cm)

L/S ratio

Solution and acidity

Procedure
Barna et al, 2005

(No title) Cd and Pb-
enriched
concrete
3.4 3.4 3.4 10 cm
3
: 1 cm
2

Deionised water, no pH
control detailed
Replace solution and take samples 3, 5, 16,
24, 48, 72hrs, then 2, 3, 3, 4 weeks after
start
Aubert et al, 2004

NF X 31-211 Ash-laden
concrete
(Unspecified)
Density 2350kg.m
-
3

10:1 Deionised water, no pH
control
(No details)
Cai et al, 2004

NEN 7345 Concrete 8 8 15 4.2:1 Deionised water, pH4 Replace solution and take samples 0.25, 1.0,
2, 4, 9, 16, 36, 64 days after start
Marion et al, 2004

NEN 7345 Paving slab
concrete
10 10 10 6:1 Deionised water (no
details regarding pH)
(Ditto)
Christensen et al
2003

NEN7345 Concrete,
concrete+PFA
+IFA
(Variable: vol. 900
1100cm
3
)
4.2:1 De-ionised water, pH4 (Ditto)
Flor et al, 2003

NEN7345 Concrete +
IBA aggreg.
(Unspecified) 5:1 (Unspecified) Leachate extracts collected 28 and 90 days
after start
Van der Sloot et
al, 2003

NEN 7345 Mortar, brick,
asphalt
(No details) 4-6:1 Deionised water (no
details regarding pH)
(Ditto)
Collivignarelli et
al, 2002
(Ditto) Ash-laden
concrete
(No details) 5:1 (No details) (Ditto)
Halliday, 2002 CEN Protocol
Dynamic Leach
Test
Ash-laden
concrete
Mortar prisms cast
according to EN
BS 196-1 (1995)
5cm
3
:1cm
2

(Volume water :
Surface Area)
Tap water, uncontrolled
pH
(Ditto)
Moudilou et al,
2002
CTG-
LEACHCRETE
Cement paste Cylinders 9cm
diam., 10cm height
(No details) Deionised water,
pH 5.0 0.2
Based on Soxhlet extraction. Sample placed
in reactor in water heated up to 40C,
immersed for 1000hrs (42 days).

64

Reference*

Method

Material

Dimensions (cm)

L/S ratio

Solution and acidity

Procedure
(No title) Fly ash
cement mortr
4 4 16 3:1 Deionised water, pH
5.8
Leachate extracts taken 3, 6, 9, 12, 15, 18,
21, 28, 35, 49, 63, 77, 91, 105, 133 days
after start
(Referenced procedure by same authors)
Nagataki et al,
2002

Note No.13, Env
Agency Japan,
1973
(no details) >5mm dimension 10:1 Deionised water,
pH 5.8 pH6.3
6hrs at 20C

Valls and
Vazquez, 2002
NEN 7345 Concrete
+ SSA
>4 x >4 x >4 5:1 Deionised water acidified to
pH4 using nitric acid
Replace solution and take samples 0.25, 1.0, 2,
4, 9, 16, 36, 64 days after start
Van der Sloot,
2001

NEN 7345 Concrete with
synth
aggregates
(No details) 5:1 (No details) Replace solution and take samples 0.25, 1.0, 2,

Hohberg et al,
2000
(Altered) NEN
7345
Concrete with
fly ash
(No details) 5:1 Deionised water, initial step
pH7 or uncontrolled pH,
followed by pH4 setting
Replace solution and take samples 0.25, 1,
2.25, 4, 7 days after start
Replace solution and take samples 1, 2, 3, 7,
14, 21, 28, 42, 70, 100 days after start
Serclerat et al,
2000
(No title) Ordinary
concrete
Circular discs:
1.4cm high,
8cm diameter
4.33:1 Deionised water,
pH12.7 (non-aggressive) or
pH7 (aggressive) Leave sample in water for 100 days without
replacing water; take aliquots periodically
Hillier et al, 1999 NVM 5432 Test
(Environ.Canada)
Ordinary
concrete
10 10 10 30:1 Deionised water (no details
regarding pH)
Replace solution, take samples 1.5h, 6h, 24h, 4
days, 16 days, 64 days, 256days after start
Lewin, 1996 (Ditto) Cement
mortar + IFA
4 x 4 x 4 5:1 De-ionised water Replace solution and take samples 0.25, 1.0,
2.25, 4, 9, 16, 36, 64 days after start
Van der Loo, 1995 (Altered) NEN
7345
Slag-laden
concrete
4 4 16 5cm
3
:1cm
2
Drinking (tap) water, no pH
control
Replace solution and take samples 0.25, 1.0, 2,

Additional notes:

References without symbols reported negligible results (i.e. below the limit of detection). Undetected Cd results were reported by Halliday (2002), Hillier et
al (1999) and Lewin (1996). Undetected Cu results were reported by Halliday (2002). Undetected Pb results were reported by Halliday (2002), Moudilou
(2002), Hillier et al (1999) and Lewin (1996). Undetected Zn results were reported by Halliday (2002)
65
exposed surface area) (Aubert et al 2004). The chemical and physical influences are
summarised in Figure 2.18 (Van der Sloot et al, 2003).

Figure 2.18: Determining factors affecting metal leaching from monoliths

Leaching tests on cementitious materials mainly commenced during the early 1980s, since
concrete or cement mortar were considered to be resistant, stable media for immobilising
pollutants from toxic and landfill waste (Fllman et al 1996). If exposed to neutral or alkaline
water, trace metals generally do not leach from cementitious materials, since they are retained
as oxides or within mineral phases under the strong alkaline pH conditions imposed by the
cement. The dissolution of Portlandite (Ca(OH)
2
) releases hydroxide (OH
-
) ions into the
water, thus raising the pH (Kamali et al, 2003).

Clay bricks impose a smaller influence on water. If they are placed in distilled water, the pH
remains neutral (7 8) (Van der Sloot et al, 2004). Karius et al (2002) reported on the
adsorption of Cd and Cu into a granulated clay brick column, through which water was
filtered. This was not due to Cd/Cu oxide precipitation, but adsorption of these metals onto
iron hydroxides, aluminium precipitates, and (to a smaller extent) silica (Karius et al, 2002).
No detailed studies reporting on the leaching of trace metals from clay bricks were found in
the literature.

Concrete containing silica fume (SF) and PFA imposes a weaker alkaline effect on the
surrounding water. This is due to the pozzolanic effect, whereby the Portlandite content is
66
decreased, and denser C-S-H is formed (Kamali et al, 2003). The resulting matrix is less
porous, and therefore less susceptible to significant leaching of metals. Indeed, the
cumulative release of metals into solution seldom relates to the total metal content in the
solid, but is more closely related to the leachant pH, and the porosity and surface area of the
sample (Van der Sloot et al, 2004; Kamali et al, 2003). Another important factor relevant to
concrete samples is the degree of carbonation, which correlates with the age of the sample.
Ambient air contains carbon dioxide, which diffuses into water or surface moisture to form
carbonic acid. The acid in turn reacts with hydrate minerals in cementitious matter, namely
Portlandite:
H
2
CO
3
+ Ca(OH)
2
CaCO
3
+ 2H
2
O

As a consequence, the pH of internal pore water can be reduced from around pH12.6 - 13.5,
to around pH9 (Neville, 1995). For this reason, Van der Sloot (2004) reported cumulative Pb
release from aged concrete to be as much as 2 orders of magnitude lower, compared with
release from fresh concrete.

2.4.7.2 Quantities of Cd, Cu, Pb and Zn Leached from Construction Materials
Regulations

There is no specific British legislation addressing the control of metal leaching from building
materials. The prime focus of leaching studies has been with incinerator ash-laden concrete,
or with concrete used within landfill structures. The NEN 7345 Netherlands Tank Leaching
Test prescribes lower and upper guideline limits of metals released from samples. This is
measured as total mg metal released per m
-2
sample surface area over 64 days (Table 2.15).
An updated version of the standard (NEN7375) has been adopted by the Environment Agency
as a method of assessing the leaching of metals emanating from various solid wastes (being
sent to landfill) into groundwater.

Table 2.15: NEN7345 Guideline Leaching Limits (reported by Valls and Vazquez, 2002)

Contaminant

Lower guideline limit
(U1) mg.m
-2

Upper guideline limit
(U2) mg.m
-2

Cadmium 1 7.5
Copper 50 350
Lead 100 800
Zinc 200 1500

67
Reported Release of Trace Metals from Monolithic Materials

Figures 2.19 2.17 illustrate the cumulative release of Cd, Cu, Pb and Zn from samples, as
sourced in the literature.

As detailed in Table 2.14, several researchers reported negligible results, even when ash was
added to the cement mortar or concrete. Even when the solution is pH-controlled, only a
minimal percentage (typically <1%) of metals present in the sample may be released into
solution (Serclerat et al, 2000). The sample materials described in the references are
dominated by cement mortars, often containing incinerator fly ash. A minority of results are
derived from concrete blocks, and only one set of results were found for clay bricks. In
general, cadmium and lead are rarely detected in sample leachates, and reported results for
both were typically a few g/l or lower. In comparison, concentrations of zinc and copper
tend to be 1 2 orders of magnitude higher. This partly reflects the natural abundances of
these elements: concentrations of cadmium and lead in soil, rock and clinker typically occur
at trace levels (g/kg range), whereas copper and zinc are minor elements, typically
occurring within the mg/kg range (Achternbosch et al, 2003).

Cadmium Leaching

Barna et al (2005) and Van der Sloot (2001) produced Cd leaching data, based on cement
mortar monoliths. The only cumulative release results exceeding the recommended 1mg.m
-2

limit (Table 2.15) were derived from cement mortar samples, which were deliberately doped
with cadmium oxide (Barna et al, 2005) (Figures 2.19, 2.20). In contrast, the results for
mortar samples used by Van der Sloot are insignificant, although controlling the pH to 7
raised concentrations by an order of magnitude.

Marion et al (2004) and Christensen et al (2003) presented data for cadmium leaching from
concrete. It is interesting to note that various concrete samples containing PFA and/or
incinerator ash which were treated with aggressive (pH4) water - contributed less
cadmium than ordinary paving slabs.

Copper Leaching

Referenced data is presented in Figures 2.21 2.23. The most noticeable trend observed in
all the figures is the elevated cumulative release from mortar samples containing GGBS. No
68
explanation for this contrast was given in the reference (Van der Sloot, 2004), although it may
be recalled that Figure 2.15 displayed the highest Cu values for GGBS. The referenced data
in the figures also covers a wider spectrum of values, from less than 0.1mg.m
-2
to above
100mg.m
-2
. Figures 2.22 and 2.23 give a vague indication that the release of copper from
ordinary (sintered) brick and concrete is generally lower, compared with concrete or mortar
containing secondary/waste materials. Typical cumulative were between 0.1 and 10mg.m
-2

approximately an order of magnitude above the cumulative release values for cadmium.
Evidence of the influence of the pH of the leaching solution can be seen in the form of
elevated cumulative release levels. Data sourced from Nagataki et al (2002) (pH6 acetate
buffer) and Christensen et al (2003) (using pH4 dilute nitric acid) are clearly positioned above
all except the data for GGBS-laden mortar.

Lead Leaching

The cumulative release data is displayed in Figures 2.25 2.26. This generally occurs within
a similar range compared with the release data for Cu, although several authors reported
negligible results for Pb.

It is uncertain whether or not the inclusion of secondary or waste materials in concrete
produced elevated concentrations in leachates. One example is the highest curve displayed in
Figures 2.25 2.26, for an ordinary (CEM I) concrete sample, as reported by Marion et al
(2004).

Zinc leaching

The cumulative release data displayed in Figures 2.26 2.28 mostly occur in the 1-10mg.m
-2

range. As with Pb leaching, there are few differing trends between ordinary samples, and
concrete/mortar containing secondary/waste materials.

2.5 CONCLUSIONS

There have been extensive studies into the formation of dioxins and furans, particularly with
regards to MSW incineration. As a consequence, there exists sufficient data regarding the
concentrations of dioxins and furans in MSW incinerator ashes.
69
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
0 10 20 30 40 50 60 70 80 90 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
Cement mortar (1)
Paving slabs (2)
Concrete + PFA + IBA (3)
Concrete + PFA + IBA ii (3)
Concrete + IBA + FGA (3)
Concrete + IBA + FGA ii (3)

Figure 2.19: Cadmium leaching data (Barna et al, 2004
1
2
; Christensen et al, 2003
3
)
70

0.1
1
10
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
Cement mortar (1)
Paving slabs (2)

Figure 2.20: Cadmium leaching data: logarithmic projection (Barna et al, 2004
1
2
3
)
71

In contrast, very few studies have been conducted into dioxins and furans in materials which
are currently used in building materials for housing, including primary materials (e.g.
Portland Cement, aggregates, lime), as well as secondary materials (e.g. GGBS, PFA). This
is possibly because the concentrations of dioxins and furans in those materials are
insignificant. Similarly, there have been a number of studies into the leaching of Cd, Cu, Pb
and Zn from concrete containing incinerator fly ash. Very few studies have focussed on
ordinary or blast furnace slag-based concrete, and no studies on clay brick monolithic samples
were found in the literature. Likewise, this may be because the leaching of Cd, Cu, Pb and Zn
from these latter materials under mildly acidic or un-acidified conditions is also insignificant.

Figure 2.21: Release of Cu from mortar, brick, etc. (Van der Sloot, 2004)

72
0
50
100
150
200
250
300
350
400
450
0 20 40 60 80 100 120 140 160 180
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
Granite-aggreg concrete (1)
Sandstone aggreg concrete (1)
GGBS cement mortar (4)
Sintered brick (4)
Portland cement mortar (4)
Concrete + PFA (5)
Concrete + PFA (5)
CEM I concrete (6)
CEM I concrete (6)
CEM III concrete (6)
mortar + 25% incin ash (2)
Ordinary concrete (3)

Figure 2.22: Copper leaching data (Van der Sloot, 2001
1
; Nagataki et al, 2002
2
; Flor et al, 2003
3
; Van der Sloot, 2003
4
; Cai et al, 2004
5
; Marion
et al 2004
6
)
73
0.001
0.01
0.1
1
10
100
1000
0.1 1 10 100 1000
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
Granite-aggreg concrete (1)
GGBS cement mortar (4)
Sintered brick (4)
Portland cement mortar (4)
Concrete + PFA (5)
Concrete + PFA (5)
CEM I concrete (6)
CEM I concrete (6)

Figure 2.23: Copper leaching data: logarithmic projection (Van der Sloot, 2001
1
2
; Flor et al, 2003
3
4
;
Cai et al, 2004
5
; Marion et al 2004
6
)
74
0
2
4
6
8
10
12
14
16
18
20
0 20 40 60 80 100 120 140 160 180
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
IBA-concrete i (3)
IBA-concrete ii (3)
CEM I concrete (4)
Concrete+PFA (2)
Concrete+PFA (2)
Concrete+PFA+IBA i (a) (2)
Concrete+PFA+IBA i (b) (2)
Concrete+PFA+IBA ii (a) (2)
Concrete+PFA+IBA ii (b) (2)
Concrete+IBA+FBA i (a) (2)
Concrete+IBA+FBA i (b) (2)
Concrete+IBA+FBA ii (a) (2)
Concrete+IBA+FBA ii (b) (2)
Cement mortar (1)
Cement mortar (1)
60% Mtr 40% ash (1)
60% Mtr 40% ash (1)
Granite-concrete (1)

Figure 2.24: leaching of lead (Van der Sloot, 2001
1
2
; Cai et al, 2004
3
4
)
75
0.01
0.1
1
10
100
0.1 1 10 100 1000
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
IBA-concrete i (3)
IBA-concrete ii (3)
CEM I concrete (4)
Concrete+PFA (2)
Concrete+PFA (2)
Concrete+PFA+IBA i (a) (2)
Concrete+PFA+IBA i (b) (2)
Concrete+PFA+IBA ii (a) (2)
Concrete+PFA+IBA ii (b) (2)
Concrete+IBA+FBA i (a) (2)
Concrete+IBA+FBA i (b) (2)
Concrete+IBA+FBA ii (a) (2)
Concrete+IBA+FBA ii (b) (2)
Cement mortar (1)
Cement mortar (1)
60% Mtr 40% ash (1)
60% Mtr 40% ash (1)
Granite-concrete (1)

Figure 2.25: leaching of lead: logarithmic projection (Van der Sloot, 2001
1
2
; Cai et al, 2004
3
4
)
76

Figure 2.26: Release of Zn from cement mortars containing IFA (Lewin et al, 1996)

63
0
10
20
30
40
50
60
0 20 40 60 80 100 120 140 160 180
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
Figure 2.27: leaching of zinc (Van der Sloot, 2001
1
2
;
Christensen et al, 2003
3
4
5
)
64
0.1
1
10
100
0.1 1 10 100 1000
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
Paving slab (5)
Concrete + PFA (3)
Concrete + PFA (3)
Concrete+PFA+FBA i (3)
Concrete+PFA+FBA i (3)
Concrete+PFA+FBA ii (3)
Concrete+PFA+FBA ii (3)
Concrete+IBA+FBA i (3)
Concrete+IBA+FBA i (3)
Concrete+IBA+FBA ii (3)
Concrete+IBA+FBA ii (3)
cement mortar (4)
Cement mortar (2)
Cement mortar (2)
60% Mtr 40% ash (2)
60% Mtr 40% ash (2)
Graniteaggreg concr (2)
Tilburyaggreg concr (2)

Figure 2.28: leaching of zinc (Van der Sloot, 2001
1
2
;
Christensen et al, 2003
3
4
5
)

65
3 MATERIALS AND METHODS

3.1 INTRODUCTION

The experimental programme comprised 2 main phases. The first was an investigation into
dioxin and furan content. The second phase comprised an examination of the leaching of
cadmium, copper, lead and zinc from selected samples, plus a study into the influence of
temperature on leaching rate. The experimental work was conducted in the order illustrated
in Figure 3.1.

Figure 3.1: Programme of experimental work of the PhD project

Development of extraction, clean-up and GC-MS/MS
analysis method for dioxin and furan studies

Section 3.3, Chapter 4
Analysis of samples for dioxins and furans

Chapter 5
Leaching of clay brick, concrete and calcium
silicate samples (some containing waste materials)
using altered NEN7375 method

Chapter 6
Collection of housing materials
from sites throughout UK

Section 3.2
(Samples listed in Appendix 3)
Shortened, heated leaching tests on selected clay brick and
concrete samples (some containing waste materials)

Chapter 7
66
3.2 THE UK SURVEY: COLLECTION OF SAMPLES

Throughout 2004, commercial samples of housing materials were collected from sites
distributed throughout the UK.

3.2.1 Sampling Strategy

The United Kingdom comprises 12 regions (Dept. of Statistics, 2004), all of which were
targeted (excluding the Isle of Man). Figure 3.2 also illustrates the population density of the
UK, whereby light regions are sparsely inhabited, and the dark regions are urbanised.

Figure 3.2: (Left) the twelve UK regions, and (right) British population density (images taken
from the National Centre for Diversity, 2004; and the Socioeconomic Data & Applications
Center, 2004, respectively)

Construction site contractors, housing associations/companies and maintenance companies
(e.g. plumbers, electricians) were contacted, and visits were arranged to collect samples from
construction sites and existing private homes. Demolition waste samples were obtained from
other research projects. Most samples were taken from new housing construction sites. The
remainder were obtained from existing housing and demolition sites. Soil samples were
collected from the majority of the visited new housing construction sites, in order to provide
background environmental dioxin and furan data. All the heavily populated locations were
visited for collecting samples from new-build sites, or were targeted for receiving core
drillings. In addition, visits were also conducted in moderately populated regions (indicated
in pale red), namely the East Midlands, Southwest England and East Anglia.
67
3.2.2 New Housing Construction Sites

Samples collected from new construction sites included clay bricks, concrete bricks/blocks,
cement, lime, mortar, plasterboard, and calcium silicate bricks. Appendix 3 contains a full list
of the housing construction sites visited, the number and type of samples collected, and the
name of the manufacturers (whenever the information was available). In all, 58 concrete
bricks/block samples, 6 plaster samples, 36 plasterboard samples, 28 cement samples, 28
mortar samples, 51 clay brick samples, 10 miscellaneous samples, and 38 soil samples were
collected, between March and September 2004. Samples were collected and received from 11
Scottish sites, 2 Northern Irish sites, 3 Welsh sites, and 29 English sites (45 in total).

3.2.3 Existing Housing

A small number of core drilling samples from existing housing were collected, mainly as this
involved contacting tradesmen and asking them to post samples by courier. 6 samples were
obtained from sites in Scotland; 10 were obtained from sites throughout England. Appendix 3
details the organisations supplying the materials, and the dates when they were received.
Figure 3.3 details the locations throughout the UK where wall drillings were obtained.

3.2.4 Demolition Waste

20 samples of demolition waste (not necessarily from housing demolition) were obtained
from another research project (see Appendix 1). All samples were provided in granular form.

3.2.5 Collection and Storage of Samples

All samples from new housing construction sites (excluding samples from Northern Ireland)
were collected by the author. All construction materials were collected in new plastic
sampling bags. Fragments of concrete or clay blocks/bricks were hammered from discarded
units, which were not contaminated by dirt or waste oil. Cement, plaster and lime were
collected, using a clean metal scoop. Plasterboard samples were sawn off new panels. All
construction materials (both collected and processed) were stored in sealed plastic bags at
room temperature in darkness. Soil samples were collected by the author using a clean metal
scoop, and placed into clean/new glass jars, which in turn were placed inside a cool box for
transportation. The soil samples were then placed inside a freezer as soon as possible in order
to prevent degradation of the dioxins and furans under microbial action (USEPA, 1994).
68

Figure 3.3: Locations of Existing Housing sampling locations

The majority of the core drillings from existing housing were received by the author from
contractors or tradesmen (Appendix 3). Plastic sampling bags were sent to the businesses
offering to collect the samples, and samples were returned to Dundee via courier. Both the
core drillings and the demolition wastes were stored in plastic liners in darkness at room
temperature. (It was not anticipated that the dioxin or furan composition within construction
materials would alter significantly at room temperature, in contrast with that in soils.)

3.3 EXTRACTION AND ANALYSIS OF DIOXINS AND FURANS
3.3.1 Introduction

Dioxins and furans usually occur at trace level in solid materials, and are therefore difficult to
separate and distinguish from more prominent chemicals and substances in a sample.
Furthermore, they are chemically sensitive and may evaporate, or degrade to form different
organic compounds. Their analysis therefore necessitates several extraction procedures and
complex instrumental analysis, using ultra-pure solvents and reagents. Depending on the type
of sample, dioxins and furans can be extracted using several different methods. However, in
all experiments, dioxins and furans must be separated from the sample, and individually
analysed using GCMS (Gas Chromatography Mass Spectrometry). This chapter describes
the methods used to isolate and extract the congeners. The next chapter is devoted to the
programming and calibration of the GC-MS/MS instrument. A detailed description of GC-
MS/MS is provided in Section 3.3.4.
69
3.3.2 Health and Safety

All laboratory surfaces, needles and glassware used were thoroughly cleaned with solvents
and detergents, prior to experimental work. Extracts were stored under refrigeration in
darkness prior to GCMSMS analysis, in order to prevent congeners degrading at room
temperature in the presence of light. As the extracts were hexane-based, GCMSMS analysis
was conducted within a week after extraction, in order to minimise congener degradation by
the hexane solvent. Whenever convenient, glassware used for each extract was not recycled.

The extraction and analysis of dioxins and furans is a hazardous enterprise, requiring the
constant use of a fume cupboard, heavily protected equipment, and eye and hand protection.
Hexane and nonane solvents are inflammable, and can release fumes which could be
carcinogenic at prolonged levels of exposure. Dioxins and furans are considered to be highly
carcinogenic and teratogenic. The copious use of hexane solvent during extraction and
evaporation near hot surfaces (namely the hotplate) required permanent use of a fume
cupboard, and constant supervision. Plastic gloves were worn at all times, as were safety
glasses, a lab coat, and in some cases, a gauze mask was also worn (especially when handling
the spiking solution). All wastes were disposed of in sealed glass containers, which were
clearly labelled.

3.3.3 Sample Extraction

In general, dioxin and furan experiments comprise 3 stages: (1) they must be separated from
the solid matrix using heat treatment in organic solvent; (2) they must then be separated from
other dissolved chemicals which could interfere with GCMS analysis; (3) the purified extracts
are analysed using GCMS. Figure 3.4 details the experimental procedures.

Standard Solutions

In the environment, dioxin and furan congener molecules predominantly contain
12
C isotopes,
with occasional
13
C isotopes. The injection of spiking compounds into samples (containing
purely
13
C-based congener molecules) has therefore been practised for over 30 years.
Injecting a set quantity of spike solution into the sample prior to extraction is an integral
procedure, mainly to investigate what proportion of congeners is lost during the extraction
procedure.

70

Figure 3.4: The Experimental Procedure for Dioxin and Furan Extraction/Analysis

In order to double-check what proportion of congeners is lost during sample processing,
blank samples (pure silica sand containing no dioxins or furans) were spiked with a
12
C-
SAMPLES
Collection,
(drying),
(crushing in ball mill),
<2mm fraction stored in
darkness
BLANK
10g placed in thimble,
immersed in hexane
SOXTHERM
EXTRACTION
SOXTHERM
EXTRACTION
140mL hexane
10/15/20uL
injected
Spike solution
containing
13
C-
congeners
Concentration to
5mL in beaker
Concentration to
0.2mL in 5mL vial
Concentration to
5mL in beaker
Concentration to
0.2mL in 5mL vial
Evaporation of
mixture to 0.02mL
Evaporation of
mixture to 0.02mL
Storage in freezer Storage in freezer
GCMS analysis
SOXTHERM
EXTRACTION
Concentration to
5mL in beaker
Concentration to
0.2mL in 5mL vial
Evaporation of
mixture to 0.02mL
Storage in freezer
10g placed in thimble,
immersed in hexane
Clean silica sand rinsed with
methylene chloride, stored
in desiccator
PAR SAMPLE
GCMS Calibration
PAR solution
containing
12
C-
congeners
20uL injected
Calibration
solutions
Precision and
Recovery analysis
Injection of 1L
into GCMS
Injection of 1L
into GCMS
CLEAN UP CLEAN UP CLEAN UP
71
containing dioxin and furan (Precision and Recovery (PAR)) solution. Approximately 1 PAR
extract was analysed per 50 sample extracts. The contents of the spike and PAR solutions are
detailed below (ng/ml):

Table 3.1: Solutions used to investigate loss of congeners during experiment (ng/ml)

Congener

Spike solution
(
13
C isotopes)*

PAR solution
(
12
C isotopes)**

2378-TCDF 100 40
2378-TCDD 100 40
12378-PeCDF 100 200
23478-PeCDF 100 200
12378-PeCDD 100 200
123478-HxCDF 100 200
123678-HxCDF 100 200
234678-HxCDF 100 200
123478-HxCDD 100 200
123678-HxCDD 100 200
123789-HxCDD 0 200
123789-HxCDF 100 200
1234678-HpCDF 100 200
1234678-HpCDD 100 200
1234789-HpCDF 100 200
OCDF 0 400
OCDD 200 400

* Certification of Analysis/Documentation: EPA-1613LCS (Wellington Laboratories, 2004)
** Certificate of Determination: EPA-1613PAR (Wellington Laboratories, 2004)

Soxtherm Extraction

GCMS instruments can only accommodate liquid or gaseous samples. Since solid samples
were collected, these were crushed, and dioxins and furans present were obtained by
extraction in heated n-hexane solvent. The EPA Method 1613 (1994) recommends the use of
toluene solvent, but this was incompatible with the (Varian) Saturn 2000 GC-MS/MS column.
Toluene also evaporates at a higher temperature than n-hexane (110C, as opposed to 69C),
which greatly prolongs the evaporation procedure. n-Hexane has successfully been used for
dioxin and furan extraction since the 1970s. The EPA Method 1613 (1994) details the
conventional Soxhlet extraction which in comparison to Soxtherm extraction, is time-
consuming, expensive and dangerous. Soxtherm extraction is a type of accelerated solvent
extraction.

72
The Soxtherm extraction units contain glass beakers; each beaker accommodates a thimble
containing 10g of the crushed solid sample. 140ml of hexane (Fisher Scientific, pesticide
residue grade) was poured into the beaker, and 10.00g of sample in a Whatman cellulose
33mm 100mm thimble was immersed into the solvent. 10l, 15l or 20l of the spiking
solution was injected into the thimble, using an SGE 10l syringe, and the contents were
heated to 265C for 2 hours. The apparatus is completely sealed; the hexane vapour is either
retained inside the beaker, or it collects in the condenser (Figure 3.5).
Figure 3.5: The Soxtherm unit, comprising the beaker below, and the toluene condensation
chamber above. An illustration of the chambers appears on the right (Gerhardt, 2001).

An hour into the extraction, the barrier was lifted, and the hexane was evaporated to below
the level of the thimble, after which the barrier between the condenser and beaker was then
sealed. During the second hour, hexane vapour collected at the top of the beaker, percolated
into the thimble, and dripped out into the liquid toluene below, carrying with it dioxins and
furans extracted from the solid sample. At the end of the extraction, the hexane was
evaporated to approximately 30ml. The re-condensed hexane was collected in a reservoir
within the back of the Soxtherm unit, and was recycled for later use.

The Efficiency of Soxtherm Extraction

The Gerhardt company (Gerhardt, 2001) conducted an experiment, to compare the extraction
of dioxins and furans using Soxtherm, with the conventional Soxhlet method. The Soxhlet
extraction is detailed in the EPA Method 1613 document, whereby solid samples are dried by
mixing with sodium sulphate, before extracting with toluene for 12-24 hours (USEPA,
1996).) Two Soxtherm extractions (using the unit illustrated in Figure 3.5) - one lasting 45
minutes (Soxtherm 45min) and the other lasting 30 minutes (Soxtherm 30min) - were
73
conducted alongside the Soxhlet extraction; all three were conducted on a single soil sample.
No replicates or other soil samples were used, and thus the results should be interpreted with
caution. For most homologue groups, Figure 3.6 shows the extraction of dioxins and furans
by Soxtherm to be slightly, but consistently, greater in comparison to the Soxhlet extraction.

1
10
100
1000
10000
100000
1000000
T
C
D
D
P
e
C
D
D
H
x
C
D
D
H
p
C
D
D
O
C
D
D
T
C
D
F
P
e
C
D
F
H
x
C
D
F
H
p
C
D
F
O
C
D
F
(
n
g
/
k
g
)
Soxtherm 45min
Soxtherm 30min
Soxhlet

Figure 3.6: Extraction of dioxin and furan homologues (Gerhardt, 2001)

There was some evidence for the longer Soxtherm extraction producing higher results than
those of the 30-minute extraction, and with some furan homologues (HxCDF, HpCDF,
OCDF), the 30-minute Soxtherm extraction was less efficient than a Soxhlet extraction
(Gerhardt, 2001).

Figure 3.7 is based on results of the levels of each toxic congener in the soil sample, based on
the three extractions. There was a tendency for the Soxtherm extractions to be more efficient
than the Soxhlet extraction (i.e. higher results were produced), although this pattern was
inconsistent. The 45-minute Soxtherm extraction also tended to produce higher results than
those from the 30-minute extraction. In conclusion, the 45-minute Soxtherm extraction is
slightly more efficient than the EPA Method 1613-based Soxhlet extraction. A 30-minute
Soxtherm extraction is inadvisable, since less dioxins and furans may be extracted from solid
samples (Gerhardt, 2001).

74
1
10
100
1000
10000
2
3
7
8
-
T
C
D
D
1
2
3
7
8
-
P
e
C
D
D
1
2
3
4
7
8
-
H
x
C
D
D
1
2
3
4
7
8
-
H
x
C
D
D
1
2
3
7
8
9
-
H
x
C
D
D
1
2
3
4
6
7
8
-
H
p
C
D
D
2
3
7
8
-
T
C
D
F
2
3
4
7
8
-
P
e
C
D
F
1
2
3
4
7
8
-
H
x
C
D
F
1
2
3
6
7
8
-
H
x
C
D
F
1
2
3
7
8
9
-
H
x
C
D
F
2
3
4
6
7
8
-
H
x
C
D
F
1
2
3
4
6
7
8
-
H
p
C
D
F
1
2
3
4
7
8
9
-
H
p
C
D
F
(
n
g
/
k
g
)
Soxtherm 45min
Soxtherm 30min
Soxhlet

Figure 3.7: Extraction of individual dioxin and furan congeners (Gerhardt, 2001)

3.3.4 Clean-up Filtration

The analysis of dioxins and furans using advanced GC-MS/MS facilities imposes a high
demand on the purity of the samples being analysed. Extraction of almost any material for
dioxins and furans will also yield larger quantities of interfering compounds such as poly-
aromatic hydrocarbons (PAHs). Those compounds not only cancel out the dioxin and furan
peaks, but can also impart damage or contamination to the GC column. Clean-up filtration
has therefore always been a requirement for dioxin and furan analysis (Eljarrat and Barcelo,
2003). Initially, EPA Method 1613 was used for clean-up. However, problems were
encountered with this method, and an alternative was devised. Both methods are discussed in
this chapter.

A range of clean-up filtration materials has, and is, widely used by analysts. The four most
frequently used materials are silica gel, alumina powder, activated carbon and florisil. The
quantity, chemistry and order of these materials will vary, depending on the nature of the
samples being analysed (Focant et al, 2001; Eljarrat and Barcelo, 2003).

75
3.3.4.2 EPA Method 1613 Clean-up Procedure (December 2004 analyses) (Figure 3.8)

Sections 13.3 and 13.4 in the EPA Method 1613 document, detail the clean-up of extracts
using silica gel and alumina, respectively. The manual details the preparation of acidic, basic
and neutral silica gel, in addition to sodium sulphate and alumina. Silica gel (60 / 200
micron) was provided by Fisher Scientific. Three types of silica gel were prepared, in
accordance with Section 7.5 of the EPA manual:

- Silica gel: this was rinsed with methylene chloride, then placed in a dessicator.
- Acid silica gel: 100g of methylene chloride-rinsed silica gel was mixed with 44g of
concentrated sulphuric acid (concentrated analytical reagent (Fisher Scientific)) and stirred
thoroughly with a clean glass rod until all lumps were disaggregated. The mixture was then
placed in a dessicator.
- Alkali silica gel: 100g of methylene chloride-rinsed silica gel was mixed with 33g of 1N
NaOH solution, and stirred thoroughly with a clean glass rod until all lumps were
disaggregated. The mixture was then placed in a dessicator.

The alumina (calcined aluminium oxide (Fisher Scientific)) was prepared by placing 100g
into an oven at 180C for 2 hours. Thereafter, the alumina was placed into a desiccator.

A 20mm 200mm CR20/20 Quick-fit chromatographic column (Bibby Sterilin Ltd) was
used. The filter was prepared as shown in Figure 3.7 from the base upwards: 6g alumina, 1g
silica gel, 4g alkali gel, 1g silica gel, 8g acid gel, 2g silica gel, and 4g sodium sulphate (lab
reagent grade (Fisher Scientific)). Prior to adding the extract, 50ml of hexane was washed
through the column to remove moisture and contaminants. After the extract was passed
through the column, another 50ml of hexane was passed through, in order to wash out any
dioxins and furans into the purified extract.

3.3.4.3 Altered Clean-up Procedure (February 2005 analyses)

It was discovered that the filter described above removed both interfering compounds, but
also a significant proportion of the dioxin and furan congeners. It is worth noting that 4
Scottish construction material extracts were cleansed using florisil, which is a more
aggressive clean-up filter. As expected, the dioxin and furan congeners were lost in the
process. An extensive literature search was conducted, in order to investigate the types and
quantities of materials used by other dioxin analysts in the last 20 years.
76

Figure 3.8: The EPA 1613 Clean-up Filter Column

A simple clean-up filter was then successfully developed for the purification of construction
material extracts (Figure 3.9). Following a procedure outlined by Martens et al (2002),
alumina powder and silica gel were heated at 105C for at least 48 hours prior to use, and
were stored in the oven in-between experiments. Immediately before being used, both
materials were left in a desiccator to cool. 1.5g (0.1g) of alumina powder was added first,
followed by 3.0g (0.2g) of silica gel. The final top layer comprised sodium sulphate - this
removed moisture from the extracts. In order to eliminate moisture, none of these materials
were allowed to stand in the open air at any time.

Prior to pouring the extract through the column, 50ml of hexane solvent was passed through
the column in order to remove both moisture and any contamination. This was collected and
discarded. As soon as the last of the solvent entered the column filter (when about 5mm of
solvent covered the filter), the sample extract was poured in.
77

Figure 3.9: Simplified Clean-up Filter Column

Some hexane was added to the Soxtherm beaker to wash out any remaining extract, and the
washings applied to the column also. A clean 100ml beaker was used to collect the purified
extract. Afterwards, 50ml of hexane was passed through the column in order to wash out
dioxins and furans trapped within the column. The materials were then disposed of, and the
column thoroughly cleaned with water and then dried.

3.3.5 Evaporation of Extracts to 20 l

The concentration of the extract from ~80ml (after clean-up) to 20l comprised three stages:
evaporation to 5ml in 100ml beakers, evaporation to ~0.2ml in 5ml vials, and the evaporation
of the extract to 20l in 100l inserts. The concentration of the extract to 20l is essential, as
GCMS instruments rarely accommodate sample intakes exceeding 1l. Concentrating an
extract from 140ml to 20l can greatly increase the concentration of interfering compounds,
hence the necessity of the clean-up filtration. All evaporation stages were conducted within a
fume cupboard, using a Cenco Instrumentation hotplate.
97
Evaporation in Beakers

As mentioned, the extracts being passed through the clean-up column were collected in a
100ml glass beaker. A hot plate capable of accommodating 4 beakers was used to evaporate
the extracts to approximately 5ml. Although the temperature was raised gradually, some
extracts spurted at the point of boiling, and sometimes with the partial loss of solvent. When
the extracts were concentrated to approximately 5ml, the beakers were taken off the hotplate,
gently shaken, and the extracts poured into 5ml vials.

Evaporation in 5ml vials

The same hotplate was used to heat the extracts contained in 5ml vials (provided by Wheaton
Scientific). The vials were supported by a metal block, which prevented the vials toppling
over. At the point of boiling, some extracts spurted, but overall, better control of heating the
extracts was achieved using these vials.

The interior of the 5ml vials comprised a conical base (Figure 3.10). Approximately 0.2ml of
solvent formed a meniscus halfway up the cone. As soon as the level of the extract reached
this height (h 2), the vial was sealed immediately. Although an inaccurate means of
retaining 0.2mL of extract, this method was adequate in this case.

Figure 3.10: Acceptable level of residual extract

Evaporation in 100ul Inserts

2.0ml glass bottles, PTFE/silicone septa, and 100ul borosilicate glass inserts were provided by
Varian. The extracts within the 100l inserts were gently heated at approximately 60C, in
order to prevent the extracts from boiling (which caused severe spurting). A steady heat was
98
maintained using the hotplate, allowing the extracts to vaporise slowly (usually between 5 and
15 minutes) (Figure 3.11).

Figure 3.11: Evaporation of extracts from ~200l to ~20l

Glycerol (Fisons specified lab reagent) was used to establish a stable heat gradient between
the interior of the aluminium hotplate, and the ends of the inserts. When the level of the
extract reached the top of the bell-shaped end of the insert, the insert was retrieved, the
glycerol wiped off using tissue, and the insert was placed inside a 2ml glass vial. The extracts
were then placed in the refrigerator at 5C until required for GC-MS/MS.

3.3.6 MS/MS (Tandem Gas Chromatography-Mass Spectrometry)
3.3.6.1 Introduction to GCMS

GCMS is a technique used to separate the different dioxin and furan congeners, and analyse
the concentration of each congener. In a gas chromatogram (Figure 3.12), the dioxins and
furans contained in a solvent are distilled. The mixture is heated, and as the temperature rises,
each congener evaporates at its own boiling point. These are carried along a long tube and
through a detector. The detector records the passing of each congener, which travels into the
mass spectrometer (Kemp, 1991).

Upon entering the mass spectrometer, the congeners are bombarded with inert atoms (helium
gas), ionising them to form charged molecules, which disintegrate into molecular fragments.
The fragments travel through the analyser tube, and are recorded at the collector assembly
point. The analyser tube is kept under vacuum, in order to prevent interference from any
substances other than helium (Kemp, 1991).

99

Figure 3.12: The gas chromatogram

Mass spectrometry is used to identify and measure the mass of each fragmented congener.
Each congener is accompanied by an isotope-laden equivalent (which originates from the
spike solution injected into the Soxtherm beakers). The spike solution dioxins and furans
contain
13
C atoms, making them slightly heavier, and causing these to fall below the dioxins
and furans from the samples (Kemp, 1991). The set concentration of the
13
C-containing
congeners is compared with the peaks produced by extracted
12
C-containing congeners, and,
thus, the concentration of congeners in the samples can be calculated.

3.3.6.2 Suitable GCMS Techniques for Dioxin and Furan Analysis

Calibration solutions used for GCMS development contained dioxin and furan congeners at
the ng/ml range. Analysis using conventional bench-top GCMS instruments was therefore
unsuitable. Advanced GCMS techniques (e.g. high-resolution GCMS, or tandem GC-
MS/MS) are required to obtain this level of detection. The most advanced technique is high-
resolution (HR) GCMS. This technique is prohibitively expensive, mainly due to the regular
maintenance that is required.

In search of a more affordable and reliable method of dioxin and furan analysis, researchers
have developed and investigated an increasing range of ion-trapping GCMS techniques. The
most successful of these alternatives is the ion-trapping MS/MS method, which has been
endorsed by analysts since the 1970s (Bonne et al, 1997).

An ion-trap MS/MS instrument was used for analysing extracts of the construction material
and soil samples. Access to using a Varian Saturn 2000 GC-MS/MS (Ion Trap) instrument
was granted by the RUM Consultancy company in Cookney, Aberdeenshire.

100
Principles of GC-MS/MS

In its simplest terms, GC-MS/MS differs from GCMS, whereby 2 MS chambers are employed
instead of a single chamber. The advantage of this alteration is that both the parent molecules
(i.e. the dioxin and furan congeners) and the daughter ions (the fragments produced under
electrocution), can be simultaneously analysed. The parent ions are isolated in the first
chamber, before being electrocuted to produce the fragments that are collected and analysed
in the second chamber.

Under selected MS/MS conditions, dioxin and furan molecules will disintegrate to form
particular fragments (daughter ions). Dioxins will lose either single or double Cl atoms, or
they may lose [COCl] or [(CO)
2
Cl] fragments, producing lighter, daughter fragments,
which in turn are analysed and recorded as peaks on chromatographs. Furans also lose Cl
atoms and [COCl] fragments; however, they also lose [COCl
2
] and [COCl
3
] fragments, e.g.
2378-TCDF. Examples with 2378-TCDD (tetra-chloro-dibenzo-dioxin) and 2378-TCDF
(tetra-chloro-dibenzofuran) are provided in Figures 3.13 and 3.14, respectively (Focant et al,
2001).

Figure 3.13: Fragmentation of TCDD under MS/MS conditions

Following the method detailed by Focant et al (2001), the Saturn 2000 GC-MS/MS was
attenuated in order to analyse the breakdown of parent molecules to produce daughter
fragments, with the loss of the [COCl] fragment. As reported in the literature, when 2378-
TCDD and 2378-TCDF (containing purely
12
C and
35.5
Cl atoms) lose the [COCl] fragment,
they form daughter ions of 257.5amu and 241.5amu, respectively (Focant et al, 2001; Helen
et al, 2001; Petrovic et al, 2002). Parent and daughter molecules regularly contain at least one
heavier hydrogen, chlorine, oxygen or carbon isotope.
12
C
12
-2378-TCDD

(No
37
Cl atoms)
(322amu)
[ C2H4O2Cl3 ]
+
+ Cl
(285.5amu) (35.5amu)

[ C11H4OCl3 ]
+
+ COCl
(257.5amu) (63.5amu)

[ C12H4O2Cl2 ]+ + Cl2
(251amu) (71amu)

[ C10H4Cl3 ]
+
+ (CO)2Cl
(230.5amu) (91.5amu)

[ C10H4Cl2 ]
+
+ 2(COCl)
(195amu) (127amu)
101

Figure 3.14: Fragmentation of TCDF under MS/MS conditions

One noteworthy example is a congener which possesses a single
37
Cl isotope; thus the
equivalent daughter fragments produced from 2378TCDD and 2378TCDF are 259amu and
243amu, respectively. Focant et al (2001) analysed such daughter fragments for all PCDD/F
congeners, and the same approach was taken for this project.

The gaseous dioxin and furan molecules enter the MS/MS unit, supported within a gas stream
of helium atoms. The mixture is then contained within the first chamber by applying a
voltage, which (1) prevents the molecules escaping, and (2) causes the molecules to fragment.
The Saturn 2000 MS/MS unit contains 3 electrodes of hyperboloidal geometry (Plomley et al,
2000) (Figure 3.15: image on right). The large end-cap electrodes contain entrance and exit
slits, into which parent molecules pass out of the GC column, and out of which the fragments
are transported into the second MS chamber (the detector). The end electrodes employ a
resonance AC voltage, which at specific settings ionises and fragments the dioxin and furan
molecules. The ring electrode connects with the end electrodes, completing the circuit
(Plomley et al, 2000).

Within this chamber (Figure 3.15: left), the electromagnetic force exerted causes the dioxin
and furan molecules to be withheld, and to follow an orbital trajectory. As a result, the dioxin
and furan molecules collide with the unexcitable helium atoms, lose their kinetic energy, and
are concentrated in the centre (Plomley et al, 2000). The Saturn 2000 MS/MS programme
was attenuated by varying the CID potential, through MRM (multiple reaction monitoring).
The CID potential involves applying a voltage, which excites the dioxin and furan congeners,
causing them to collide with helium atoms until they fragment; since helium atoms must be
present, this is termed chemically induced dissociation (CID).
12
C
12
-2378-TCDF

(No
37
Cl atoms)
(304amu)
[ C12H4OCl3 ]
+
+ Cl
(268.5amu) (35.5amu)

[ C11H4Cl3 ]
+
+ COCl
(241.5amu) (63.5amu)

[ C12H4O2Cl2 ]+ + Cl2
(233amu) (71amu)

[ C10H4Cl3 ]
+
+ COCl2
(205amu) (99amu)

[ C10H4Cl2 ]
+
+ COCl3
(169.5amu) (134.5amu)
102

Figure 3.15: The MS/MS Chamber

GC-MS/MS enables the analyst to study the simultaneous elution and fragmentation of
several compounds. This is necessary, firstly as each native (sample-derived)
12
C-based
congener emerges from the GC column alongside the labeled (spike solution-derived)
13
C-
based congeners. Secondly, GC is a form of distillation, whereby the temperature is raised,
and compounds with successively higher boiling points are evaporated and are carried into the
MS/MS chamber. Some compounds (especially hexa-chlorinated dioxins and furans) enter
the MS/MS at the same time. Using MS/MS, the analyst can separate out each of the
congener peaks from a multiple peak on a chromatograph.

3.4 LABORATORY METHODS USED FOR TRACE METAL ANALYSIS

Cd, Cu, Pb and Zn content and leaching were investigated using an altered NEN7345 method,
as well as shorter leaching methods each lasting 1 week. Analysis methods included XRF,
voltammetry and atomic absorption spectroscopy (AAS). XRF was used to analyse the total
trace metal content in crushed solid samples, whilst voltammetry and AAS were used to
analyse trace metals in leachates. Voltammetry was used as often as possible to analyse
leachate extracts, due to its lower limit of detection. However, the voltammetry instrument
was periodically inoperative, and this necessitated the use of AAS analysis for extracts of
samples leached using accelerated tests (i.e. 1-week leaching tests).

3.4.1 Total Trace Metal Analysis using XRF
3.4.1.1 Introduction to XRF

Analysis of the content of trace metals was conducted using XRF (X-ray fluorescence). This
was performed using a Philips Magix XRF spectrometer (with a Cu K source). XRF has a
103
proven record for the detection of trace metals, namely in particulate matter. However,
detection of elements below 100mg/kg is considered to be inaccurate (Willard et al, 1988).
XRF is characterised by the atomic excitation of a substance when it is bombarded by X-rays.
When X-rays enter a sample, the constituent atoms of the sample may absorb the X-rays.
However, if the energy of the incoming X-rays is considerable, the innermost electrons of an
atom may absorb the energy, causing the electrons to be ejected (Figure 3.16 (a)). As a result,
an outer electron is drawn into the vacant inner orbit, emitting X-rays in the process (Figure
3.16 (b)) (Amptek, 2004).

Figures 3.16 a, b: The excitation of electrons by X-rays

The X-rays emitted are collected and filtered by a collimator (composed of thin parallel
plates), before being diffracted by an analysing crystal (Figure 3.17). Once the X-rays pass
the crystal, they pass through a secondary and auxiliary collimator, before finally being
received by the scintillation detector. The analysing crystal turns at an angle , whilst the
secondary and auxiliary collimators turn at an angle (2 ); this trajectory covers the range
of angles of emitted X-rays, which in turn correspond with different elements and their
compounds (Amptek, 2004).

Figure 3.17: XRF instrumentation
104
3.4.1.2 Preparation of XRF Samples

About 5g of each sample (excluding Portland cement) was crushed using the ball mill, before
being ground into a fine powder using a mortar and pestle. The crushed powder was oven-
dried overnight to remove water moisture. Most samples required mixing with a few drops of
a water-soluble polymer solution, in order to fuse the particles together. Each sample
(including Portland cement samples) was compressed into a disc for about 10-15 minutes.
The intact samples were then inserted into the XRF spectrometer and automatically analysed.

3.4.2 Analysis of Metals at Trace Levels Using Voltammetry

Conventional methods of analysing metals in aqueous solution include atomic absorption
spectroscopy (AAS) and flame emission spectroscopy (FES/AES). These methods are
sufficient, provided that the metals in question exist at or above ppm (mg/l) level. However,
the release of metals from the leaching of cementitious materials often produces a leachate
which is characterised by metal concentrations occurring in the g/l range. Voltammetry is
capable of analysing concentrations of Cd, Cu, Pb and Zn - even at the upper ppt (mg/l)
range.

For analysis of leachates, ASV (anodic (electrode)-stripping voltammetry) was conducted
using a Metrohm 757-Computrace instrument. ASV analysis is performed in three stages
(Figures 3.18 a c). In Stage A, a mercury electrode is immersed into the leachate (the
mercury drop is around 0.2mm in diameter, and hangs off the capillary). After the leachate is
stirred, a current is passed through the mercury, which becomes negatively charged (Stage B),
and the positively charged metal cations are adsorbed onto the mercury. After a specified
period of time (3 minutes), a voltage sweep is induced, whereby the voltage is raised from -
1.5V to 0.0V, causing the metals to be oxidised and released back into solution.

The metal concentrations in the solution are quantified by analysing the current passing
through the mercury electrode. Two electrodes (the mercury and the potassium chloride
electrodes) are placed almost against one another in the solution; as metals are re-released
back into solution, more current passes between the electrodes. If the current is recorded
against the voltage, the rise in the current would be characterised as a series of steps (Figure
3.18). This is because different metals dissolve (are oxidised) back into solution at specific
voltages (Jyothi et al, 2003).

105
Cd (solid) Cd
2+
+ 2 electrons -0.64V
Cu (solid) Cu
2+
Pb (solid) Pb
2+
Zn (solid) Zn
2+

Figures 3.18: The three stages in voltammetric determination (hanging mercury drop), and
oxidisation voltages

Using the Metrohm software, the current signal can be interpreted, whereby the difference
between the change in background current (using a clear reference solution) and the leachate
can be translated into individual peaks for each metal. The height of the peaks is therefore
used to indicate the quantity of each metal (Figure 3.19).

Figure 3.19: conversion of the voltage sweep signal into metal concentration peaks

Because the leachates are acidified to <pH2, they alone are unsuitable for analysis. Instead,
they are diluted by 5:1 using ammonium acetate buffer, which itself was prepared to produce
106
a solution at pH4.6-4.8. 2.765ml of concentrated ammonia solution and 3.062ml of acetic
acid were mixed with distilled water to produce a 250mL of the buffer. 2ml of sample and
8ml of buffer were injected into the voltammetry sample cell. Between each sample, the
cell was rinsed thoroughly, using washes of distilled water and dilute nitric acid.

The sample concentration was automatically determined during voltammetry analysis by
injecting two aliquots of 0.1ml of standard solution, which throughout the majority of
analyses was composed of 100g/l Cd, 250g/l Cu, 1250g/l Pb and 500g/l Zn. Initially,
the standard solution contained 12,500g/l Pb, although this affected the readings, and the
concentration was therefore reduced by one order of magnitude. Under optimum conditions,
the lowest detectable concentrations were reported by the manufacturer to be 0.05g/l for
cadmium, copper, lead and zinc (Metrohm, 2006). However, using the same voltammetry
apparatus as that used in this study, Brindle (2005) specified detection limits of 0.1g/l for
cadmium, and 2.0g/l for copper, lead and zinc. These detection limits were used for
processing the voltammetry data generated in this project.

3.4.3 Atomic Absorption Spectrometry (AAS)

For some analyses, atomic absorption spectrometry needed to be conducted. The apparatus
for this is illustrated in Figure 3.20. Acetylene gas is used as the fuel (producing a turquoise
flame), and the temperature of the flame is controlled by the ratio of acetylene and air
(oxidant). Using a Unicam 989 AA Spectrometer, 1.00ml of sample extract was
automatically fed into the AAS flame. The liquid extract enters a chamber, wherein the
temperature is raised until the metal atoms are distilled from the condensate; the latter is
discharged into a waste container. Although AAS no longer provides the lowest limits of
detection for most elements, it is still a reliable and routine means of analysis of trace metals
in solutions.

The flame raises the temperature to a level at which metal atoms become separated from the
extract solution components (i.e. water). However, the temperature and the structure of the
flame are carefully selected, so that the atoms are contained within the cool zone of the
flame. This allows the incident radiation of a specific energy (emitted by a lamp specifically
designed for analysis of a selected metal), to bombard the atoms, and electronically activate
them into a higher state of energetic excitation. The change in the incident radiation (aimed
also at the detector beyond the flame) is recorded, and the quantity (and thus the
concentration in the extract) is automatically calculated.
107

Figure 3.20: AAS instrumentation

Using the same AAS instrument, Halliday (2002) reported that the limits of detection for
copper, lead and zinc, were 8.3, 46.7, and 19.6 g/l, respectively. However, Cd was not
analysed using AAS, since it was seldom detectable in the extracts processed using
voltammetry. Another complication was the variation in background noise, which produced
different outputs for blanks (distilled water) over time. As a result, the raw AAS data was
graphically analysed, and sample concentrations were calculated by subtracting blank values,
whilst taking background noise variations into account.

3.5 LEACHING OF Cd, Cu, Pb AND Zn FROM MONOLITHIC SAMPLES

Concrete, calcium silicate and clay brick samples were assessed for their potential for
leaching Cd, Cu, Pb and Zn into the environment. This was conducted on 35 selected UK
Survey samples using a standardised (NEN7345) monolith leaching test. Although much
research using this test has been focussed on concrete-encapsulated hazardous waste (namely
incinerator ashes), building materials can be buried under soil, or exposed to rainwater or
standing surface water, hence a 64-day leaching test for monolithic samples is considered
relevant (Van der Sloot and Djikstra, 2004). Tapwater leachant was considered to best
represent the composition of surface and rain water (Halliday, 2002).

Most tests reported in the literature endure for several weeks, and some researchers have
studied the leaching of samples over several months or even a few years. Such tests are
108
impractical for general use by the construction industry. A range of accelerated leaching tests
were therefore developed. A variety of accelerated leaching tests were conducted, which
employed alterations to parameters including temperature, time, leachant composition, and
pH control. Accelerated leaching tests were also conducted on Samples A to J, as well as a
clay brick sample (CB) and a concrete sample (CN). All concrete samples were obtained
from other research projects. The results of the accelerated leaching tests are presented in
Chapter 7. Samples A to J, CB and CN included some concrete samples containing waste or
secondary materials, including GGBS (Samples D and CN), PFA (Samples A, J), silica fume
(Sample F) and SSA (Samples H and CN). Distilled water leachate was used for all
accelerated tests, so that minor changes in dissolved metal composition in leachates could be
examined (whereas the dissolved metal concentrations of tapwater obscured those emanating
from the samples). Accelerated leaching tests lasted 7 days (in accordance with a method by
Hohberg et al (2000)), and factors determining diffusion such as temperature and pH were
altered in order to investigate if the leaching process could be speeded up (in contrast with
the standard 64 days leaching time). Samples A to J were used throughout all the accelerated
leaching tests (as well as for a standard 64-day test).

The CB and CN samples were used for leaching in pH4-acidified water at temperatures
ranging from 20C to 150C, since it was doubted if results from tests at very high
temperatures (i.e. above 60C) would be successful. Following these tests, Samples A to J
were leached using the same solution up to temperatures of 100C.

For all leaching tests, pH checks of leachant were performed using a Hanna Instrument
electrode. The pH of leachates was measured after stirring the leachate - either before new
leachate was used, or just before the leachate with the sample within was decanted and
filtered prior to storage and analysis.

3.5.1 Preparation and Testing of Monolithic Samples using the NEN7345 standard

The samples were cut into monolithic cuboids using a diamond saw, and immersed in water
inside sealed plastic containers. 36 were immersed in un-acidified tap water, and 4 with
distilled water (volume - sample surface area ratio = 5ml: 1cm
-2
). Full details of the samples
are contained in Tables 3.2 3.4. For each sample batch, a blank (tap-water) sample was
subjected to the same conditions, processing and analysis. Tap-water leachant was used for
most samples in accordance with BSI Document 95/106424 (European Cement Association,
1995), as tapwater more closely reflects the composition of water which concrete and clay
bricks are exposed to in the environment (in contrast with distilled water).
109
Many of the samples contained at least one dimension of less than 4cm; the smallest reported
dimension found in the literature was 15mm (Sakanakura et al, 2003). All samples were
stored in sealed plastic liners prior to use, in order to prevent the ingress of air, and thus retard
carbonation. During leaching, the samples were immersed continually in water inside a
sealed plastic container. All containers were rinsed with dilute nitric acid prior to use.
During the experiment, the leachate was periodically renewed, and filtered extracts of the
previous leachate were acidified to <pH2 (using nitric acid) and stored under refrigeration.

Using the NEN7345 leaching test, the leachant was replaced (or replenished) 0.25, 1, 2.25,
4. 9, 16, and 36 days after commencing the experiment. After 64 days, the final leachate was
obtained, and the monolith sample was air-dried, retained, and later pulverised for use in XRF
analysis. With accelerated leaching methods, the total duration was reduced to 7 days
(following a similar approach taken by Hohberg et al, 2000), whilst the earlier leachate
replenishments were conducted 0.25, 1, 2.25 and 4 days after commencing the experiments.
Whenever the leachate was replaced, the old leachate was shaken vigorously, and filtered
through a Whatman filter paper. Aliquots of leachate were stored in plastic test-tubes, and
acidified to <pH2 for preservation during long-term storage under refrigeration.

Calculation of Leaching of Metals from Monolithic Samples

As mentioned in the previous chapter, several researchers have reported leaching results, as
expressed as the cumulative release (over time) of a metal (in mg), per square metre (m
-2
) of
sample surface area. The results described in Chapters 6 and 7 were calculated according to
Equation 3.1:
3.1
i
n
i
i
n
i
i n
fA
V c
E

= =
|
|
.
|
\
|
= =
1 1

Whereby : c
i
= [sample extract concentration] [blank concentration]

n
= total cumulative leaching over whole experiment (mg.m
-2
)
E
i
= leached amount during single leaching period during experiment (mg.m
-2
)
c
i
= concentration in extract derived from sample (g/l)
V = volume of water used (l, litres)
(f = conversion from 1000g to 1mg)
A = surface area of sample (m
-2
)
(n = no. of leaching periods (between replenishments) during experiment)

3.5.2 Leaching from UK survey samples under the NEN7345 test

A selection of concrete, clay brick and calcium silicate samples (collected from new-build
construction sites around the UK) were subjected to leaching. Details of the samples (some
110
duplicated) are provided in Tables 3.2 and 3.3. Due to the scale of the experiment, for the
majority of samples, tapwater was used as the leachant, in accordance with a leaching method
used by Halliday (2002). Sample dimensions varied as many remaining bricks and blocks
from the UK survey collection possessed dimensions approaching or less than 4cm. This
variation was compensated by maintaining a constant leachant volume to sample surface area
ratio of 5cm
-3
: 1cm
-2
.

3.5.3 Samples A J and the CB and CN samples

12 samples obtained from another research project (an aircrete, 8 concrete and 3 clay brick
samples) were subjected to the NEN7345 leaching test method, as well as a variety of
accelerated leaching tests. Sample containers were initially rinsed with dilute nitric acid prior
to use, and for the 64-day leaching tests the smallest sample dimension was 3.5cm (which is
considered to be reasonable (Van der Sloot, 2006 personal communication)). Further
details of Samples A to J, CB and CN are listed in Table 3.4. For the 64-day leaching
test the same volume to sample surface area ratio was used as with the UK survey samples.
However, for the accelerated (7-day) leaching tests, a V/V (volume-to-volume) ratio of 5cm
-3
:
1cm
-3
(leachant: sample) was used in accordance with the method by Hohberg et al (2000).

A variety of accelerated leaching tests were conducted, which employed alterations to
parameters including temperature, time, leachant composition, and pH control. These
accelerated leaching tests and their altered parameters are summarised in Table 3.5, and
detailed in the following three sections. It has been postulated that according to Ficks Law
of Diffusion, the rate of release of trace metals into solution should increase with increasing
temperature (Van der Sloot, 2001).

3.5.4 Leaching of Samples A to J under NEN7345 test (Table 3.6)

Monoliths of samples A to J were cut using a diamond saw, and extracts were prepared and
analysed throughout the period during which accelerated leaching tests were developed and
tested. The first leaching tests were identical to the NEN7345 leaching tests employed during
leaching of the selected UK survey samples. Duplicates of these samples were prepared and
subjected to leaching using tapwater. However, the duplicate monoliths of samples F to H
were exposed to air, and single monoliths from these samples were tested instead.

The leachant was replenished 0.25, 1, 2.25, 4, 9, 16, and 36 days after commencing the
experiment. The last leachate extracts were obtained 64 days after commencement. During
111
each replenishment, the pH of the leachate was monitored, partly to ensure that no air ingress
into the sample containers occurred.

Table 3.2: Details of concrete/calcium silicate block samples used for NEN7345 tests

Sample No. and Details

Dimensions
(mm)

Water type

Volume (ml)

CONCRETE/CALCIUM SILICATE

NEN 1 (First leaching experiment)
1 20 20 80 Tap water 160
2
Concrete block (James Burrells Ltd)
(Johnnie Johnson HA, Belford)
20 20 80 Tap water 160
4 Concrete block (unknown manuf.)
(Northern Ireland H.E., Newry)
25 25 60 Tap water 187.5
6 Concrete block (Laird Brothers)
(Angus HA, Arbroath)
75 20 25 Tap water 187.5
8 Grey concrete (Plasmor Stranlight)
(Mosscare HA, Manchester)
20 20 80 Tap water 160
NEN 2 (Second leaching experiment)
13 Concrete block (Plasmor Stranlight)
(Johnnie Johnson HA, Stockport)
20 25 60 Tap water 150
15 Concrete block (Masterblock)
(Magna Homes, Yeovil)
20 30 60 Tap water 180
17 Calcium silicate block (unknown)
(Cosmopolitan Housing, Kirkby)
25 40 40 Tap water 200
19 Concrete brick (Plasmor Stranlight)
20 20 55 Tap water 110
NEN 3 (Third leaching experiment)
21 30 25 50 Tap water 187.5
22
Conc. Brick (Taylor Maxwell)
(Canmore HA, Edinburgh)
30 25 50 Tap water 187.5
24 Concrete block (unknown)
(Leeds Fed. HA, Leeds)
55 20 25 Tap water 137.5
26 Calcium silicate (Ibstock)
(CDS Housing, Liverpool)
55 25 25 Tap water 175
28 Aircrete (Thermalite)
(Bellway Homes, Ipswich)
20 25 55 Tap water 137.5
NEN 4 (Fourth leaching experiment)
33 Concrete slab (unknown)
(Charlton Traingle HA, London)
55 25 25 Tap water 175
35 Grey concrete block
(Gordon & Sons Manufacturing)
(Stewart Milne Homes Stonehaven)
50 20 30 Tap water 150
37 Concrete brick (PJ Edenhall)
(Cube HA, Glasgow)
60 20 23 Distilled
water
135
39 55 25 25 Tap water 175
40
Concrete block (Pattersons of
Airdrie) (Link HA, Airdrie)
70 20 25 Distilled watr 160

112
Table 3.3: Details of clay brick samples used for NEN7345 tests

CLAY BRICK

Sample No. and Details

Dimensions
(mm)

Water type

Volume (ml)
NEN 1
3 Clay brick (unknown)
(Northern Ireland H.E., Newry)
20 15 80 Tap water 120
5 Grey clay brick (Ibstock)
(Berwickshire HA, Duns)
65 20 25 Tap water 162.5
7 Grey clay brick (recycled)
(Ty Gwalia HA, Swansea (Site 1))
60 25 25 Tap water 187.5
9 Clay brick (Leicester Red)
(Victoria, London)
65 25 25 Tap water 203
10 Lime clay brick (Baggeridge Brick)
70 20 20 Tap water 140
NEN 2
11 65 20 20 Tap water 130
12
Clay brick (Ibstock)
(Portsmouth HA (Site 1))
65 20 20 Tap water 130
14 Red clay brick (Taylor Maxwell)
(Charlton Triangle HA, London)
20 20 60 Tap water 120
16 Clay brick (Redwall Contractors)
(Wickersley, Rotherham)
25 20 65 Tap water 160
18 (Leicester Red) clay brick
(Enfield, London)
20 30 60 Tap water 180
20 Clay brick (Baggeridge)
(Western Challenge Housing,
Poole)
65 20 25 Tap water 160
NEN 3
23 Clay brick (Ibstock)
(Fairfield HA, Perth)
65 20 25 Tap water 162.5
25 Red glazed clay brick (Hanson)
(Wimpey Homes, Norwich)
40 20 25 Tap water 100
27 Clay brick (unknown)
(Persimmon Homes, Peterborough)
60 25 25 Tap water 187.5
(Bovis Homes, Leicester)
60 20 25 Tap water 150
30 Lime clay brick (Ibstock)
(Mercian HA, Wolverhampton)
60 20 25 Tap water 150
NEN 4
31 60 20 25 Tap water 150
32
Clay Brick (Brickability)
(United Welsh HA, Cardiff)
60 20 25 Tap water 150
(Ardenglen HA, Glasgow)
65 23 27 Tap water 200
36 Lime clay brick (Baggeridge)
(Johnnie Johnson HA, Wallsend,
Newcastle)
30 30 30 Distilled
water
135
38 (Furnes) clay brick
(Johnnie Johnson HA, Stockport)
60 20 17 Distilled
water
105

113
Table 3.4: samples subjected to accelerated leaching tests

Sample

Details
(matrix compositions are indicated by mass proportions)
A Aircrete block (Thermalite) (West Highland HA)
B Concrete block (Bodychell Recycling Ltd) (Cairn HA)
C Clay brick (Ibstock)
D GGBS-concrete (sample JC GGBS1)
(matrix: 60% Portland cement, 40% GGBS)
E Recycled (clay brick) aggregate-based concrete
F Silica fume-concrete (sample JC BK SF-5)
(matrix: 93% Portland cement, 7% silica fume)
G Ordinary concrete (sample JC BK 12-2 25/11; matrix: 100% Portland cement)
H Sewage sludge ash-concrete (400NA BT30 JEH)
(matrix: 70% Portland cement, 30% SSA)
I Clay brick (Red Scotland Ltd)
J PFA-concrete (PFA-30) (matrix: 70% Portland cement, 30% PFA)
CB Clay brick (Red Scotland)
CN Concrete (matrix: 50% Portland cement, 20% GGBS, 30% PFA)

Table 3.5: accelerated leaching tests conducted on samples

Samples

Duration

Leachate

pH setting

Temperature
Samples A J 64 days Tap-water (none) 25C
25C
60C
Samples A J; CB, CN 7 days Distilled water Initial pH4*
100C
25C
60C**
Samples A J 7 days Phosphate buffer Constantly
set at pH6.0
60C
* Leachant solution acidified to pH4 using nitric acid
** Samples heated to 60C within Soxtherm unit beakers
Samples oven-heated to 60C

Table 3.6: dimensions of monoliths of Samples A to J leached using 64-day test

Sample

Replicate 1

Leachant vol.

Replicate 2

Leachant vol.
A 3cm 3cm 9cm 405ml 3cm 3cm 8.5cm 385ml
B 9.5cm 3cm 2cm 285ml 9.5cm 3cm 2cm 337.5ml
C 4.5cm 6cm 3.5cm 475ml 4.5cm 6cm 3.5cm 475ml
D 8cm 3cm 8cm 360ml 8.5cm 8.5cm 3cm 450ml
E 7.5cm 3cm 3.5cm 400ml 7.5cm 3cm 3.5cm 400ml
F 4cm 4cm 4cm 320ml - -
G 4cm 4cm 4cm 320ml - -
H 4cm 4cm 4cm 320ml - -
I 4.5cm 4.5cm
6.5cm
555ml* 4.5cm 4.5cm
6.5cm
590ml*
J 3.5cm 4cm 5.5cm 405ml 3cm 3.5cm 6cm 315ml
* Samples contained missing sections due to clay brick frog holes
114
3.5.5 Accelerated leaching using heating of pH4-acidified distilled water

The NEN7345 method specifies that the distilled water leachant may be acidified to pH4,
using nitric acid conditions used by several researchers in the field. pH4 water leachate was
prepared by adding 65l of 1:10 nitric acid to 1000ml of distilled water. pH checks of the
freshly prepared leachate were taken before experimentation, and during each replenishment.
The temperature of the leachant was raised using the Soxtherm unit beakers, whereby the
monolithic samples were placed inside the beakers.

3.5.6 Tests on CB and CN samples (Table 3.7)

Experimentation was conducted on duplicates of the clay brick and the SSA and GGBS-laden
concrete samples, using the Soxtherm unit beakers. Samples were leached at room
temperature, 60C, 100C and 150C. Due to internal atmospheric pressure inside the
Soxtherm beakers, the leachate did not boil. The extracts were analysed using voltammetry.
Duplicates of each sample were cut into 2cm 2cm 5cm blocks using a diamond saw, and
wrapped in cling-film until use. Separate duplicates of the concrete and clay brick were
exposed to room temperature, 60C, 100C, or 150C. After leaching, each block was air-
dried in a fume cupboard, and wrapped in cling-film before further analysis (XRF). The
samples were cooled, and the pH of the leachate was measured again. Due to the very high
temperatures, it was impractical to conduct regular pH checks throughout the experiment
(since cooling the extracts often lasted over 20 minutes).

Table 3.7: CB and CN Test Samples

CB
Sample

Dimensions (cm)

Vol. buffer
(ml)

CN
Sample

Dimensions (cm)

Vol. buffer
(ml)
20C 20C
CB 20C i 5.0 2.1 2.3 121 CN 20C i 4.7 2.5 2.2 129
CB 20C ii 5.3 2.0 2.0 106 CN 20C ii 4.5 2.1 1.9 90
60C 60C
CB 60C i 4.7 1.9 1.9 85 CN 60C i 5.1 2.1 2.1 112
CB 60C ii 5.0 2.1 2.0 105 CN 60C ii 5.0 2.1 2.1 110
100C 100C
CB 100C i 4.8 2.1 2.1 106 CN100C i 5.3 2.0 2.2 116.5
CB100Cii 4.5 2.0 2.0 90 CN100C ii 5.0 2.0 2.0 100
150C 150C
CB150Ci 4.8 2.0 2.0 96 CN150C i 1.8 5.2 2.4 115
CB150Cii 4.8 2.1 2.2 111 CN150C ii 5.0 2.2 2.2 121

115
3.5.7 Tests on Samples A to J using pH4-acidified water (Table 3.8)

Following the aforementioned tests on the CB and CN sample monoliths, monoliths of
samples 1-10 (excluding samples 2 and 5) were tested using the same experiment, with the
omission of heating to 150C.

Three single blocks of Samples A-J (excluding samples 2 and 5 which had previously been
exhausted) were tested, at room temperature, 60C, and 100C the latter tests using the
Soxtherm units. These were approximately 2cm 2cm 5cm dimensions, which were cut
and prepared using the same methods as with previous blocks, and subjected to leaching for 1
week. These were the last of the accelerated leaching experiments conducted, and limited
volumes of samples 1, 3, 4 and 6 to 10 remained. Samples 2 and 5 had been exhausted during
previous leaching experiments (involving the use of pH6 buffer see next section). Table
3.11 details the samples and their dimensions. The samples were leached for 1 week, and
leachates were replaced 6 hours, 24 hours, 54 hours, and 4 days after commencement. The
pH was closely monitored with all samples. The sample: leachant ratio was set to a volume-
to-volume (cm
-3
) ratio of 1:5.

3.5.9 Leaching of Samples A to J using pH6 phosphate buffer

Based on a similar method employed by Nagataki et al (2001), a shortened method was tested
by heating samples, and maintaining a constant pH 6.0 ( 0.1). This experiment was designed
to reflect a consistent exposure of building materials to neutral water. (Originally, tests to
sustain mildly acidic pH (pH4) were considered, this was considered impractical.)

Materials and Methods

Samples A J were used for experiments involving the use of pH6.0 phosphate buffer.
Samples were treated at room temperature in plastic containers, or heated to 60C, either
using the Soxtherm units, or within an oven. All samples were sliced with a diamond-saw
cutter into approximately 5cm 2cm 2cm blocks, so that these could be inserted into the
Soxtherm beakers. The samples were leached for 1 week, and leachates were replaced 6
hours, 24 hours, 54 hours, and 4 days after commencement. The pH was closely monitored
with all samples. The sample: leachant ratio was set to a volume-to-volume (cm
-3
) ratio of
1:5, according to Hohberg et al (2000).

116
Table 3.8: Details of samples tested using pH4-acidified distilled water
Sample Dimensions (cm) Volume of Leachant used (ml)

Samples treated at room temperature
A 5.3 1.8 2.3 110
C 6.3 2.2 2.5 173
D 6.6 2.0 1.5 99
F 5.6 2.0 1.7 95
G 5.7 1.6 1.6 73
H 5.0 2.2 2.0 110
I 6.4 2.3 2.3 168
J 4.9 1.6 2.3 90

Samples treated at 60C
A 4.7 2.3 2.3 124
C 6.3 2.3 2.2 159
D 4.8 1.8 2.2 95
F 2.1 2.0 5.6 118
G 5.6 1.7 1.7 81
H 4.6 2.2 2.0 101
I 6.3 2.3 2.2 159
J 4.7 2.1 1.5 74

Samples treated at 100C
A 4.0 2.2 2.6 115
C 6.5 2.3 2.0 150
D 4.6 2.1 1.9 94
F 5.7 1.8 1.9 97
G 5.7 1.7 1.3 90 (altered ratio to submerge sample)
H 5.2 1.6 2.0 83
I 6.3 2.2 2.1 145
J 5.0 2.2 1.2 66

Treatment of Samples using (pH6) Dilute Phosphate Buffer

Samples A -J were leached using dilute pH6 buffer at room temperature, and at 60C (either
using the Soxtherm machine, or by placing in an oven). Due to limited sample volume,
samples B and E were only subjected to tests at room temperature, and under Soxtherm
conditions. Tables 3.9-3.11 detail the samples and the experimental settings. The phosphate
buffer was prepared by adding 1.746g of di-sodium phosphate (Na
2
HPO
4
), and 13.681g of di-
hydrogen phosphate (NaH
2
PO
4
) to 1000ml of distilled water. The pH was set to pH6.0
(0.05), at room temperature, in order to mimic typical British rainwater and soil-water pH.
Blanks (dilute buffer solution) were prepared alongside the samples produced at room
temperature and at 60C in the oven.

117
Table 3.9: Samples treated at 60C in Soxtherm units using phosphate buffer
(Replicate 1) (Replicate 2)

Sample

Dimensions (cm)

Vol. buffer (ml)

Sample

Dimensions (cm)

Vol. buffer (ml)
A 5.3 2.0 2.1 111 A 5.2 2.0 2.1 110
B 2.2 1.5 5.4 89 B 2.4 2.0 5.1 122
C 2.0 2.1 5.1 107 C 2.0 2.5 4.5 113
D 2.4 2.7 3.0 97 D 2.3 3.1 3.0 107
E 2.3 2.3 5.2 137 E 2.5 2.6 4.2 135
F 4.8 1.7 1.7 70 F 4.8 1.6 1.6 85
G 4.8 1.8 1.8 78 G 4.9 1.6 1.8 80
H 1.7 1.6 5.0 80 H 1.8 1.5 5.0 80
I 5.1 2.1 2.1 112 I 5.5 2.3 2.3 137
J 4.5 2.6 2.2 129 J 4.5 2.7 2.1 130

Table 3.10: Samples treated at room temperature using phosphate buffer
(Replicate 1) (Replicate 2)

Sample

Dimensions (cm)

Vol. buffer (ml)

Sample

Dimensions (cm)

Vol. buffer (ml)
A 1.9 2.3 5.2 115 A 4.8 1.9 1.8 82
B 2.0 1.3 5.0 65 B
C 2.2 2.0 4.5 100 C 5.2 2.0 2.2 125
D 2.2 2.3 5.1 125 D 2.2 2.0 5.0 110
E 1.3 1.9 3.6 45 E
F 1.7 2.5 4.8 105 F 5.0 2.0 2.0 100
G 2.3 2.5 5.3 150 G 5.6 2.1 2.0 117
H 1.8 1.8 5.6 90 H 5.7 2.1 2.2 131
I 2.4 2.0 5.0 120 I 5.0 2.2 2.1 120
J 5.7 2.0 2.0 115 J 5.7 2.3 2.0 130

Table 3.11: Samples treated at 60C in oven using phosphate buffer

Sample

Dimensions (cm)

Vol. buffer (ml)

Sample

Dimensions (cm)

Vol. buffer (ml)
A 5.1 2.2 2.2 120 G 5.5 2.1 2.1 120
C 5.0 2.3 2.3 130 H 4.8 2.1 2.2 110
D 4.9 1.9 2.1 100 I 5.3 2.7 2.5 180
F 5.0 2.0 2.1 105 J 5.7 2.2 1.8 110

118
4 GC-MS/MS: CONFIGURATION AND CALIBRATION

Prior to injecting and analysing sample extracts, several tests were conducted using the GC-
MS/MS instrument, in order to establish the correct temperature settings for the GC (gas
chromatographer) oven, calibrate the instrument using the standard calibration solutions
(EPA, 1994), assess the limit of detection, and assess the accuracy of the analysis method.

4.1 GC TEMPERATURE PROGRAMME

The first stage of GC-MS/MS programming was to produce a GC temperature ramp which
allowed all the dioxin and furan congener peaks to appear on the chromatogram as the
temperature was raised. Dioxins and furans generally vaporise between 250C and 330C,
which is a high temperature range for gas chromatography. Thus a suitable column was
required. A Phenomenex DB5-MS GC column (60m length 0.25mm diameter) was
connected between the MS/MS unit and a Varian 8200 auto-sampler. For chromatographic
analysis, the Saturn V6.1 software was used.

During GC development, the temperature programme was reduced from 55 minutes to 35
minutes. No MS/MS conditions were applied as yet, since the main objective was to identify
each of the congener peaks, with the assistance of a NIST library search database. As seen in
Figure 4.1, the dioxin and furan peaks occurred alongside several interfering peaks. Since the
chromatogram was produced using one of the calibration solutions (CS5), the occurrence of
such peaks was unavoidable during analysis of samples. Once a successful GC programme
was developed (Table 4.1), the next task was to fine-tune the MS/MS settings, in order to
remove both the interfering peaks, as well as the background noise.

Table 4.1: Gas chromatography and temperature settings

GC Settings

Temperature Programme
Gas Type Helium Initial Temperature 95C (hold for 1
minute)
Gas flow 0.8ml/minute 95C 235C Rate: 25C/minute
Sample Injection 1l 235C Hold for 10 minutes
Ion Trap
Temperature
200C 235C 275C Rate: 10C/minute
275C Hold for 3 minutes
275C 315C Rate: 10C/minute
Initial GC Injector
Temperature
250C
315C Hold for 7.4 minutes

9
7

F
i
g
u
r
e

4
.
.
1
:

R
a
w

c
h
r
o
m
a
t
o
g
r
a
p
h
i
c

a
n
a
l
y
s
i
s

o
f

c
a
l
i
b
r
a
t
i
o
n

s
o
l
u
t
i
o
n

98
4.2 OBTAINING THE DIOXIN AND FURAN SIGNALS

Whilst a suitable GC temperature programme was being developed, the elution (retention)
times of the dioxin and furan peaks were closely monitored. This was essential, if certain
fragment masses are to be isolated and identified at certain time intervals. In order to isolate
the dioxin and furan signals from the background interference, a dioxin and furan window
was created, whereby at certain time intervals, a restricted mass range was recorded on the
chromatogram (Figure 4.2).

Selected mass ranges were analysed during specific time intervals, during which dioxin and
furan peaks within each homologue group were produced. For example, at a set time interval,
for TCDD and TCDF analysis, only the molecules fragmenting to form 241+243amu plus
257+259amu fragments are monitored. As detailed in Table 4.2, the order of elution occurs
with increasing degree of chlorination over time, from tetra-chlorinated furans to octa-
chlorinated species (as compounds with more chlorine atoms are characterised by higher
boiling points (ATSDR, 1998; 1994). The Varian Saturn-2000 GC-MS/MS software enables
the analyst to be able to separately analyse
12
C-based congener peaks alongside the spike
solution-derived
13
C-containing congeners. It can also remove non-PCDD/F molecules or
fragments from the MS/MS unit. At certain broadband amplitudes (or voltage settings),
dioxin and furan molecules are withheld in the first MS chamber, whilst other molecules
escape. For each congener, the excitation (CID) voltage was raised from 0.5V to 5.0V
through increments of 0.5V, in order to determine the optimum potential. Due to their low
toxicity, it was decided that the identification of OCDD and OCDF was not important.

The dioxin and furan window partially isolates the congener peaks, whereby only
compounds with masses similar to the dioxin and furan compounds are shown. Further
resolution is then performed by selecting specific mass fragments. An example of the
analysis of tetra-chlorinated congeners is provided in Figure 4.3. Since some dioxin and furan
congeners contain one
37
Cl atom (as opposed to the common
35.5
Cl atom) mass fragments will
vary by 2 (amu) units.
12
C
12
-2378-TCDF fragments to produce 2 daughter ions, with masses
of 241amu and 243amu. Figure 4.4 illustrates an example of isolating the tetra-chlorinated
congener peaks. Channel 1 depicts
12
C
12
-2378-TCDF, Channel 2 depicts
13
C
12
-2378-TCDF,
Channel 3 depicts
12
C
12
-2378-TCDD, and Channel 4 depicts
13
C
12
-2378-TCDD. These peaks
appear on the right-hand-side of the figure. The spectra produced by each congener are
illustrated on the left-hand-side of Figure 4.4. Within each spectrum, the masses of the
daughter ions and the parent ion are represented by prominent markers (e.g. for
12
C
12
-2378-
TCDF, the parent ion mass is 304amu.)

9
9

F
i
g
u
r
e

4
.
2
:

F
u
l
l

c
h
r
o
m
a
t
o
g
r
a
m
,

s
h
o
w
i
n
g

t
h
e

D
i
o
x
i
n
-
F
u
r
a
n

W
i
n
d
o
w

1
0
0

F
i
g
u
r
e

4
.
3
:

P
r
o
g
r
a
m

u
s
e
d

t
o

i
d
e
n
t
i
f
y

i
n
d
i
v
i
d
u
a
l

c
o
n
g
e
n
e
r

p
e
a
k
s

1
0
1

F
i
g
u
r
e

4
.
4
:

C
h
r
o
m
a
t
o
g
r
a
p
h
s

o
f

e
a
c
h

t
e
t
r
a
-
c
h
l
o
r
i
n
a
t
e
d

c
o
n
g
e
n
e
r

(
o
f

2
3
7
8
-
T
C
D
F

a
n
d

2
3
7
8
-
T
C
D
D
)

102
Table 4.2: Mass spectrometric criteria for the congeners

Congener

Parent
Ion

Daughter
Ions
Excitation
amplitude
(m/z)

CID
energy (V)

Time
interval
(min)
12
C
12
-2378TCDF
13
C
12
-2378TCDF
306
318
241/243
252/254
106
147
1.5
1.1
12
C
12
-2378TCDD
13
C
12
-2378TCDD
322
334
257/259
268/270
135
140
2.0
2.0
11.314.0
12378PeCDF 340
352
277/279
288/290
147
150
1.6
1.6
23478PeCDF 340
352
277/279
288/290
175
150
1.6
1.6
14.016.6
12378PeCDD 356
368
293/295
304/306
158
163
1.3
1.3
16.618.0
123478HxCDF 374
386
311/313
322/324
207
171
2.0
2.0
123678HxCDF 374
386
311/313
322/324
207
171
2.0
2.0
234678HxCDF 374
386
311/313
322/324
207
171
2.0
2.0
18.019.6
123478HxCDD 390
402
327/329
338/340
173
178
1.3
1.3
123678HxCDD 390
402
327/329
338/340
173
178
1.3
1.3
123789HxCDD 390
402
327/329
338/340
173
178
1.3
1.3
19.620.5
123789HxCDF 374
386
311/313
322/324
207
171
2.0
2.0
20.521.5
1234678HpCDF 408
420
345/347
356/358
203
209
1.5
1.5
21.522.9
1234678HpCDD

426
438
361/363
372/374
188
193
2.0
2.0
23.425.3
1234789HpCDF

408
420
345/347
356/358
203
209
1.5
1.5
25.328.0

4.3 CALIBRATION
4.3.1 Calibration Standard Solutions

4 GC-MS calibration solutions were provided by Wellington Scientific, USA.
Chromatographs for the calibration solutions are contained in Appendix 4. Concentrations of
native (
12
C-containing) congeners and labelled (
13
C-containing) congeners are listed in
Table 4.3. Concentrations of labelled congeners in the solutions are constant (100 g/l),
whereas the concentrations of native congeners vary in increasing order from CS1 to the CS5
solutions.

103
Table 4.3: Congener concentrations in calibration solutions (g/l)
CS1 CS2 CS4 CS5
(
12
C) (
13
C) (
12
C) (
13
C) (
12
C) (
13
C) (
12
C) (
13
C)
2378TCDF 0.5 100 2 100 40 100 200 100
2378TCDD 0.5 100 2 100 40 100 200 100
12378PeCDF 2.5 100 10 100 200 100 1000 100
23478PeCDF 2.5 100 10 100 200 100 1000 100
12378PeCDD 2.5 100 10 100 200 100 1000 100
123478HxCDF 2.5 100 10 100 200 100 1000 100
123678HxCDF 2.5 100 10 100 200 100 1000 100
234678HxCDF 2.5 100 10 100 200 100 1000 100
123478HxCDD 2.5 100 10 100 200 100 1000 100
123678HxCDD 2.5 100 10 100 200 100 1000 100
123789HxCDD 2.5 100 10 100 200 100 1000 100
123789HxCDF 2.5 100 10 100 200 100 1000 100
1234678HpCDF 2.5 100 10 100 200 100 1000 100
1234678HpCDD 2.5 100 10 100 200 100 1000 100
1234789HpCDD 2.5 100 10 100 200 100 1000 100

4.3.2 Calibration Results: Discussion

The CS1, CS2, CS4 and CS5 calibration solutions were analysed twice. 8 analyses of the
13
C-
containing congeners were therefore conducted. The peak areas (in counts) for the
13
C-
containing congeners (all at set concentrations of 100ng/ml), showed considerable variation;
as shown in Appendix 4, Table 4.4 and Figure 4.5. The values for some congeners vary by
over 20% of the median. Amongst the lower-chlorinated congeners, it appeared that the
maximum values were mostly produced during the second analysis of the CS1 solution. For 6
of the 15 congeners, the lowest peaks were produced during the first run of the CS4 solution.

Table 4.4: Statistical data regarding
13
C-congeners in calibration solutions

Average
Peak Area
Standard
deviation
Lowest value
(% below mean)
Highest value
(% above mean)
2378TCDF 5679.75 755.26 29.10 10.97
2378TCDD 3978.75 338.24 16.53 9.31
12378PeCDF 5363.88 514.71 12.73 16.37
23478PeCDF 5148.88 388.39 14.25 10.06
12378PeCDD 3823.88 590.53 32.06 22.99
123478HxCDF 5877.13 415.95 7.54 12.40
123678HxCDF 5716.63 576.13 3.81 10.69
234678HxCDF 5450.75 364.56 12.64 5.21
123478HxCDD 3462.38 500.64 34.00 11.74
123678HxCDD 3567.38 331.56 17.59 6.35
123789HxCDD 3673.38 511.91 22.80 18.94
123789HxCDF 4850.50 244.36 8.32 7.18
1234678HpCDF 3768.00 335.67 15.29 8.94
1234678HpCDD 126.38 24.45 31.95 31.36
1234789HpCDD 3550.63 354.47 17.54 11.61

104
The distributions of the peak area values are plotted in Figure 4.5 (excluding values for
13
C-
1234678-HpCDD). Some congener data sets (e.g.
13
C-234678-HxCDF) show an even
distribution, whereas other data sets (e.g.
13
C-123478-HxCDD) are skewed. There is no
indication that the spread of the data correlated with the peak area values themselves. Nor is
there any correlation between the spread of a data set, with any group of congeners (i.e. the
size of the distribution is not affected by any homologue of congeners).

4.3.3 Correlation between
12
C-congener Peak Areas and Theoretical Concentrations

The correlation between the theoretical concentrations of each congener and their recorded
peak areas were analysed. Correlation charts for all fifteen congeners are presented in Figures
4.7 to Figure 4.21. Within each figure, the data is presented on a normal scale on the left, and
on a logarithmic scale on the right. As mentioned, each calibration solution was analysed
twice. (Results for the first run are represented by diamonds, and the second by squares.)
Overall, the recorded calibration peak areas exhibited a close relationship with the calibration
solution concentration, although discrepancies occurred with peak areas produced from the
CS1 and CS2 solutions. The second calibration study produced similar peak area results for
the CS1 and CS2 calibration solutions.

Tetra-chlorinated Congeners

A strong correlation between peak areas and the calibration solution concentrations was
produced, as shown on normal plots (Figures 4.6a and 4.7a). Nevertheless, at lower
concentrations, the plotted line appeared curved, particularly with the second set of calibration
results, whereby the peak areas for 2378-TCDF and 2378-TCDD were similar for solutions
CS1 and CS2 (Figures 4.6 b and 4.7 b).

Penta-chlorinated congeners

As seen with the calibration results for the tetra-chlorinated congeners, the results for the
penta-chlorinated congeners exhibits a strong overall correlation between peak areas and
calibration solution concentrations, and the data plots are almost equal (Figures 4.9a to 4.10a).
Nevertheless, the correlation is not observed for the CS1 and CS2 peaks for the second
calibration; the peak areas for CS1 exceed those for the CS2 solution (Figures 4.9b to 4.10b).

1
0
5

0
1
0
0
0
2
0
0
0
3
0
0
0
4
0
0
0
5
0
0
0
6
0
0
0
7
0
0
0 2
3
7
8
T
C
D
F
2
3
7
8
T
C
D
D
1
2
3
7
8
P
e
C
D
F
2
3
4
7
8
P
e
C
D
F
1
2
3
7
8
P
e
C
D
D
1
2
3
4
7
8
H
x
C
D
F
1
2
3
6
7
8
H
x
C
D
F
2
3
4
6
7
8
H
x
C
D
F
1
2
3
4
7
8
H
x
C
D
D
1
2
3
6
7
8
H
x
C
D
D
1
2
3
7
8
9
H
x
C
D
D
1
2
3
7
8
9
H
x
C
D
F 1
2
3
4
6
7
8
H
p
C
D
F 1
2
3
4
7
8
9
H
p
C
D
F
C o u n t s

F
i
g
u
r
e

4
.
5
:

p
e
a
k

a
r
e
a
s

(
c
o
u
n
t
s
)

f
o
r

1
3
C
-
c
o
n
g
e
n
e
r
s

i
n

c
a
l
i
b
r
a
t
i
o
n

s
o
l
u
t
i
o
n
s

(
i
n

t
h
e
o
r
y

c
o
n
c
e
n
t
r
a
t
i
o
n
s

o
f

e
a
c
h

c
o
n
g
e
n
e
r

w
e
r
e

e
q
u
a
l

i
n

a
l
l

s
o
l
u
t
i
o
n
s
)

106
0
2000
4000
6000
8000
10000
12000
0 100 200 300
Concentration (ug/l)
10
100
1000
10000
100000
0.1 1 10 100 1000

12
C-2378-TCDF (concentration in units of g/l)
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
0 50 100 150 200 250
10
100
1000
10000
100000
0.1 1 10 100 1000

12
C-2378-TCDD (concentration in units of g/l)
0
10000
20000
30000
40000
50000
60000
70000
0 500 1000 1500
100
1000
10000
100000
1 10 100 1000

12
C-12378-PeCDF (concentration in units of g/l)

107
0
10000
20000
30000
40000
50000
60000
70000
0 500 1000 1500
100
1000
10000
100000
1 10 100 1000

12
C-23478-PeCDF (concentration in units of g/l)
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
0 500 1000 1500
10
100
1000
10000
100000
1 10 100 1000

12
C-12378-PeCDD (concentration in units of g/l)

Hexa-chlorinated congeners

In general, correlations between peak areas and the calibration solution concentrations are
evident (Figures 4.11a 4.17a), although differences between the data plots for the calibration
runs were observed for the hexa-chlorinated dioxins (Figures 4.14a 4.16a). The logarithmic
projection of the data shows a consistent correlation between peak areas and calibration
solution concentration for the first calibration results, whereas for the second calibration
results, the peak areas for CS1 exceeded those of CS2 (Figures 4.11b 4.17b).
0
10000
20000
30000
40000
50000
60000
0 500 1000 1500
100
1000
10000
100000
1 10 100 1000

12
C-123478-HxCDF (concentration in units of g/l)
108
0
10000
20000
30000
40000
50000
60000
0 500 1000 1500
100
1000
10000
100000
1 10 100 1000

12
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
0 500 1000 1500
100
1000
10000
100000
1 10 100 1000

12
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
0 500 1000 1500
100
1000
10000
100000
1 10 100 1000

12
C-123478-HxCDD (concentration in units of g/l)
0
5000
10000
15000
20000
25000
30000
35000
40000
0 500 1000 1500
100
1000
10000
100000
1 10 100 1000

12
109
0
5000
10000
15000
20000
25000
30000
35000
40000
0 500 1000 1500
100
1000
10000
100000
1 10 100 1000

12
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
0 500 1000 1500
100
1000
10000
100000
1 10 100 1000

12

Hepta-chlorinated congeners

The overall correlation between peak areas and calibration solution concentration appears
slightly less consistent for 1234678-HpCDD (Figure 4.19a), compared with the results for the
hepta-chlorinated furans (Figures 4.18a and 4.20a). The CS1 peak areas results for 1234678-
HpCDD are also significantly higher than those for the CS2 solution almost by one order of
magnitude (Figure 4.19b). Interestingly, the peak areas for CS1 and CS2 for both calibration
analyses of 1234789-HpCDD directly correlate with the concentration (Figure 4.20b).
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
0 500 1000 1500

100
1000
10000
100000
1 10 100 1000

12
C-1234678-HpCDF (concentration in units of g/l)
110
0
5000
10000
15000
20000
25000
30000
0 500 1000 1500

100
1000
10000
100000
1 10 100 1000

12
C-1234678-HpCDD (concentration in units of g/l)
0
5000
10000
15000
20000
25000
30000
35000
40000
0 500 1000 1500

100
1000
10000
100000
1 10 100 1000

12
C-1234789-HpCDF (concentration in units of g/l)

4.4 GC-MS/MS LIMIT OF DETECTION AND PEAK RESOLUTION
4.4.1 Visual Determination of Peaks

Ideally, congener peaks should appear as distinct, bell-shaped peaks (or sharp points), which
are neither frayed nor fragmented. Figure 4.21 illustrates a sizable congener peak amongst
noticeable background interference peaks.

Figure 4.21: Possible interpretations of the Limit of Detection
111
Assuming that the spectra for the congener peak give a clear indication that the congener is
present defining the peak baseline could follow 3 different principles (refer to graph on right
on Figure 4.21). It is specified in the EPA Method 1613 manual (EPA, 1994) that the
baseline is twice the height of adjacent background peaks beside the sample peak. If this
approach was taken with the illustrated peak in Figure 4.21, the baseline could skim near the
top of the peak. If the baseline crosses the top of the background interference peaks, a
substantially greater proportion of the peak may be said to attribute to the elution of a
congener. However, an analyst may take a more pedantic view, and question the omitted
trunk of the peak below the height of the interference peaks (as highlighted in hatched blue).
One may go further, and question what lies beneath the peak (as indicated beneath).

In studying the chromatographs produced from the construction material extracts, it was
decided to define the baseline of a peak (the limit of detection) as being of the same height as
the largest adjacent background peak. (An adjacent peak was that which occurred within
the same window as the congener).

4.4.2 Solutions used for Determining the Limit of Detection (LOD)

Twelve diluted aliquots of selected calibration solutions were prepared and analysed, in order
to determine the limit of detection. One aliquot of the CS4 solution, 8 aliquots of CS2, and 3
aliquots of the CS1 calibration solutions, were diluted in different quantities of hexane (Table
4.5). Native (
12
C) congener peaks with heights exceeding the background concentration were
examined. In Table 4.5, rows highlighted in grey denote solutions which contained no
detectable concentrations of any dioxin or furan congeners.

Table 4.5: Prepared diluted calibration solutions for determining LOD
Solution

Volume of calibration
solution
Volume of hexane
0.1 CS4 5l CS4 45l
0.5 CS2 10l CS2 10l
0.25 CS2 10l CS2 30l
0.2 CS2 10l CS2 40l
0.1 CS2 10l CS2 90l
0.033 CS2 3.3l CS2 96.6l
40
th
CS2 5l (0.1 CS2) 15l
80
th
CS2 5l (40
th
CS2) 5l
160
th
CS2 5l (80
th
CS2) 5
CS1 10
TH
5l CS1 45l
CS1 50
TH
2l (CS1 10
TH
) 8l
CS1 250
TH
2l (CS1 50
TH
) 8l
112
4.4.3 Limit of Detection: Chromatographic Data

Table 4.6 details the peak areas recorded for the more concentrated solutions, and also for the
(0.2 CS2) solution. At lower peak areas, the shape, height and characteristics of the peaks
were often inconsistent. Peaks became jagged, and some were split down the middle. The
accompanying spectra were less convincing, with only one of the two fragments (e.g. 241,
243 for 2378-TCDF) being present. Parent ion spectra peaks were sometimes absent. A
moderate chromatograph peak (or culmination of peaks), slightly above the background level,
occurring at the appropriate retention time, was often the only evidence of the congener being
detected. Where no evidence on the chromatograph or the spectra was found, a value of zero
counts was noted. This explains the absence of some congeners in Table 4.6.

Table 4.6: Results of the Limit of Detection tests
12
C Congeners
0
.
1

C
S
4

0
.
5

C
S
2

0
.
2
5

C
S
2

0
.
2
5

C
S
2

0
0
1

0
.
2

C
S
2

0
.
2

C
S
2

0
0
1

0
.
1

C
S
2

0
.
1

C
S
2

0
0
1

Concentration (ng/mL)

4

1

0.5

0.5

0.4

0.4

0.2

0.2

2378-TCDF (counts) 144 65 0 15 8 0 0 0
2378-TCDD (counts) 203 0 0 26 0 0 0 0

Concentration (ng/mL)

20

5

2.5

2.5

2

2

1

1

12378-PeCDF (counts) 481 185 0 114 140 12 0 0
23478-PeCDF (counts) 479 176 18 105 33 50 0 0
12378-PeCDD (counts) 323 38 65 49 11 0 0 0
123478-HxCDF (counts) 440 170 84 55 91 0 0 0
123678-HxCDF (counts) 403 108 30 61 35 0 0 0
234678-HxCDF (counts) 335 194 116 56 0 33 0 0
123478-HxCDD (counts) 261 0 0 50 0 0 0 0
123678-HxCDD (counts) 287 39 0 69 0 0 0 0
123789-HxCDD (counts) 256 51 0 41 0 0 0 0
123789-HxCDF (counts) 370 87 29 48 33 10 0 0
1234678-HpCDF (counts) 478 50 0 100 21 0 0 0
1234678-HpCDD (counts) 503 107 0 90 4 25 0 0
1234789-HpCDF (counts) 404 48 0 83 0 0 0 0

4.4.4 Determining the Limit of Detection

Peak area data for all congeners were compiled, and compared against their theoretical
concentrations using linear regression, using a method described by Hubaux and Vos (1970).
113
The limit of detection comprises two limits: the decision limit (the lowest signal level (i.e.
peak area) which can be distinguished from the background noise), and the detection limit
(under which a sample is indistinguishable from a blank). Hubaux and Vos (1970) defined
the limit of detection as the sample content (in this project, the concentration of a
congener), which corresponds with the upper confidence limit of the signal (e.g. peak area),
which in turn occurs above the X/Y intercept of the linear regression graph. This principle is
illustrated in Figure 4.22, whereby y
C
is the decision limit, and X
D
is the detection limit,
which in turn corresponds with y
C
at the lower confidence level. Linear regression was
performed using the data detailed in Table 4.6, and the computed line-fit plot is illustrated in
Figure 4.23.

Figure 4.22: Decision and detection limits (from Hubaux and Vos, 1970)
-100
0
100
200
300
400
500
600
0 5 10 15 20 25
Concentration of congeners
S
i
g
n
a
l

(
p
e
a
k

a
r
e
a
,

c
o
u
n
t
s
)
Y
Predicted Y

Figure 4.23: Line-fit plot of linear regression analysis of limit of detection data
(dotted lines indicate 95% confidence limit)
SIGNAL
X
D

y
C

Upper confidence
limit

Predicted line-fit

Lower confidence
limit
y
O

CONTENTS
114
The linear relationship between chromatographic signal (peak area: counts) and the
concentration of congeners (g/ml) was calculated as (Sincich et al, 1999):

4.1 Signal = [19.948 Concentration] 9.217

The confidence interval (set at a limit of 95%) was calculated using Equation 4.2, by
multiplying the square root of the variance by 2:
4.2 ( )
2
% 95
2 . . s I C =

The decision and detection limits were calculated as follows (Equations 4.3, 4.4):

4.3
2
2 s y y
O C
+ =
4.4
|
|
.
|
\
|
+
=
948 . 19
2
2
s y
x
C
D

Using these equations, the decision (peak area) limit was calculated to be approximately 81.9
counts, and the detection limit for dioxin/furan congeners was calculated to be approximately
8.2g/ml. Using Equation 4.5 and the TEF values detailed in Chapter 2, Table 2.11, the
toxicity detection limit value translates as approximately 23.6g ITEQ / ml, if all congeners
were present at 8.2g/ml.
4.5
=
=
n
i
i i
C TEF TEQ
1
) (

Assuming that a sample extract is 20l, and the original sample is 10g, the above value would
translate as approximately 47.2ng ITEQ / kg.

4.5 PAR EXTRACTS AND BLANKS

The purpose of using blanks was to assure that the chromatographic results were not
contaminated by outside dioxins and furans (e.g. from glassware). No solid sample was
used, and no spike, PAR or internal standards were injected into the hexane solvent. The
hexane solvent was heated using the Soxtherm apparatus, and subjected to the clean-up and
evaporation procedures. As anticipated, no dioxin or furan peaks were detected in any blank
samples.
115
The PAR (precision and recovery) test was used to assess the recovery of
12
C-based dioxins
and furans. In accordance with the EPA manual (EPA, 1994), 10g of silica sand was rinsed
with methylene chloride, and allowed to dry in the fume cupboard. The sample was then
added to the thimble, immersed into hexane solvent, and 10l of PAR standard was injected
into the sample. The PAR sample was processed using the Soxtherm extraction, clean-up and
evaporation methods, and analysed using GC-MS/MS.

4.6 THE INTERNAL STANDARD

In mainstream dioxin and furan analysis, researchers inject 10l of internal standard into the
final extract, shortly before the extract is subjected to GCMS processing. With the majority
of sample extracts produced in December 2004, 5l aliquots were injected into the
(approximately) 20l samples, theoretically raising the volume to 25l. The internal standard
contains 200ng/ml of
13
C
12
-1234-TCDD (Spectrum 1A), which was detected alongside
13
C
12
-
2378-TCDD, and which shares the same spectra as
13
C-2378-TCDD (Figure 4.24). The peak
area results for internal standard peaks are recorded in Table 4.7. The results alone indicate a
wide variation in the peak areas produced, which can at least partly be attributed to variation
in the volume of the final extracts.

Table 4.7: Internal standard peak areas
Sample

Internal
standard Peak
Sample Internal
standard peak
Sample Internal
standard peak
D21 1444 D32 1331 D41 1500
D22 1995 D33 1209 D42 176
D23 1154 D34 1451 D43 1420
D25 1041 D35 1852 D44 793
D26 1224 D36 870 D47 1564
D27 1318 D37 1438 D48 1096
D28 1228 D38 1615 D51 1726
D30 1674 D39 1804 D52 1021
D31 1008 D40 1518

The recorded internal standard peak areas for the sample extracts were plotted on a histogram,
as illustrated in Figure 4.25. The median occurred within the 15001600 count (peak area)
interval, two intervals below the 17001800 interval. The average was calculated to be 1326
counts, with a standard deviation of 385 counts (or 29%). This margin of error affects the
dioxin and furan peak limits of detection, and those of sample extracts and spike solutions.

1
1
6

F
i
g
u
r
e

4
.
2
4
:

T
e
t
r
a
-
c
h
l
o
r
i
n
a
t
e
d

c
o
n
g
e
n
e
r

c
h
r
o
m
a
t
o
g
r
a
p
h
s
,

w
i
t
h

i
n
t
e
r
n
a
l

s
t
a
n
d
a
r
d

p
e
a
k

118
0
1
2
3
4
5
6
4
0
0
6
0
0
8
0
0
1
0
0
0
1
1
0
0
1
2
0
0
1
3
0
0
1
4
0
0
1
5
0
0
1
6
0
0
1
7
0
0
1
8
0
0
1
9
0
0
2
0
0
0
M
o
r
e
Internal standard peak area (counts)
F
r
e
q
u
e
n
c
y

Figure 4.25: Histogram of internal standard peak areas

Figure 4.26 provides possible proof of the variations in the volume of final extracts. There is
a moderate correlation between the peak areas of
13
C
12
-1234-TCDD and
13
C
12
-2378-TCDD -
the correlation co-efficient was calculated to be 0.897. In light of these variations, the
calculated concentration of congeners (in ng/ml) in 20l sample extracts may have possessed
an error margin of 40%.

0
100
200
300
400
500
600
700
0 500 1000 1500 2000 2500
Internal standard (counts)
2
3
7
8
-
T
C
D
D

(
c
o
u
n
t
s
)

Figure 4.26: Correlation between internal standard and
13
C-2378 TCDD peak areas

119
5 DIOXINS AND FURANS IN HOUSING CONSTRUCTION
MATERIALS AND SOILS: RESULTS AND DISCUSSION

5.1 INTRODUCTION

In December 2004, 46 new housing construction site samples (mostly from Scottish
locations), were extracted and analysed. In February 2005, 154 new housing construction site
samples, 15 existing housing samples, 13 demolition waste samples, 8 PFA samples, and 22
soil samples were extracted and analysed for dioxins and furans (212 in total).

5.2 ANALYSIS OF GC-MS/MS DATA
5.2.1 Calculating the Concentration in Solid Samples

Conversion factors are used for determining the concentration of congeners (in ng/ml) when
compared with peak areas (in counts). The concentration in the original sample is then
computed. Equation 5.1 was used to determine the levels in the sample (actual mass, not
oven-dried mass) (USEPA, 1994):
5.1
|
|
.
|
\
|
(
(
|
|
.
|
\
|
=
S
g
V
f
A
C
ex
1000

C = Concentration of congener in sample (ng/kg)
A = Peak area (counts)
f = Conversion factor (counts / ng / ml )
V
ex
= Volume of extract (ml)
S = Mass of sample (g)

Assuming that the sample is exactly 10.00 grams (0.01g), the equation is simplified to
Equation 5.2:
5.2
|
|
.
|
\
|
=
f
A
C 2
5.2.2 Results for Dioxins and Furans in Samples

No dioxins or furans originating from the samples were detected. Native (
12
C-based) dioxins
and furans were occasionally detected in extracts, which were processed immediately after re-
calibrating the GC-MS/MS using the CS5 calibration solution. Since the CS5 calibration
solution contained comparatively high concentrations of
12
C-based congeners, the 12C-based
congener peaks observed in subsequent sample extracts did not attribute to the presence of
dioxins or furans in the samples. Instead, residues from the CS5 solution may have been
absorbed into the sample extracts processed after calibration.
120
5.2.2.1 Results for Samples Analysed in December 2004

39 construction material samples from Scottish housing sites were processed (using the clean-
up filter illustrated in Figure 3.8) and analysed. Table 5.1 details the sample types, and the
housing association sites from which they originated. No sample-derived or spike solution-
derived dioxins or furans were detected in most of the samples, and it was apparent that the
clean-up method had removed most congeners. Due to the poor recovery of spike-solution-
based congeners, the detection limit could not be specified. Chromatographs for samples
D22, D23, D30, D38, D39 and D40 contained
12
C-based dioxin and furan peaks, which were
derived from calibration using the CS5 solution.

Table 5.1: Samples analysed in December 2004

Concrete

Clay Bricks

Mortar

Cement

Plasterboard
Ardenglen H.A. D1 D3 D25, 43 D4
Angus H.A. D34, D38* D37 D33
Berwickshire H.A. D40 D39
Cairn H.A. D2, 12 D11
Canmore H.A. D8
Cube H.A. D22 D21 D26, 44 D7
Fairfield H.A. D28, 30 D27 D32
Link H.A. D13 D9 D10
Pavillon H.A. D49
Stewart Milne Homes D35 D14 D24, 36,
41*

Ty Gwalia D15, 50-52*
United Welsh H.A. D16
West Highland H.A. D5 D23, 42 D6

5.2.2.2 Results for Samples Analysed in February 2005

218 samples were processed using the clean-up filter illustrated in Figure 3.9. These included
162 samples from new-build housing, 22 soil samples, 8 PFA samples, 13 demolition waste
samples, and 13 samples from existing housing. 139 samples were successfully processed
and analysed (approximately 63%). Peaks on another 28 sample chromatographs were
distorted due to contamination, especially with soil extracts. With soils and demolition
wastes, the clean-up filtration of extracts often produced a solid or sticky residue trapped on
the filter, or a cloudy extract (which was discarded). Only 5 demolition waste samples and 11
soil samples were successfully processed and analysed. The chromatographs of PFA sample
extracts were mostly distorted with background contamination, and only one PFA sample
chromatograph could be accurately analysed. A further 33 sample chromatographs showed no
peaks - possibly because the GC-MS/MS needle obtaining the extracts missed the sample
121
vials. Tables 5.2 to 5.16 detail the results of successfully processed samples. Overall, no
sample-derived dioxins or furans were detected in any of the samples, and results are
therefore expressed as being below the limit of detection specified in Chapter 4, page 113.

Table 5.2: Toxicity levels in samples collected in East Anglia (ng ITEQ / kg)

Housing Association

Sample reference number
N122 N180 N181 Bellway Homes,
Norwich <47.5 <47.5 <47.5
N178 N182 N185 N186 Wimpey Homes,
Ipswich <47.5 <47.5 <47.5 <47.5

Table 5.3: Toxicity levels in samples collected in East Midlands (ng ITEQ / kg)

Housing Association

N123 Bovis Homes,
Leicester <47.5
N125 Derwent HA, Derby
<47.5
N124 Persimmon Homes,
Peterborough <47.5

Table 5.4: Toxicity levels in samples collected in London (ng ITEQ / kg)

Housing Association

N85 N86 N87 N92 Charlton Triangle Ltd,
Charlton <47.5 <47.5 <47.5 <47.5
N18 N23 N84 Network Housing HA,
Victoria <47.5 <47.5 <47.5
N20 N89 N100 Patchwork HA,
Enfield <47.5 <47.5 <47.5

Table 5.5: Toxicity levels in samples collected in Northeast England (ng ITEQ / kg)

Housing Association

N29 N36 N58 N130 Johnnie Johnson HA,
Belford <47.5 <47.5 <47.5 <47.5
N34 N44 N60 Johnnie Johnson HA,
Wallsend <47.5 <47.5 <47.5
N37 N59 N61 N88 Tees Valley HA,
Sunderland <47.5 <47.5 <47.5 <47.5
122
Table 5.6: Toxicity levels in samples collected in Northwest England (ng ITEQ / kg)

Housing Association

N53 N55 N73 CDS Housing,
Liverpool <47.5 <47.5 <47.5
N46 N69 N74 N128 Cosmopolitan HA,
Olive Mt Heights,
Liverpool
<47.5 <47.5 <47.5 <47.5
N56 N63 N129 Cosmopolitan HA,
Kirkby <47.5 <47.5 <47.5
N47 N50 N51 N57 Johnnie Johnson HA,
Stockport <47.5 <47.5 <47.5 <47.5
N40 N72 Mosscare HA, Gorton,
Manchester <47.5 <47.5

Table 5.7: Toxicity levels in samples collected in the English south coast (ng ITEQ / kg)

Housing Association

N103 N106 Berkeley Homes,
Gosport <47.5 <47.5
N97 N98 N99 Pavillon HA, Fleet
<47.5 <47.5 <47.5
N105 N108 N175 Portsmouth HA Site 1,
Portsmouth <47.5 <47.5 <47.5
N96 N101 N102 Portsmouth HA Site 2,
Portsmouth <47.5 <47.5 <47.5

Table 5.8: Toxicity levels in samples collected in southwest England (ng ITEQ / kg)

Housing Association

N126 N177 Magna Homes, Yeovil
<47.5 <47.5
N177 Western Challenge,
Poole <47.5

Table 5.9: Toxicity levels in samples collected in the West Midlands (ng ITEQ / kg)

Housing Association

N15 N24 N32 N33 Jephson HA,
Bedworth <47.5 <47.5 <47.5 <47.5
N16 N19 N25 N27 N28 Mercian HA,
Wolverhampton <47.5 <47.5 <47.5 <47.5 <47.5
N17 N21 N22 Optima HA,
Birmingham <47.5 <47.5 <47.5

123
Table 5.10: Toxicity levels in samples collected in Yorkshire (ng ITEQ / kg)

Housing Association

N70 N71 N76 Leeds Federated HA,
Leeds <47.5 <47.5 <47.5
N45 N82 N94 Redwall Contractors,
Sheffield <47.5 <47.5 <47.5
Parkgate, Rotherham <47.5 <47.5 <47.5
Wickersley <47.5 <47.5 <47.5

Table 5.11: Toxicity levels in samples collected in Northern Ireland (ng ITEQ / kg)

Housing Association

N132 N135 N136 N138 N139 N140 Fathom Park, Newry
<47.5 <47.5 <47.5 <47.5 <47.5 <47.5
N142 N144 Fairmount, Armagh
<47.5 <47.5

Table 5.12: Toxicity levels in samples collected in Scotland (ng ITEQ / kg)

Housing Association

Ns6 Angus HA, Arbroath
<47.5
N10 Ardenglen HA,
Glasgow <47.5
N11 N12 Cairn HA, Inverness
<47.5 <47.5
Ns8 Canmore HA,
Edinburgh <47.5
Ns5 Cube HA, Glasgow
<47.5
Ns7 N9 Link HA, Airdrie
<47.5 <47.5

Table 5.13: Toxicity levels in samples collected in Wales (ng ITEQ / kg)

Housing Association

N109 N114 Ty Gwalia, Site 1,
Swansea <47.5 <47.5
N111 N112 N113 Ty Gwalia, Site 2,
Swansea <47.5 <47.5 <47.5
N115 N120 UWHA, Cardiff
<47.5 <47.5
124
Table 5.14: Toxicity levels in samples collected in existing housing (ng ITEQ / kg)

Samples (Reference number)

N149 N150 N151 N152 N154 N156 N157 N158 N160 N161
<47.5 <47.5 <47.5 <47.5 <47.5 <47.5 <47.5 <47.5 <47.5 <47.5

Table 5.15: Toxicity levels in demolition samples (ng ITEQ / kg)

Samples (Reference number)

N164 N165 N166 N168 N171
<47.5 <47.5 <47.5 <47.5 <47.5

Table 5.16: Toxicity levels in soil and PFA samples (ng ITEQ / kg)

Samples (Reference Number)

N
1
8
7

N
1
8
8

N
1
9
5

N
1
9
9

N
2
0
0

N
2
0
1

N
2
0
3

N
2
1
1

N
2
1
3

N
2
1
5

N
2
1
7

N
2
1
8

Soil
<47.5 <47.5 <47.5 <47.5 47.5* 47.5* <47.5 <47.5 <47.5 <47.5 <47.5 <47.5
N207
PFA
<47.5
* Minor peaks of hepta-chlorinated furans were detected on the chromatographs, but the mass spectra did not
produce distinctive patterns (see below).

With two soil samples (Table 5.16: N200, N201), peaks were detected on the chromatographs
alongside the
13
C-based 1234678-HpCDF and 1234678-HpCDD congener peaks. The spectra
for these peaks were unconvincing, although dioxins and furans may have been present in the
soil samples at detectable concentrations. Furthermore, the peak areas were either below or
equal to the decision limit (y
C
) peak area of 81.9 counts, as specified in Chapter 4, page 113.
The peaks and their associated spectra are illustrated in Figures 5.1 and 5.2. It was not
possible to study this further, since access to the GC-MS/MS was withdrawn immediately
following processing of the soil samples (as the consultancy was using the machine
commercially from then on).

5.3 RECOVERY OF DIOXINS AND FURANS

The EPA Method 1613 document (EPA, 1994) specifies minimum limits of congener
recovery. Table 7 in the document prescribes minimum recoveries (%) for each congener, as
detailed in Table 5.17.

1
2
5

F
i
g
u
r
e

5
.
1
:

p
o
s
s
i
b
l
e

d
e
t
e
c
t
i
o
n

o
f

1
2
3
4
6
7
8
-
H
p
C
D
F

a
n
d

1
2
3
4
6
7
8
-
H
p
C
D
D

i
n

s
o
i
l

s
a
m
p
l
e

N
2
0
0

(
T
y

G
w
a
l
i
a

s
i
t
e

2
,

S
w
a
n
s
e
a
)

1
2
6

F
i
g
u
r
e

5
.
2
:

p
o
s
s
i
b
l
e

d
e
t
e
c
t
i
o
n

o
f

1
2
3
4
6
7
8
-
H
p
C
D
F

a
n
d

1
2
3
4
6
7
8
-
H
p
C
D
D

i
n

s
o
i
l

s
a
m
p
l
e

N
2
0
1

(
M
a
g
n
a

H
o
m
e
s
,

Y
e
o
v
i
l
)

127
Table 5.17: Minimum prescribed recoveries of dioxins and furans (USEPA, 1996)

Dioxin congeners

Min. recovery

Furan congeners

Min. recovery
2378-TCDF 24% 2378-TCDD 25%
12378-PeCDF 24%
23478-PeCDF 21%
12378-PeCDD 25%
123478-HxCDF 26% 123478-HxCDD 32%
123678-HxCDF 26% 123678-HxCDD 28%
123789-HxCDF 29%
234678-HxCDF 28%
123789-HxCDD n/a
1234678-HpCDF 28%
1234789-HpCDF 26%
1234678-HxCDD 23%

Throughout both experiments (December 2004 and February 2005), 4 spike solutions were
used. Since 10l of spike solution was originally injected into the sample, and the final
extract was approximately 20l, the peak areas of
13
C-based (spike solution-derived)
congeners would be 50% the area of those in the spike solution itself assuming that 100% of
congeners are recovered. The recovery (R%) of each
13
C-based congener for each sample
was calculated using Equation 5.3:
5.3 R (%)
|
|
.
|
\
|
|
|
.
|
\
|
=
ion SpikeSolut
Sample
ion SpikeSolut
act SampleExtr
l
l
A
A
10
20

Whereby A = Chromatograph peak area (counts)

5.3.1 Recovery of Congeners in Samples Processed in December 2004

Table 5.18 details the recoveries of congeners determined for samples, extracted in December
2004, and in February 2005, respectively. Results highlighted in light grey indicate
recoveries moderately below the acceptable limit. Results highlighted in dark grey indicate
poor or minimal recoveries (below 10%). Overall, the recoveries of all
13
C-containing spike
solution dioxins and furans were disappointing. 12378-PeCDD, 123789-HxCDD, 1234678-
HpCDD and 1234789-HpCDF were not detected in any samples. The peaks for 12378-
PeCDD and 1234789-HpCDF were missing from the chromatograms, and the GC-MS/MS
time intervals had to be corrected. No recovery values occurred above the EPA Method 1613
minimum limits (with occasional exceptions among 12378-PeCDF, 123478-HxCDF, 123789-
HxCDF and 1233678-HpCDF peaks). Furthermore, the HxCDD congener peaks were poorly
isolated from one another, and their appearance on the chromatograms was occasional; the
large recoveries (samples D21 and D32) may not be solely attributed to 123678-HxCDD.

1
2
8

T
a
b
l
e

5
.
1
8
a
:

R
e
c
o
v
e
r
y

o
f

1
3
C
-
b
a
s
e
d

c
o
n
g
e
n
e
r
s

i
n

s
a
m
p
l
e
s

D
1

t
o

D
2
0

a
n
a
l
y
s
e
d

i
n

D
e
c
e
m
b
e
r

2
0
0
4

(
u
n
i
t
s

e
x
p
r
e
s
s
e
d

i
n

p
e
r
c
e
n
t
a
g
e
s
)

2 3 7 8 - T C D F
2 3 7 8 - T C D D
1 2 3 7 8 - P e C D F
2 3 4 7 8 - P e C D F
1 2 3 7 8 - P e C D D
1 2 3 4 7 8 - H x C D F
1 2 3 6 7 8 - H x C D F
2 3 4 6 7 8 - H x C D F
1 2 3 4 7 8 - H x C D D
1 2 3 6 7 8 - H x C D D
1 2 3 7 8 9 - H x C D D
1 2 3 7 8 9 - H x C D F
1 2 3 4 6 7 8 - H p C D F
1 2 3 4 6 7 8 - H p C D D
1 2 3 4 7 8 9 - H p C D F
D
1

8
.
0
6

8
.
9
4

1
1
.
2
4

7
.
3
4

0

9
.
8
1

1
0
.
3
7

8
.
2
6

0

0

0

9
.
2
2

0

0

0

D
2

1
.
2
4

3
.
3
7

1
.
7
6

0

0

0
.
8
1

1
.
7
8

0

0

0

0

0

0

0

0

D
3

1
0
.
1
5

1
1
.
8
3

1
5
.
2
2

9
.
2
8

0

1
0
.
2
8

1
0
.
3
7

1
0
.
5
5

4
2
.
7
5

0

0

1
3
.
4
1

0

0

0

D
4

1
0
.
0
1

1
1
.
6
9

1
8
.
4
0

1
0
.
0
7

0

1
2
.
1
3

1
7
.
0
6

1
1
.
4
5

6
.
1
4

1
2
.
9
1

0

1
2
.
4
7

1
3
.
5
7

0

0

D
5

4
.
1
2

5
.
4
6

1
0
.
0
1

4
.
6
0

0

9
.
6
0

8
.
1
4

1
0
.
7
1

6
.
4
3

1
2
.
1
9

0

1
1
.
2
9

7
.
5
3

0

0

D
6

5
.
2
2

5
.
8
6

6
.
7
4

5
.
6
5

0

1
1
.
3
1

7
.
3
5

8
.
0
5

3
.
4
5

5
.
6
5

0

9
.
0
2

9
.
6
7

0

0

D
7

2
.
7
0

3
.
8
0

0

0

0

7
.
0
3

2
.
5
6

0

0

0

0

2
1
.
0
5

0

0

0

D
8

3
.
3
2

4
.
6
3

0

0

0

3
.
8
1

3
.
2
2

2
.
4
1

0

0

0

0

0

0

0

D
1
0

1
.
5
4

3
.
1
8

3
.
9
4

1
.
6
9

0

6
.
4
7

6
.
3
2

8
.
3
8

3
.
6
3

4
.
8
8

0

5
.
4
7

6
.
7
8

0

0

D
1
1

0

0

0

0

0

0

0

0

0

0

0

0

0

0

0

D
1
2

8
.
6
6

7
.
9
3

1
5
.
8
9

4
.
8
6

0

1
1
.
1
8

1
0
.
9
9

8
.
7
9

0

9
.
2
7

0

9
.
9
1

0

0

0

D
1
3

0

0

0

0

0

0

0

0

0

0

0

0

0

0

0

D
1
4

0

0

0

0

0

0

0

0

0

0

0

0

0

0

0

D
1
5

0

0

1
.
6
1

0

0

0
.
9
9

3
.
3
9

0
.
8
2

0

0

0

1
.
4
8

0

0

0

D
1
6

0

0

0

0

0

0

0

0

0

0

0

0

0

0

0

D
1
7
P
A
R

1
4
.
0
3

1
3
.
4
6

1
2
.
9
0

8
.
0
3

0

9
.
3
0

7
.
4
2

7
.
9
1

6
.
7
4

5
.
6
0

9
.
5
5

7
.
7
2

4
.
2
1

0

0

D
1
7

8
.
0
2

1
2
.
7
4

1
7
.
1
7

1
1
.
2
6

0

1
6
.
5
8

1
4
.
7
9

1
1
.
0
8

1
4
.
5
6

9
.
9
3

0

2
0
.
6
1

1
7
.
0
1

0

0

D
1
8
P
A
R

7
.
6
9

8
.
4
0

9
.
2
0

3
.
8
6

0

7
.
4
6

8
.
0
4

4
.
6
1

4
.
3
4

4
.
3
8

7
.
5
9

6
.
4
4

5
.
1
2

0

0

D
1
8

4
.
1
5

4
.
3
8

9
.
9
6

3
.
2
4

0

1
2
.
3
0

9
.
9
6

5
.
9
3

8
.
1
3

3
.
8
1

0

5
.
3
7

2
.
0
5

0

0

D
1
9
P
A
R

0

2
.
3
0

5
.
9
8

2
.
1
3

0

4
.
4
0

4
.
2
4

0

2
.
9
5

4
.
5
7

0

1
.
9
7

3
.
9
4

0

0

D
1
9

1
.
5
8

4
.
4
9

5
.
1
7

2
.
0
9

0

9
.
0
8

6
.
8
2

0

4
.
4
4

2
.
3
8

0

3
.
6
5

3
.
3
5

0

0

D
2
0
P
A
R

0

0

3
.
6
1

0

0

5
.
1
7

3
.
9
4

0

3
.
1
0

2
.
0
1

0

0

4
.
7
1

0

0

D
2
0

0

0

4
.
0
3

0

0

5
.
6
1

5
.
0
8

0

0

1
.
4
3

0

0

5
.
1
1

0

0

1
2
9

T
a
b
l
e

5
.
1
8
b
:

R
e
c
o
v
e
r
y

o
f

1
3
C
-
b
a
s
e
d

c
o
n
g
e
n
e
r
s

i
n

s
a
m
p
l
e
s

D
2
2

t
o

D
5
1

a
n
a
l
y
s
e
d

i
n

D
e
c
e
m
b
e
r

2
0
0
4

(
u
n
i
t
s

e
x
p
r
e
s
s
e
d

i
n

p
e
r
c
e
n
t
a
g
e
s
)

2 3 7 8 - T C D F
2 3 7 8 - T C D D
1 2 3 7 8 - P e C D F
2 3 4 7 8 - P e C D F
1 2 3 7 8 - P e C D D
1 2 3 4 7 8 - H x C D F
1 2 3 6 7 8 - H x C D F
2 3 4 6 7 8 - H x C D F
1 2 3 4 7 8 - H x C D D
1 2 3 6 7 8 - H x C D D
1 2 3 7 8 9 - H x C D D
1 2 3 7 8 9 - H x C D F
1 2 3 4 6 7 8 - H p C D F
1 2 3 4 6 7 8 - H p C D D
1 2 3 4 7 8 9 - H p C D F
D
2
2

8
.
8
7

9
.
8
8

9
.
8
2

5
.
7
2

0

1
4
.
7
8

1
1
.
7
7

9
.
0
7

0

7
6
.
7
2

0

9
.
1
7

0

0

0

D
2
3

9
.
3
1

9
.
2
3

1
3
.
3
7

4
.
9
6

0

1
4
.
8
5

1
7
.
0
4

1
0
.
1
8

0

0

0

7
.
9
1

0

0

0

D
2
4

0

0

0

0

0

0

0

0

0

0

0

0

0

0

0

D
2
5

7
.
4
2

1
5
.
2

9
.
0
3

5
.
1
3

0

1
2
.
3
4

1
1
.
7
7

6
.
3
2

5
.
5
3

4
1
.
7
5

0

7
.
2
5

0

0

0

D
2
6

8
.
6
2

7
.
5
4

9
.
1
1

5
.
0
2

0

1
3
.
1
1

2
0
.
1
4

8
.
1
5

7
.
2
8

8
1
.
9
8

0

5
.
5
5

0

0

0

D
2
7

9
.
9
6

9
.
7
2

1
6
.
8
6

6
.
3
1

0

2
0
.
3
7

1
4
.
0
1

9
.
8
1

0

7
.
2
7

0

6
.
1
4

0

0

0

D
2
8

0

0

0

3
.
1
3

0
.
8
6

0

6
.
1
7

1
0
.
2
3

2
.
3
9

1
1
3
.
3
8

0

0

1
.
1
1

0

0

D
3
0

1
6
.
3
2

1
9
.
1
1

2
4
.
6
9

8
.
8
0

0

2
6
.
0
3

2
8
.
0
1

2
5
.
0
8

0

2
4
.
5
3

0

1
9
.
1
5

2
9
.
4
1

0

0

D
3
2

1
0
.
9
6

8
.
3
6

1
4
.
4
4

3
.
4
5

0

1
6
.
9
0

1
6
.
3
6

9
.
2
6

5
.
8
8

6
6
.
8
2

0

1
0
.
6
5

0

0

0

D
3
3

9
.
1
4

1
3
.
4
1

1
5
.
2
2

9
.
5
0

0

1
7
.
9
3

1
9
.
7
7

1
2
.
3
2

0

0

0

1
1
.
0
9

0

0

0

D
3
4

1
7
.
5
6

1
9
.
9
7

1
2
.
7
3

1
1
.
9
8

0

1
2
.
9
2

1
7
.
3
5

1
1
.
9
6

0

0

0

8
.
8
0

0

0

0

D
3
5

1
8
.
5
2

1
5
.
6
3

2
0
.
6
3

1
2
.
5
7

0

2
7
.
1
9

3
1
.
2
3

2
1
.
4
6

0

1
4
.
1
8

0

1
8
.
7
1

0

0

0

D
3
6

1
2
.
8
9

1
3
.
4
1

1
9
.
2
8

1
2
.
9
5

0

2
3
.
5
9

2
6
.
5
9

2
2
.
3
8

0

1
7
.
5
7

0

1
6
.
4
9

1
5
.
6
1

0

0

D
3
7

1
5
.
4
6

2
1
.
1
7

2
1
.
7
0

1
1
.
4
9

0

2
2
.
1
7

2
1
.
9
4

1
8
.
5
2

0

0

0

1
2
.
7
9

0

0

0

D
3
8

1
9
.
4
5

2
0
.
0
8

3
0
.
3
1

1
9
.
8
6

0

3
2
.
2
6

3
2
.
2
9

2
2
.
8
1

0

2
8
.
4
6

0

1
1
.
7
6

3
0
.
5
3

0

0

D
3
9

1
7
.
8
7

1
8
.
7
8

1
3
.
5
9

9
.
1
2

0

2
8
.
4
1

2
3
.
4
2

1
7
.
1
7

0

1
2
.
7
6

0

1
8
.
3
4

9
.
6
2

0

0

D
4
0

1
7
.
7
6

1
7
.
3
2

1
4
.
0
1

1
0
.
6
3

0

1
4
.
0
7

1
3
.
7
6

1
0
.
9
1

0

9
.
4
6

0

7
.
6
9

0

0

0

D
4
1

0

0

0

0

0

0

0

0

0

0

0

0

0

0

0

D
4
2

0

0

0

0

0

0

0

0

0

0

0

0

0

0

0

D
4
3

1
8
.
4
5

1
5
.
1
4

2
7
.
8
9

1
7
.
4
3

0

1
4
.
7
2

2
6
.
3
4

2
5
.
0
8

0

0

0

1
8
.
1
9

1
9
.
1
0

0

0

D
4
4

1
2
.
6
8

9
.
6
1

7
.
4
7

5
.
1
8

0

8
.
2
3

1
3
.
1
4

9
.
7
5

0

4
.
2
8

0

9
.
9
1

0

0

0

D
4
5

1
4
.
8
8

1
6
.
0
1

1
9
.
9
2

1
4
.
7
3

0

1
8
.
1
2

1
8
.
3
4

1
3
.
0
0

0

0

0

1
1
.
7
6

1
0
.
5
9

0

0

D
4
6

3
.
1
3

4
.
9
4

5
.
6
9

0

0

4
.
7
6

7
.
8
1

1
.
3
5

0

0

0

0

0

0

0

D
4
9

2
2
.
2
0

1
7
.
0
4

2
2
.
4
8

5
.
8
8

0

1
7
.
4
2

1
9
.
7
1

1
3
.
2
4

0

0

0

1
7
.
9
0

0

0

0

D
5
1

2
8
.
0
7

2
3
.
5
6

2
2
.
4
8

1
2
.
2
5

0

2
4
.
3
6

2
1
.
8
1

2
3
.
6
1

0

7
.
7
6

0

1
1
.
4
6

0

0

0

D
5
2

2
4
.
2
6

3
2
.
9
5

2
5
.
4
0

1
2
.
4
6

0

2
4
.
0
4

2
1
.
1
9

2
2
.
9
9

0

0

0

1
9
.
2
3

1
4
.
6
4

0

0

130
Although usually below the minimum recovery limits, the recoveries of tetra, penta, and hexa-
chlorinated furans (as well as for 2378-TCDD) generally surpassed the recoveries of HxCDD,
and hepta-chlorinated congener peaks. Amongst the former group, recoveries for samples
D30 through D40 appear to be marginally improved, compared with results for the other
samples. It was evident that the EPA Method 1613 clean-up filter removed a substantial
majority of the dioxins and furans passing through the column. The poor performance of the
experiment in December 2004 necessitated the development of a shorter, simpler column (see
Chapter 3, page 73).

5.3.2 Recoveries of Congeners in Extracts Processed in February 2005

With the altered clean-up filter, considerable improvement in dioxin and furan congener
recoveries was realised. Recovery data for all successfully processed samples are provided in
Tables 5.19 to 5.28. Figures 5.3 to 5.6 illustrate the range of recoveries (decimal fraction
values) for congeners in different homologues. Recoveries of tetra-chlorinated congeners
were usually moderate or acceptable; the recoveries of penta-chlorinated congeners performed
slightly better in comparison. Among the hexa-chlorinated congeners, recoveries were often
moderate or weak (<10%), although acceptable recoveries were possible (particularly with
samples N161 through N174). With hepta-chlorinated congeners, acceptable recoveries were
rarely achieved, and weak (<10%) or negligible recoveries were common.
0
5
10
15
20
25
30
35
40
45
50
Fraction of congeners recovered
F
r
e
q
u
e
n
c
y

Figure 5.3a: Proportion of tetra-chlorinated congeners retained throughout experiment
131
0
10
20
30
40
50
60
F
r
e
q
u
e
n
c
y

Figure 5.4: Proportion of penta-chlorinated congeners retained throughout experiment
0
10
20
30
40
50
60
70
80
90
100
F
r
e
q
u
e
n
c
y

Figure 5.5: Proportion of hexa-chlorinated congeners retained throughout experiment
0
5
10
15
20
25
30
35
40
45
50
F
r
e
q
u
e
n
c
y

Figure 5.6: Proportion of hepta-chlorinated congeners retained throughout experiment
132

In conclusion, developing the modified clean-up filter enabled moderate proportions of
congeners to be retained in the samples. Nevertheless, more than half of all dioxins and
furans were still being removed or lost throughout the preparation of sample extracts.
13
C-
based-1234678-HpCDD was either not detected, or the peak was too small to produce
acceptable spectra.

5.4 CONCLUSIONS AND RECOMMENDATIONS

For the majority of construction material samples analysed in February 2005, it can be said
that dioxin and furan levels did not exceed 50ng ITEQ / kg. Due to background interferences
in chromatographs, the same conclusion cannot be extended to either soil samples or PFA.

Larger sample aliquots may be necessary (perhaps 30g, or 50g), since construction materials
contain very low concentrations of dioxins and furans, as reported in the literature (Chapter
2). The clean-up method may have to be altered in order to accommodate PFA, demolition
waste and soil samples. This may require the use of toluene solvent to wash out dioxins and
furans, and perhaps the standard nitrogen-gas evaporation stage afterwards. Wash-ups were
regularly included during GC-MS/MS analysis (one for every 3 to 5 samples). Nevertheless,
some sample analyses were affected by previous calibration solution analyses. The volume
of the final extract in the 100l vials was difficult to determine with precision. Internal
standard must therefore be injected into each and every sample; alternatively, a 100l vial (or
one of similar size) with a 20l level mark could be used instead. It is probable that the wide
variation in congener recoveries may be attributed to the volume of the final extract.
143
Table 5.19: recoveries (percentages): February analyses (first 20 samples)

Acceptable recovery Below prescribed recovery (above 10%)
<10% recovery Not detected

Sample
2
3
7
8
-
T
C
D
F

2
3
7
8
-
T
C
D
D

1
2
3
7
8
-
P
e
C
D
F

2
3
4
7
8
-
P
e
C
D
F

1
2
3
7
8
-
P
e
C
D
D

1
2
3
4
7
8
-
H
x
C
D
F

1
2
3
6
7
8
-
H
x
C
D
F

2
3
4
6
7
8
-
H
x
C
D
F

1
2
3
4
7
8
-
H
x
C
D
D

1
2
3
6
7
8
-
H
x
C
D
D

2
3
4
6
7
8
-
H
x
C
D
D

1
2
3
7
8
9
-
H
x
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
D

1
2
3
4
7
8
9
-
H
p
C
D
F

* Minimum acceptable recoveries (EPA Method 1613 Table 7)

* 24 25 24 21 25 26 26 28 32 28 29 28 23 26
Ns1 12 14 20 19 24 29 24 28 18 19 23 10
Ns2 3 3 1 3 3 3 4 2 3 2 5 4 4
Ns3 17 18 20 17 15 19 17 14 8 7 11 7 5
Ns4 19 18 21 19 29 24 20 17 8 10 18 8 6
Ns5 21 24 25 24 23 26 21 19 8 9 17 7 5
Ns6 29 26 32 32 48 65 51 33 29 20 56 19 18
Ns7 27 30 35 26 37 40 31 28 18 20 20 14 11
Ns8 13 15 12 10 13 11 9 10 7 6 7
N9 5 4 4 3 3 3 2 3 3
N10 22 24 29 27 22 34 32 26 18 21 27 21 23
N11 12 13 13 10 11 11 10 8 5 6 7 4 7
N12 16 26 18 18 18 15 15 13 8 8 12 5 3
N15 16 24 23 16 19 23 13 13 9 5 8
N16 21 31 36 31 34 53 38 34 21 24 35 17 23
N17 17 31 18 35 34 51 34 35 23 26 45 11 14
N18 9 23 21 20 18 17 24 12 11 13 10 13 5
N19 13 28 34 33 32 47 45 35 34 27 28 16 20
N20 24 36 33 39 33 46 33 29 23 14

34 14 22
Table 5.20: recoveries (percentages): February analyses (samples 21 40)

Sample
2
3
7
8
-
T
C
D
F

2
3
7
8
-
T
C
D
D

1
2
3
7
8
-
P
e
C
D
F

2
3
4
7
8
-
P
e
C
D
F

1
2
3
7
8
-
P
e
C
D
D

1
2
3
4
7
8
-
H
x
C
D
F

1
2
3
6
7
8
-
H
x
C
D
F

2
3
4
6
7
8
-
H
x
C
D
F

1
2
3
4
7
8
-
H
x
C
D
D

1
2
3
6
7
8
-
H
x
C
D
D

2
3
4
6
7
8
-
H
x
C
D
D

1
2
3
7
8
9
-
H
x
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
D

1
2
3
4
7
8
9
-
H
p
C
D
F


* 24 25 24 21 25 26 26 28 32 28 29 28 23 26
N21 16 20 21 27 24 32 25 23 15 11 11 14
N22 16 20 21 27 23 32 25 23 15 11 11 14
N23 14 13 15 11 9 10 12 7 3 4 6
N24 7 9 8 8 10
N25 15 17 29 23 21 42 30 28 27 17 34 19 26
N26 3

144
N27 11 9 6 5 8 12 5 6
N28 18 17 17 15 11 17 13 15 11 6 08
N29 14 15 21 19 14 22 17 16 16 13 15 12 15
N30 5 4
N31 15 16 18 11 8 22 19 15 12 6 15 6 9
N32 23 27 30 32 32 41 44 31 23 23 30 23 30
N34 15 13 22 16 9 20 15 12 6 3 6
N35 13 10 12 8 13
N36 29 39 44 31 46 62 53 42 41 44 47 29 29
N37 17 24 30 28 26 35 33 27 13 11 20 14 14
N38 18 17 21 17 12 22 15 11 11 9 11
N39 8 10 8 9
N40 33 36 45 29 36 60 43 35 36 23

37 24 27


Sample
2
3
7
8
-
T
C
D
F

2
3
7
8
-
T
C
D
D

1
2
3
7
8
-
P
e
C
D
F

2
3
4
7
8
-
P
e
C
D
F

1
2
3
7
8
-
P
e
C
D
D

1
2
3
4
7
8
-
H
x
C
D
F

1
2
3
6
7
8
-
H
x
C
D
F

2
3
4
6
7
8
-
H
x
C
D
F

1
2
3
4
7
8
-
H
x
C
D
D

1
2
3
6
7
8
-
H
x
C
D
D

2
3
4
6
7
8
-
H
x
C
D
D

1
2
3
7
8
9
-
H
x
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
D

1
2
3
4
7
8
9
-
H
p
C
D
F


* 24 25 24 21 25 26 26 28 32 28 29 28 23 26
N42 8 19 11 4
N44 9 16 23 18 26 37 26 22 26 15 18 12 10
N45 25 25 36 32 44 39 42 36 25 20 30 20 18
N46 24 37 40 54 52 70 38 65 48 39 71 32 48
N47 21 26 27 31 30 44 44 31 17 21 30 18 18
N50 15 15 19 9 12 13 13 15 15 4 10
N51 14 23 24 17 26 31 23 15 15 14 18 9 8
N53 23 32 31 36 39 43 25 30 30 21 29 19 18
N55 4 3 12 11 9 13 8 9 7 5 6
N56 26 28 33 32 33 49 40 40 29 17 34 18 14
N57 18 24 35 18 50 22 28 26 23 13 22 17 21
N58 21 28 31 24 49 29 28 23 14 19 21 22 19
N59 26 29 54 43 52 43 43 37 41 22 37 31 27
N60 24 32 38 28 59 34 21 27 19 26

22 20 16

Table 5.22: recoveries (percentages): February analyses (samples 61-80)


145
Sample
2
3
7
8
-
T
C
D
F

2
3
7
8
-
T
C
D
D

1
2
3
7
8
-
P
e
C
D
F

2
3
4
7
8
-
P
e
C
D
F

1
2
3
7
8
-
P
e
C
D
D

1
2
3
4
7
8
-
H
x
C
D
F

1
2
3
6
7
8
-
H
x
C
D
F

2
3
4
6
7
8
-
H
x
C
D
F

1
2
3
4
7
8
-
H
x
C
D
D

1
2
3
6
7
8
-
H
x
C
D
D

2
3
4
6
7
8
-
H
x
C
D
D

1
2
3
7
8
9
-
H
x
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
D

1
2
3
4
7
8
9
-
H
p
C
D
F


* 24 25 24 21 25 26 26 28 32 28 29 28 23 26
N61 4 6 8 8 8 10 11 4 8 8
N62 26 35 55 37 44 28 29 33 20 20 33 35 13
N63 37 49 42 39 25 22 27 28 29 21

29 20 9
N65PAR 11 46 42 36 43 42 38 35 27 25 0.27 43 20 16 21
N66PAR 17 50 51 49 55 51 48 48 38 38 0.35 59 41 45 48
N69 21 19 32 24 31 26 29 22 11 12 18 9 14
N70 25 29 46 32 59 41 40 36 37 30 35 37 35
N71 18 23 32 30 47 35 36 32 20 20 27 28 18
N72 24 27 38 44 54 44 50 40 40 28 46 40 45
N73 24 26 39 28 50 36 41 28 23 25 32 22 18
N74 20 24 27 25 26 19 22 17 9 12 15 13 9
N75 24 20 34 25 46 24 22 17 16 11 15 14 11
N76 30 34 46 36 56 40 46 42 23 28 37 28 26
N77 35 40 56 53 53 42 43 40 40 35 39 33 35
N78 37 48 50 57 73 61 75 68 37 49 38 31 43
N79 22 24 49 36 35 41 42 35 19 5 45 22 23
N80 34 35 40 35 53 47 48 38 31 27

37 34 24

Table 5.23: recoveries (percentages): February analyses (samples 81-100)


Sample
2
3
7
8
-
T
C
D
F

2
3
7
8
-
T
C
D
D

1
2
3
7
8
-
P
e
C
D
F

2
3
4
7
8
-
P
e
C
D
F

1
2
3
7
8
-
P
e
C
D
D

1
2
3
4
7
8
-
H
x
C
D
F

1
2
3
6
7
8
-
H
x
C
D
F

2
3
4
6
7
8
-
H
x
C
D
F

1
2
3
4
7
8
-
H
x
C
D
D

1
2
3
6
7
8
-
H
x
C
D
D

2
3
4
6
7
8
-
H
x
C
D
D

1
2
3
7
8
9
-
H
x
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
D

1
2
3
4
7
8
9
-
H
p
C
D
F


* 24 25 24 21 25 26 26 28 32 28 29 28 23 26
N82 17 24 35 34 46 31 28 25 18 24 30 25 25
N83 23 29 33 30 35 31 36 25 17 21 27 18 6
N84 5 5 5 5 5 7 6 7 2 5
N85 18 26 27 22 26 16 22 17 11 9 15 10 11
N86 21 33 53 52 63 56 62 49 41 38 42 30 44
N87 10 12 14 12 12 15 15 12 8 9 10 11 11
N88 11 12 13 8 5 9 7 6 6
N89 22 39 49 45 48 38 34 30 21 23 28 18 11
N92 10 32 32 41 59 58 64 61 52 46

52 36 50
146
N94 11 22 27 28 30 27 20 19 15 13 24 13 12
N95 13 21 27 23 16 17 14 10 2 4 17 7 5
N96 15 22 34 40 39 36 40 37 23 21 32 28 18
N97 6 21 29 27 28 27 23 13 15 9 21 16 14
N98 11 21 31 25 28 25 25 24 19 17 14 17 16
N99 10 19 34 23 23 26 25 26 19 23

24 23 13



Sample
2
3
7
8
-
T
C
D
F

2
3
7
8
-
T
C
D
D

1
2
3
7
8
-
P
e
C
D
F

2
3
4
7
8
-
P
e
C
D
F

1
2
3
7
8
-
P
e
C
D
D

1
2
3
4
7
8
-
H
x
C
D
F

1
2
3
6
7
8
-
H
x
C
D
F

2
3
4
6
7
8
-
H
x
C
D
F

1
2
3
4
7
8
-
H
x
C
D
D

1
2
3
6
7
8
-
H
x
C
D
D

2
3
4
6
7
8
-
H
x
C
D
D

1
2
3
7
8
9
-
H
x
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
D

1
2
3
4
7
8
9
-
H
p
C
D
F


* 24 25 24 21 25 26 26 28 32 28 29 28 23 26
N101 27 28 41 31 65 43 46 37 29 32 39 25 31
N103 40 43 56 41 55 54 54 41 36 31 31 27 31
N105 2 2 3 2 3 2 6 3 3 3 2
N106 22 26 34 30 39 32 29 29 26 24 23 29 24
N108 19 17 20 11 11 15 19 14 9 10 8 12
N109 24 25 32 31 36 29 28 26 17 21 20 23 19
N111 35 33 55 36 44 48 47 41 27 27 42 24 23
N112 30 39 42 37 29 33 43 32 24 23 37 33 30
N113 31 29 42 37 29 33 43 32 24 23 37 33 30
N114 27 32 31 31 37 30 31 26 16 16 25 14 15
N115 26 22 39 33 23 29 28 25 18 8 17 23 15
N120 10 9 14 12 15 16 14 13 11 11

17 9 15



Sample
2
3
7
8
-
T
C
D
F

2
3
7
8
-
T
C
D
D

1
2
3
7
8
-
P
e
C
D
F

2
3
4
7
8
-
P
e
C
D
F

1
2
3
7
8
-
P
e
C
D
D

1
2
3
4
7
8
-
H
x
C
D
F

1
2
3
6
7
8
-
H
x
C
D
F

2
3
4
6
7
8
-
H
x
C
D
F

1
2
3
4
7
8
-
H
x
C
D
D

1
2
3
6
7
8
-
H
x
C
D
D

2
3
4
6
7
8
-
H
x
C
D
D

1
2
3
7
8
9
-
H
x
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
D

1
2
3
4
7
8
9
-
H
p
C
D
F

147


* 24 25 24 21 25 26 26 28 32 28 29 28 23 26
N123 25 28 38 26 40 32 26 26 25 23 31 15 24
N124 24 25 32 28 29 27 26 19 12 14 15 12 11
N125 32 34 43 34 27 33 35 24 11 14 31 12 18
N127 17 13 19 13 12 11 16 7 5 5
N129 18 20 28 21 22 15 13 8 11 9 8 8 6
N130 33 36 34 34 41 36 41 30 28 20 25 24 20
N132 18 16 25 21 26 31 22 23 20 17 21 23 18
N135 41 38 47 48 56 56 58 42 25 36 36 23 32
N136 58 58 73 62 65 57 49 42 38 39 41 41 32
N138 33 40 50 43 43 39 40 33 26 25 20 29 24
N139 36 41 51 56 53 57 53 40 42 42 58 31 33
N140 51 49 57 56 53 57 52 40 42 42

58 31 32



Sample
2
3
7
8
-
T
C
D
F

2
3
7
8
-
T
C
D
D

1
2
3
7
8
-
P
e
C
D
F

2
3
4
7
8
-
P
e
C
D
F

1
2
3
7
8
-
P
e
C
D
D

1
2
3
4
7
8
-
H
x
C
D
F

1
2
3
6
7
8
-
H
x
C
D
F

2
3
4
6
7
8
-
H
x
C
D
F

1
2
3
4
7
8
-
H
x
C
D
D

1
2
3
6
7
8
-
H
x
C
D
D

2
3
4
6
7
8
-
H
x
C
D
D

1
2
3
7
8
9
-
H
x
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
D

1
2
3
4
7
8
9
-
H
p
C
D
F


* 24 25 24 21 25 26 26 28 32 28 29 28 23 26
N142 63 61 90 82 82 94 98 80 76 69 85 86 76
N144 36 26 39 45 49 51 65 51 37 26 40 45 67
N149 14 16 17 20 15 15 19 13 14 9 13 15 16
N150 10 9 14 13 10 12 17 12 8 7 8
N151 35 34 39 49 43 37 48 32 29 45 34 22 27
N152 39 40 46 44 45 29 36 21 26 22 28 28 23
N154 44 46 68 68 69 59 85 62 63 54 66 33 47
N156 29 38 49 44 43 37 39 27 20 19 26 17 21
N157 24 22 23 31 28 23 37 31 11 13 21 26 13
N158 17 28 24 21 17 29 32 36 15 19 19 20 38
N160 46 48 59 56 71 56 42 54 54 52

51 33 62

148


Sample
2
3
7
8
-
T
C
D
F

2
3
7
8
-
T
C
D
D

1
2
3
7
8
-
P
e
C
D
F

2
3
4
7
8
-
P
e
C
D
F

1
2
3
7
8
-
P
e
C
D
D

1
2
3
4
7
8
-
H
x
C
D
F

1
2
3
6
7
8
-
H
x
C
D
F

2
3
4
6
7
8
-
H
x
C
D
F

1
2
3
4
7
8
-
H
x
C
D
D

1
2
3
6
7
8
-
H
x
C
D
D

2
3
4
6
7
8
-
H
x
C
D
D

1
2
3
7
8
9
-
H
x
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
D

1
2
3
4
7
8
9
-
H
p
C
D
F


* 24 25 24 21 25 26 26 28 32 28 29 28 23 26
N161 24 29 31 29 37 26 36 29 29 25 15 18 16
N164 29 25 28 32 35 30 44 38 27 26 31 22 21
N165 35 33 40 35 48 24 56 44 36 38 40 35 44
N166 29 30 38 36 34 27 50 37 35 21 32 29 45
N168 18 23 22 13 25 27 37 24 12 17 25 15 12
N171 36 36 48 52 40 43 65 38 43 37 48 27 46
N175 46 47 56 48 48 51 63 54 45 36 40 29 41
N177 37 45 45 51 41 30 62 40 29 30 33 16 32
N178 23 19 19 18 10 9 18 16 6 6 8 6
N179 20 20 11 11 15 7 12 7 12
N180 35 30 32 26 31 15 18 17 9 15

17 11 14



Sample
2
3
7
8
-
T
C
D
F

2
3
7
8
-
T
C
D
D

1
2
3
7
8
-
P
e
C
D
F

2
3
4
7
8
-
P
e
C
D
F

1
2
3
7
8
-
P
e
C
D
D

1
2
3
4
7
8
-
H
x
C
D
F

1
2
3
6
7
8
-
H
x
C
D
F

2
3
4
6
7
8
-
H
x
C
D
F

1
2
3
4
7
8
-
H
x
C
D
D

1
2
3
6
7
8
-
H
x
C
D
D

2
3
4
6
7
8
-
H
x
C
D
D

1
2
3
7
8
9
-
H
x
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
D

1
2
3
4
7
8
9
-
H
p
C
D
F


* 24 25 24 21 25 26 26 28 32 28 29 28 23 26
N182 40 44 37 40 36 24 31 24 20 18 18 11 14
N185 20 16 13 14 12 7 13 7 12
N186 11 8 8 3 9 6
N187 40 36 43 37 35 36 26 34 29 32 13 19 35
N195 20 23 28 25 20 12 22 20 16 10

15 11 14
149
N200 14 14 13 13 20 17 21 16 7 8 9 12 24



Sample
2
3
7
8
-
T
C
D
F

2
3
7
8
-
T
C
D
D

1
2
3
7
8
-
P
e
C
D
F

2
3
4
7
8
-
P
e
C
D
F

1
2
3
7
8
-
P
e
C
D
D

1
2
3
4
7
8
-
H
x
C
D
F

1
2
3
6
7
8
-
H
x
C
D
F

2
3
4
6
7
8
-
H
x
C
D
F

1
2
3
4
7
8
-
H
x
C
D
D

1
2
3
6
7
8
-
H
x
C
D
D

2
3
4
6
7
8
-
H
x
C
D
D

1
2
3
7
8
9
-
H
x
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
F

1
2
3
4
6
7
8
-
H
p
C
D
D

1
2
3
4
7
8
9
-
H
p
C
D
F


* 24 25 24 21 25 26 26 28 32 28 29 28 23 26
N201 7 7 5 4 9 8 11 12 4 10 8 12
N203 15 16 13 14 16 13 20 14 8 11 15 8 12
N204 12 17 7 7 9 9 12 8 7 4 7
N207 13 12 9 11 11 12 21 11 8 6 7 15 14
N211 11 12 7 9 11 11 14 10 8 10 13
N213 11 11 8 8 8 7 5 8 5
N215 7 8 4 4 6 7 4 5 6 5
N217 8 12 9 7 11 11 11 7 7 10 8 11
N218 8 9 9 4 12 19 7 5 4

9 16 17

150
6 LEACHING OF CADMIUM, COPPER, LEAD AND ZINC
FROM SELECTED UK SURVEY SAMPLES

6.1 INTRODUCTION

A selection of concrete, calcium silicate and clay brick samples (from the UK survey, or
obtained from other projects) were subjected to the tank leaching test, as detailed in Chapter
3, in order to determine the significance of cadmium, copper, lead and zinc leaching.
Although there are no British or EU legislation which directly addresses the leaching of trace
metals from housing construction materials, the Landfill (England & Wales) Regulations
2005 (Statutory Instrument No. 1640) prescribes maximum cumulative release limits from
monolithic wasteforms, as determined using the NEN7375 method (Table 6.1).

Table 6.1: Cumulative release regulatory limits (Office of Public Sector Information, 2006)

Element

Max. cumulative release
(mg/m
-2
, 64 days)

Max. cumulative release
(mg/m
-2
, 4 days)

Cadmium 1 0.25
Copper 60 15
Lead 20 5
Zinc 100 25

Twenty concrete cuboids and twenty clay brick cuboids were produced (obtained the UK
Survey collection discussed in Chapter 3, section 3.5), and assessed for their potential for
leaching cadmium, copper, lead and zinc into the environment.

6.2 DATES AND TIMES OF SAMPLE PROCESSING AND ANALYSIS

Table 6.2 details the dates of when the samples and their extracts were processed and
analysed. Wherever possible, all extracts were analysed in duplicate. Analysis of extracts
using voltammetry was started during August 2005, whereby single extracts of Samples 1
30 were analysed until the end of September 2005. Subsequently, analysis of extracts was
delayed until May 2006, when the Sample 1 to 30 extracts were analysed a second time, and
extracts of Samples 31 to 40 were analysed twice. During the seven-month delay between
analyses, it is possible that the concentration of dissolved metals in the extracts became
depleted (Drinking Water Inspectorate, 2005).

151
Table 6.2: Processing of UK Survey samples: dates of analysis

Sample Batch

Date of sample processing

Dates of extract analysis

Max. storage period
Samples 1-10
NEN 1
20/07/2005 22/09/2005 (1
st
replicates)
21/07/2005 06/09/2005;
(2
nd
replicates)
22/05/2006 28/05/2006

48 days

312 days
Samples 11-20
NEN 2
26/072005 29/09/2005 (1
st
replicates)
07/09/2005 19/09/2005;
(2
nd
replicates)
28/05/2006 30/05/2006

55 days

308 days
Samples 21-30
NEN 3
08/08/2005 11/10/2005 (1
st
replicates)
20/09/2005 28/09/2005;
(2
nd
replicates)
31/05/2006 02/06/2006

52 days

297 days
Samples 31-40
NEN 4
18/08/2005 21/10/2005 (1
st
replicates)
04/04/2006 13/04/2006;
(2
nd
replicates)
16/05/2006 20/05/2006

239 days

275 days

6.3 pH OF SAMPLE LEACHATES

The pH of the leachates is illustrated in Figures 6.2 to 6.6. The sample leachates were not
subjected to any pH control or alteration during the four series of experiments. It was
therefore anticipated that concrete sample leachates would be strongly alkaline (due to the
presence of Ca(OH)
2
. Although early concrete leachates exhibited very high pH values, over
time, the majority of concrete sample leachates were characterised by descending alkalinity.
One possible explanation for this may have been intrusion of air through the plastic lids into
the containers, which would have introduced carbon dioxide into the water, which in turn
forms carbonic acid, which in turn reacts with the lime in the concrete (Anders et al, 1999).
The change in pH may also be attributed to the depletion of alkaline constituents in the
concrete blocks. Carbonation progresses at a decreasing rate as the dissolving CO2 has to
penetrate the pore system within the concrete, including the already carbonated surface
(wherein CaCO3 may have precipitated and filled cavities) (Neville, 1996 p499).

Figures 6.1 (a d) comprise photographs of the containers used. Figure 6.6 illustrates that the
pH was less susceptible to air intrusion with samples held inside the tall white boxes with
screw-top lids. (Plastic boxes were used as glass tanks with sealing lids were not available.)
As illustrated in all Figures 6.2 6.5, clay brick leachate pH ranged between neutral (pH7)
and slightly alkaline (pH8) similar to the pH values of the blank (tap-water) samples, and
theoretical values given by Van der Sloot (2004).

152
6.1(a) 6.1(b)
6.1(c) 6.1 (d)

Figures 6.1 (a d): containers used for the UK Survey samples for leaching tests

Figure 6.1 (a): Blue-lid container (blue squares/triangles, Figure 6.6)
Figure 6.1 (b): Small clear container (grey squares/triangles, Figure 6.6)
Figure 6.1 (c): White-lid container (white squares/triangles, Figure 6.6)
Figure 6.1 (d): Other container (Red triangles, Figure 6.6)

6.4 LEACHING OF UK SURVEY SAMPLES: RESULTS AND DISCUSSION

Tables 6.3 to 6.10 list the raw data produced using voltammetry during analysis of the UK
survey sample leachate extracts. (Note: CB denotes clay brick samples; CN denotes
concrete samples; CaSi denotes calcium silicate samples, and Th denotes thermalite
samples.) For almost all sample extracts, the trace metal concentration was either below the
limit of detection or below the concentration of the blank extracts (when tapwater was the
leachatte).

1
5
3

6 7 8 9
1
0
1
1
1
2
1
1
0
1
0
0
1
0
0
0
1
0
0
0
0
T
i
m
e

(
h
o
u
r
s
)
p H
s
a
m
p
l
e

1
s
a
m
p
l
e

2
s
a
m
p
l
e

3
s
a
m
p
l
e

4
s
a
m
p
l
e

5
s
a
m
p
l
e

6
s
a
m
p
l
e

7
s
a
m
p
l
e

8
s
a
m
p
l
e

9
s
a
m
p
l
e

1
0
b
l
a
n
k

F
i
g
u
r
e

6
.
2
:

p
H

o
f

S
a
m
p
l
e
s

1

1
0

l
e
a
c
h
a
t
e
s

(
t
r
i
a
n
g
l
e
s

d
e
n
o
t
e

c
l
a
y

b
r
i
c
k
s
,

s
q
u
a
r
e
s

d
e
n
o
t
e

c
o
n
c
r
e
t
e
)

1
5
4

6 7 8 9
1
0
1
1
1
2
1
1
0
1
0
0
1
0
0
0
1
0
0
0
0
T
i
m
e

(
h
o
u
r
s
)
p H
s
a
m
p
l
e

1
1
s
a
m
p
l
e

1
2
s
a
m
p
l
e

1
3
s
a
m
p
l
e

1
4
s
a
m
p
l
e

1
5
s
a
m
p
l
e

1
6
s
a
m
p
l
e

1
7
s
a
m
p
l
e

1
8
s
a
m
p
l
e

1
9
s
a
m
p
l
e

2
0
b
l
a
n
k

F
i
g
u
r
e

6
.
3
:

p
H

o
f

S
a
m
p
l
e
s

1
1

2
0

l
e
a
c
h
a
t
e
s

(
t
r
i
a
n
g
l
e
s

d
e
n
o
t
e

c
l
a
y

b
r
i
c
k
s
,

s
q
u
a
r
e
s

d
e
n
o
t
e

c
o
n
c
r
e
t
e
)

1
5
5

0 2 4 6 8
1
0
1
2
1
1
0
1
0
0
1
0
0
0
1
0
0
0
0
T
i
m
e

(
h
o
u
r
s
)
p H
s
a
m
p
l
e

2
1
s
a
m
p
l
e

2
2
s
a
m
p
l
e

2
3
s
a
m
p
l
e

2
4
s
a
m
p
l
e

2
5
s
a
m
p
l
e

2
6
s
a
m
p
l
e

2
7
s
a
m
p
l
e

2
8
s
a
m
p
l
e

2
9
s
a
m
p
l
e

3
0
b
l
a
n
k

F
i
g
u
r
e

6
.
4
:

p
H

o
f

S
a
m
p
l
e
s

2
1

3
0

l
e
a
c
h
a
t
e
s

(
t
r
i
a
n
g
l
e
s

d
e
n
o
t
e

c
l
a
y

b
r
i
c
k
s
,

s
q
u
a
r
e
s

d
e
n
o
t
e

c
o
n
c
r
e
t
e
)

1
5
6

0 2 4 6 8
1
0
1
2
1
4
1
1
0
1
0
0
1
0
0
0
1
0
0
0
0
T
i
m
e

(
h
o
u
r
s
)
p H
s
a
m
p
l
e

3
1
s
a
m
p
l
e

3
2
s
a
m
p
l
e

3
3
s
a
m
p
l
e

3
4
s
a
m
p
l
e

3
5
s
a
m
p
l
e

3
6
s
a
m
p
l
e

3
7
s
a
m
p
l
e

3
8
s
a
m
p
l
e

3
9
s
a
m
p
l
e

4
0
(
D
i
s
t
i
l
l
e
d

w
a
t
e
r

b
l
a
n
k

u
s
e
d
:

p
H

m
e
a
s
u
r
e
m
e
n
t

n
o
t

p
o
s
s
i
b
l
e
)

F
i
g
u
r
e

6
.
5
:

p
H

o
f

S
a
m
p
l
e
s

3
1

4
0

l
e
a
c
h
a
t
e
s

(
t
r
i
a
n
g
l
e
s

d
e
n
o
t
e

c
l
a
y

b
r
i
c
k
s
,

s
q
u
a
r
e
s

d
e
n
o
t
e

c
o
n
c
r
e
t
e
)

1
5
7

5 6 7 8 9
1
0
1
1
1
2
1
3
1
1
0
1
0
0
1
0
0
0
1
0
0
0
0
T
i
m
e

(
h
o
u
r
s
)
p H
K
E
Y
B
l
u
e

s
q
u
a
r
e
:

c
o
n
c
r
e
t
e

i
n

b
l
u
e
-
l
i
d

c
o
n
t
a
i
n
e
r
B
l
u
e

t
r
i
a
n
g
l
e
:

c
l
a
y

b
r
i
c
k

i
n

b
l
u
e
-
l
i
d

c
o
n
t
a
i
n
e
r
G
r
e
y

s
q
u
a
r
e
:

c
o
n
c
r
e
t
e

i
n

s
m
a
l
l

c
l
e
a
r

c
o
n
t
a
i
n
e
r
G
r
e
y

t
r
i
a
n
g
l
e
:

c
l
a
y

b
r
i
c
k

i
n

s
m
a
l
l

c
l
e
a
r

c
o
n
t
a
i
n
e
r

W
h
i
t
e

s
q
u
a
r
e
:

c
o
n
c
r
e
t
e

i
n

w
h
i
t
e
-
l
i
d

c
o
n
t
a
i
n
e
r

W
h
i
t
e

t
r
i
a
n
g
l
e
:

c
l
a
y

b
r
i
c
k

i
n

w
h
i
t
e
-
l
i
d

c
o
n
t
a
i
n
e
r
R
e
d

t
r
i
a
n
g
l
e
:

c
l
a
y

b
r
i
c
k

i
n

o
t
h
e
r

c
o
n
t
a
i
n
e
r

F
i
g
u
r
e

6
.
6
:

I
n
f
l
u
e
n
c
e

o
f

s
a
m
p
l
e

c
o
n
t
a
i
n
e
r
s

o
n

p
H
158
Some distinct contrasts between groups of sample results can be seen, particularly for copper
results (Figures 6.7, 6.8). The main contrast can be seen between the first and second
replicate results (indicated by bold and dotted lines respectively): in general, the second
replicate results occur within an increasingly lower range over time. Further proof of this
contrast is provided in Figures 6.7 and 6.8 which illustrate the tapwater blank concentrations
(in g/l) recorded for both sets of sample replicates (whereby the Leaching Stage indicates the
replenishment stage, i.e. 2 = 2
nd
replenishment (1 day), or 5 = 5
th
replenishment (9 days)).

For leachate extracts of samples 36 38 and 40 (treated using distilled water), the
concentrations of zinc and copper were minor, and lead and cadmium were undetected.
Figures 6.10 and 6.11 illustrate the cumulative release of copper from cementitious samples
(concrete, calcium silicate, aircrete), and clay bricks, respectively. Figures 6.12 and 6.13
illustrate the cumulative release of copper from cementitious samples (concrete, calcium
silicate, aircrete), and clay bricks (respectively). These figures only provide the cumulative
release data for samples, for which copper and zinc concentrations occurred above the limit of
detection (2g/l). In all figures, data for analyses of second replicates (Table 6.2) is
connected using dotted lines. For copper, cumulative release ranges from approximately -
16mg.m
-2
to +3mg.m
-2
for cementitious samples similar to the approximate -15mg.m
-2
to
0mg.m
-2
range for clay bricks. Likewise (although within a smaller range), zinc cumulative
release values for both cementitious and clay brick samples occur approximately between
6mg.m
-2
and +3mg.m
-2
.
0
20
40
60
80
100
120
140
160
1 2 3 4 5 6 7 8
Leaching stage
C
o
n
c
e
n
t
r
a
t
i
o
n

(
u
g
/
l
)
(samples 1 - 10) i
(samples 1 - 10) ii
(samples 11 - 20) i
(samples 11 - 20) ii
(samples 21 - 30) i
Average
Distilled
Distilled ii

Figure 6.7: blank leachate concentrations (copper)

159
0
20
40
60
80
100
120
140
1 2 3 4 5 6 7 8
Leaching stage
C
o
n
c
e
n
t
r
a
t
i
o
n

(
u
g
/
l
)
(samples 1 - 10) i
(samples 1 - 10) ii
(samples 11 - 20) i
(samples 21 - 30) i
Average
Distilled
Distilled ii

Figure 6.8: blank leachate concentrations (zinc)

Cadmium and lead were seldom detected (as indicated in Tables 6.3 - 6.4 and Tables 6.7 to
6.8, respectively). During analysis of the first four replenishments of leachates of samples 1
to 10, lead was detected at concentrations typically ranging up to approximately 20g/l;
however, this was the result of a concentrated calibration solution during voltammetry
analysis, which originally contained 12.5mg/l Pb; this was reduced to 1.25mg/l Pb, after
which lead was rarely detected. As a result, no cumulative leaching graphs based on
cadmium or lead leaching are provided in this chapter.

This pattern owes mainly to the higher concentrations of copper detected within the tapwater
blank extracts. Interestingly, the same pattern is not very evident amongst the zinc results
(Figures 6.12 and 6.13), although a few second replicate results tend to occur at the lower
end of the spectrum of zinc cumulative release results.

There is also a noticeable contrast between the data relating to samples treated with tapwater,
and those treated with distilled water (samples 37 38 and 40). In addition, the results for
sample 39 (which was the same as sample 40 refer to Table 3.2, Chapter 3) were calculated
by subtracting the distilled water blank values, even though sample 39 was treated using
tapwater. The results for sample 39 therefore mainly indicated the significance of the
tapwater concentrations. Within Figure 6.10, the sample 39 results rise to between +2 and +3
mg.m
-2
for copper leaching. This contrasts with the sample 39 results for zinc leaching,
which are either minimal (for the first replicate), or descend towards -3mg.m
-2
. The leaching
160
of copper from samples 37 and 40 (Figure 6.9) and sample 38 are minimal, seldom straying
from 0mg.m
-2
. These contrasts amongst samples 31 40 are more clearly illustrated in
Figures 6.14 to 6.17.

One anomalous pattern noticed (and shown in Tables 6.9 and 6.10) was an exceptionally high
concentration of zinc in extracts of the final leaching stage for Samples 21 to 24, sometimes
exceeding 1000g/l. This pattern was not repeated elsewhere in the experiments, and so
might have owed to the voltammetry cell being contaminated (possibly PFA dust) from other
experiments taking place in the lab at that time.

6.5 DISCUSSSION

13 concrete, 2 calcium silicate, one aircrete (Thermalite) and 19 clay brick samples (all of
them commercially used) were subjected to leaching using tap-water without pH control.
This contrasts with the approaches reported in the literature described in Chapter 2, whereby
other researchers in the field often defined the formula of concrete mixes, and prepared them
in the lab, often adding a secondary/waste material (e.g. incinerator fly ash, PFA) to the
concrete mix. As mentioned, no studies regarding leaching on clay bricks, calcium silicate or
aircrete bricks were sourced in the literature. Another unique feature of this study on these
UK survey samples was the use of voltammetry analysis, which was not mentioned in any of
the references cited and listed in Table 2.14.

In general, there is no indication that any of the samples leached cadmium, copper, lead or
zinc to such as degree as to exceed the limits indicated in Table 6.1. For the concrete samples
this was anticipated, given that the pH of the leachant was not tempered, and often ascended
to between pH9 and pH12. Under these moderately strong alkaline conditions, Cd, Cu and
Zn are fused within the solid cement matrix (Achternbosch et al, 2003), and do not leach into
pore-water. Hillier et al (1999) subjected Ordinary Portland cement-based concrete samples
to leaching, but could not detect Cd or Pb in any of the extracts. Marion et al (2004) also
subjected Ordinary Portland cement-based concrete samples to leaching, but only Zn was
regularly detected in leachates (in contrast with Cd, Pb and Cu).

The results for calcium silicate (samples 17 and 26) were among the lowest recorded in
Figures 6.10 and 6.12, probably due to the composition of calcium silicate (XRF analyses
showed this almost entirely comprised silica (SiO
2
) and lime (CaO)), and also due to the
strongly alkaline pH of the Sample 17 and 26 leachates (Figures 6.3 and 6.4). Given these
factors, it is unlikely that any significant quantities of trace metals would have leached.
161
The clay brick samples imposed a more neutral to weakly alkaline influence on the leachants.
However, the concentrations of Cu and Zn in clay brick sample extracts were generally
comparable with those of the concrete sample extracts. Given that no data regarding leaching
from clay brick monoliths was found in the literature, the reasons for these patterns cannot be
identified. However, studies by Karius et al (2002) on granular (crushed) clay brick leaching
columns revealed that iron and aluminium minerals in clay brick strongly adsorbed Cd and
Cu from distilled water. Similar adsorption may have occurred with the clay bricks used in
this study.

It was apparent that the concentrations of dissolved metals in the tap-water obscured the
leaching of trace metals from samples which might have possibly been observed. Figures
6.10 and 6.11 show a marked contrast between Cu results for Samples 36 40 (immersed in
distilled water, for which a distilled water blank reference was used), and Cu results for other
samples. (However, such a contrast was less evident for Zn results in Figures 6.12 or 6.13.)
Tests conducted on a stream of tap-water alongside the analyses of samples 1 40 revealed
that the composition of tap-water varied widely, and enriched concentrations of zinc, lead and
copper were found in the first few ml of tap-water poured out after standing over-night
(Figure 6.9). Copper concentrations in the tap-water ranged between approx. 100g/l and
200g/l, which is similar to the concentrations in some of the leachates indicated in Figure
6.7. Copper concentrations also remained at this range throughout the test, although zinc
concentrations tended to decrease.
0.1
1
10
100
1000
1 10 100 1000 10000
Vol. tapwater poured out (ml)
C
o
n
c
.

i
n

t
a
p
w
a
t
e
r

(
m
i
c
r
o
g
r
a
m
s

p
e
r

l
i
t
r
e
)
Zn
Cd
Pb
Cu

Figure 6.9: concentrations of metals in tap-water

Judging by the enriched concentrations of Cu and Zn in the tapwater test (Figure 6.9), it is
understandable why the concentrations in sample leachates were often exceeded by those
162
within tap-water-based blanks. This may indicate that trace metals (including zinc and
copper) initially dissolved within the tapwater added to the samples may have been absorbed
onto the samples, partly owing to the alkaline pH of the leachate itself encouraging
precipitation (Anders et al, 1999).

Nevertheless, the range of cumulative release values (at 64 days) for Cu occur across a broad
spectrum, both for cementitious (concrete, clay brick, calcium silicate) and clay brick
samples. (A smaller range was recorded with regards to Zn concentrations). Another factor
affecting the reported Cu and Zn concentrations might have been the nature of the
voltammetry analysis itself. This is fairly evident in Tables 6.5 and 6.9, which detail the
results for the first sample extract replicates (Cu and Zn, respectively). The first replicates of
extracts of Samples 1 to 10 were the first extracts of this project to be analysed, followed by
those of Samples 11 to 20, then those of Samples 21 to 30. Some difficulties with
background noise were encountered when processing the first few extracts, which might
explain the comparatively high results for some extracts of Samples 1 to 10 (first replicates).
The background noise and the peak heights stabilised as the voltammetry analyses continued.
However, in general, the peaks appeared to shrink as extracts of Samples 21 to 30 were being
analysed. The voltammetry machine broke down as the last extracts (first replicates) of
Samples 21 to 30 were being processed, partly due to the mercury tank inside the machine
running dry. There may have been a connection between the decline in peak heights and the
subsequent voltammetry machine breakdown. Once the machine was fixed, the extracts of
Samples 31 to 40 (both replicates), and the second replicates of Samples 1 30 were
analysed. Raw data for Cu and Zn in those extracts (Tables 6.6 and 6.10) appear to be more
consistent.

A peculiar feature in the UK survey leaching results was the absence of Pb peaks, despite the
very low detection limits of the voltammetry machine. These contrast with leaching results
reported and discussed back in Chapter 2 (namely in Figure 2.26), whereby the range of
cumulative release results at 64 days for Pb for concretes containing Ordinary Portland
cement and primary aggregates ranged from approx. 1 to 10mg.m
-2
similar to the ranges for
Cu and Zn in Figures 2.24 and 2.29 (0.02 8mg.m
-2
, 3 11mg.m
-2
, respectively)*. The scant
occurrence of Pb peaks in UK survey sample extracts may again reflect the composition of
tap-water samples (Figure 6.9), whereby the concentrations of Pb were typically about an
order of magnitude below that of Zn, and often much lower compared with that of Cu.

* Data in Figures 2.24, 2.26 and 2.29: based on granite and sandstone aggregate-bearing concretes (Van der Sloot
et al, 2001), CEM I concrete (Marion et al, 2004), Ordinary Portland cement mortars (Van der Sloot et al, 2001),
Ordinary Portland cement-based concrete (Flor et al, 2003).
163
6.6 CONCLUSION

Based on the evidence relating to samples 36 to 38 and 40, the leaching of copper and zinc
from concrete and clay brick samples appeared to be minimal. It is also probable that no
discernable quantities of cadmium or lead were leached out of any of the samples. In general,
the concentrations of zinc and copper in sample extracts were exceeded by those in the blank
(tapwater) extracts. This is attributed to the precipitation of metals out of solution under the
pH conditions (pH7 pH8 for clay bricks, and >pH10 for cementitious samples) (Van der
Sloot, 2004).

It was also observed that for samples 1 to 30, the concentrations of copper and zinc in tap-
water blank extracts were comparatively higher alongside analyses of the second replicate
sample extracts, compared with the tap-water blanks analysed alongside analyses of the first
replicate sample extracts eight months earlier. It has been reported that concentrations of
dissolved metals in acidified water samples may be depleted after 6 months of storage, and
the causes of enriched concentrations after prolonged storage may owe to gradual extraction
of metals from the sample container material (Drinking Water Inspectorate, 2005).

Overall, it may be concluded that the leaching of cadmium, copper, lead and zinc from the
selected UK survey samples was insignificant, although precise evidence for this is limited,
mainly due to the use of unacidified tapwater as a leachant.

164
Table 6.3: Raw voltammetric analyses of cadmium in leachates first replicates (g/l)
(time indicated in days)

Sample

Extracts
(bold figures indicate no. of days extract was obtained after start of experiment)

Time 0.25 1 2 4 9 16 36 64
1 (CN) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 1.4 1.5
2 (CN) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 2.9 1.5
3 (CB) 3.4 * <0.1 <0.1 <0.1 <0.1 <0.1 1.4
4 (CN) <0.1 * <0.1 <0.1 * <0.1 1.2 0.7
5 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 1.2 0.7
6 (CN) 1.0 <0.1 <0.1 <0.1 <0.1 1.3 1.2 1.4
7 (CB) <0.1 * <0.1 <0.1 <0.1 1.2 1.0 2.0
8 (CN) 0.9 <0.1 <0.1 1.4 <0.1 <0.1 <0.1 0.9
9 (CB) 1.7 <0.1 <0.1 1.1 <0.1 0.7 1.3 <0.1
10 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 1.1
Blank1 <0.1 <0.1 <0.1 1.3 <0.1 <0.1 <0.1 1.4
11 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.9 1.2
12 (CB) 0.1 0.7 <0.1 <0.1 <0.1 <0.1 <0.1 1.2
13 (CN) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 1.1 1.0
14 (CB) <0.1 <0.1 <0.1 * 1.1 <0.1 * 1.4
15 (CN) <0.1 <0.1 <0.1 <0.1 <0.1 0.3 * 0.6
16 (CB) 1.7 <0.1 <0.1 * <0.1 1.2 0.9 1.1
17 (CaSi) 0.2 <0.1 <0.1 1.5 <0.1 <0.1 0.9 *
18 (CB) <0.1 <0.1 <0.1 0.2 <0.1 <0.1 <0.1 1.2
19 (CN) <0.1 <0.1 <0.1 0.7 <0.1 1.6 0.8
20 (CB) <0.1 <0.1 0.2 <0.1 <0.1 1.7 1.1
Blank2 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.7
21 (CN) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 3.8
22 (CN) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 1.2
23 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 4.0
24 (CN) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 1.9
25 (CB) * <0.1 <0.1 <0.1 <0.1 * <0.1 1.6
26 (CaSi) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 1.4
27 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 1.6
28
(Therm) 0.5 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.9
29 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
30 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
Blank3 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.3
31 (CB) 2.4 1.7 1.2 1.5 0.6 <0.1 <0.1 1.3
32 (CB) 4.4 1.4 2.3 1.0 0.6 <0.1 <0.1 1.6
33 (CN) 6.3 1.9 1.2 <0.1 0.5 <0.1 <0.1 1
34 (CB) 3.8 2.1 1.1 1.8 <0.1 <0.1 <0.1 1
35 (CN) 4.4 1.5 1.1 1.0 * <0.1 <0.1 1.3
36(CB)
1.7 * 1.4 0.4 <0.1 <0.1 <0.1 <0.1

37(CN)
1.2 0.7 1.0 0.6 <0.1 0.3 <0.1 1.9

38(CB)
1.7 1.7 <0.1 * 0.8 <0.1 <0.1 1.8

39 (CN) 1.4 2.0 1.3 1.3 0.1 <0.1 <0.1 1.7
40(CN)
1.7 1.5 1.8 <0.1 <0.1 <0.1 <0.1 4.2

Blank4
2.4 2.2 1.1 2.3 <0.1 <0.1 0.8 1.4

* Inaccurate data on voltammetry read-out
Distilled water used

165
Table 6.4: Raw voltammetric analyses of cadmium in leachates second replicates (g/l)

Sample

Extracts

Time 0.25 1 2 4 9 16 36 64
1 (CN) <0.1 <0.1 <0.1 * <0.1 <0.1 <0.1 *
2 (CN) 0.3 0.2 <0.1 <0.1 0.2 <0.1 <0.1 <0.1
3 (CB) 0.4 0.5 0.3 1.0 <0.1 <0.1 <0.1 <0.1
4 (CN) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
5 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.2 <0.1
6 (CN) <0.1 <0.1 <0.1 <0.1 0.2 <0.1 * <0.1
7 (CB) <0.1 0.3 <0.1 <0.1 <0.1 0.6 <0.1 <0.1
8 (CN) <0.1 <0.1 <0.1 <0.1 0.4 <0.1 <0.1 <0.1
9 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
10 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
Blank1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
11 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
12 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
13 (CN) <0.1 <0.1 0.1 0.3 <0.1 <0.1 <0.1 <0.1
14 (CB) <0.1 <0.1 <0.1 <0.1 * <0.1 <0.1 <0.1
15 (CN) <0.1 <0.1 0.9 0.3 <0.1 0.2 1.3 <0.1
16 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
17 (CaSi) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
18 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
19 (CN) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
20 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
Blank2 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
21 (CN) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 7.1
22 (CN) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
23 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 0.5
24 (CN) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
25 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
26 (CaSi) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
27 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
28
(Therm) * <0.1 <0.1 <0.1 <0.1 <0.1 * <0.1
29 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
30 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
Blank3 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
31 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
32 (CB) <0.1 <0.1 1.3 <0.1 <0.1 <0.1 <0.1 <0.1
33 (CN) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
34 (CB) <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
35 (CN) <0.1 <0.1 <0.1 <0.1 * <0.1 <0.1 <0.1
36(CB)
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

37(CN)
1.3 0.3 0.4 0.2 0.3 <0.1 <0.1 <0.1

38(CB)
<0.1 <0.1 * <0.1 <0.1 <0.1 <0.1 <0.1

39 (CN) 0.3 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
40(CN)
<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

Blank4
<0.1 <0.1 1.2 <0.1 <0.1 <0.1 <0.1 <0.1


166
Table 6.5: Raw voltammetric analyses of copper in leachates first replicates (g/l)

Sample

Extracts

Time 0.25 1 2 4 9 16 36 64
1 (CN) * 69.4 52.7 40.4 34.0 13.1 8.3 13.9
2 (CN) * * 48.9 56.1 17.9 21.9 9.1 9.3
3 (CB) 40.5 * 43.8 44.0 29.1 15.6 22.0 25.6
4 (CN) 60.9 32.8 23.7 24.0 * 10.8 11.0 10.4
5 (CB) 53.1 39.4 46.4 46.9 33.5 18.2 30.2 9.9
6 (CN) 70.1 33.2 24.4 21.0 9.6 14.1 14.2 26.4
7 (CB) 60.7 * 87.0 73.5 32.0 22.7 39.5 28.2
8 (CN) 32.3 29.2 24.3 15.4 8.0 6.1 10.8 17.8
9 (CB) 42.6 56.5 64.6 48.4 27.7 21.9 30.3 26.7
10 (CB) 43.5 61.5 42.8 27.3 21.4 16.1 11.9 17.1
Blank1 68.1 51.9 48.0 40.8 32.8 43.0 51.8 79.0
11 (CB) 70.8 33.9 34.4 29.4 14.1 11.0 11.9 18.9
12 (CB) 34.4 33.8 24.7 17.7 14.0 15.6 26.2 24.5
13 (CN) 27.0 18.7 24.5 18.7 6.8 4.9 5.9 16.2
14 (CB) 41.2 20.7 35.9 * 22.6 18.7 * 42.5
15 (CN) 36.6 16.8 0 9.1 7.4 5.0 * 10.4
16 (CB) 37.8 16.3 6.8 * 5.5 5.5 5.3 13.4
17 (CaSi) 15.1 8.6 5.1 9.0 5.9 4.8 3.6 *
18 (CB) 30.5 30.0 12.3 10.5 6.2 4.2 9.1 14.5
19 (CN) 35.7 <2 13.8 16.8 * 7.4 4.4 21.3
20 (CB) 32.4 24.4 18.0 17.3 * 17.5 27.6 34.8
Blank2 94.1 41.9 69.0 830.0 69.0 42.5 69.0 97.3
21 (CN) 2.3 2.8 <2 <2 2.1 4.3 <2 10.5
22 (CN) <2 <2 <2 <2 1.5 1.1 <2 9.3
23 (CB) 3.6 3.6 3.1 3.6 3.6 2.4 6.6 14.3
24 (CN) 6.0 <2 3.3 3.3 2.9 2.2 10.0 9.3
25 (CB) * 2.7 2.7 2.8 2.4 5.1 3.4 21.4
26 (CaSi) 3.2 2.4 <2 <2 1.7 <2 <2 7.7
27 (CB) 3.3 4.0 3.1 4.5 4.0 3.3 6.4 14.2
28
(Therm) 3.3 2.0 <2 <2 1.7 <2 <2 6.1
29 (CB) 4.3 12.8 2.1 4.1 2.4 3.8 6.5 10.4
30 (CB) 3.5 6.5 2.5 4.8 3.8 4.9 5.4 10.9
Blank3 16.3 13.9 13.3 20.8 17.5 27.3 32.9 121.5
31 (CB) 61.8 51.6 46.7 48.4 5.5 37.4 32.6 62.8
32 (CB) 62.9 51.1 52.4 43 55.6 34.6 35.6 38.6
33 (CN) 35.7 15.9 19.4 14.4 24.1 4.7 9.2 19.4
34 (CB) 44.9 53.9 36.2 41.5 44.2 35.6 36.7 33.9
35 (CN) 22 22.1 10.1 16.6 * 7.7 10 18
36(CB)
7.9 * 11.9 7.7 9 4.4 4.6 10.9

37(CN)
5 4.5 4.3 5.6 8 4.4 6.5 20.9

38(CB)
13.2 12.3 10 30 15 9.7 6.7 14.1

39 (CN) 51.4 40.5 24.4 22.3 15.6 7.1 8.6 15.1
40(CN)
12.1 9.5 7.3 11.4 5.5 5.9 5 15.2

Blank4
33 9.2 8 7 19.1 2.2 5.4 24.8


167
Table 6.6: Raw voltammetric analyses of copper in leachates second replicates (g/l)

Sample

Extracts

Time 0.25 1 2 4 9 16 36 64
1 (CN) 39.8 52 23 * 15.1 12.2 12.5 *
2 (CN) 30.4 16.8 17.6 20.9 14.7 11.9 20 7.6
3 (CB) 39 31.3 37.3 49.9 24.6 28.9 4.1 19.6
4 (CN) 35.6 32.7 30.1 20.4 13 5.7 8.9 5.2
5 (CB) 31.4 39.8 60.4 38.4 63.1 42.3 33.7 6.9
6 (CN) 16.2 20.7 15.5 18 10.5 13.1 * 24.5
7 (CB) 57 46.2 53.6 52.1 46 34.4 25.4 26.6
8 (CN) 31.7 24 22.3 18.2 12.9 11.4 14.1 15.8
9 (CB) 58.3 29.5 48.7 30 45.5 42.7 33.1 18.8
10 (CB) 56 34 40.5 30.3 37.4 94.6 24.1 14.7
Blank1 57.7 37.1 60.6 43.7 58.7 60.5 72.4 80.3
11 (CB) 100.9 48.9 55.2 31.7 23.9 24.4 19.3 17.8
12 (CB) 61.4 54.2 57 40.2 29.4 26 32.9 23.5
13 (CN) 49.7 32.4 35.3 28 15.4 7.8 8.2 12.4
14 (CB) 63.3 45.5 49.4 37.9 * 30.3 39.7 37.6
15 (CN) * 31.5 31.8 13.6 11.2 7.6 8.7 10.5
16 (CB) 68.8 24.1 24.6 15.1 13.5 11.9 10.6 11.8
17 (CaSi) 48.6 14.1 9.8 11.4 11.4 6.4 7.8 *
18 (CB) 41.6 27.1 22.7 19.9 17.5 13.6 12.1 12.2
19 (CN) 27.1 25 18.9 33.5 18.6 16 12.8 14.3
20 (CB) 58.6 37.1 33.2 30.3 3.3 30.6 8.7 25
Blank2 140.7 70.8 110.3 100.3 77.1 92.6 79.7 107
21 (CN) 11.9 13.9 8.2 9.9 11.4 11.4 6.5 10.3
22 (CN) 10.7 11 6.5 7.2 8.9 7.6 10.8 12.1
23 (CB) 22 18.6 18.8 17.2 13.8 15.5 14.8 13.4
24 (CN) 32.9 18.1 15.4 18.8 11.4 12.8 10.2 8.8
25 (CB) 24.3 15.8 10.2 14 15.6 18 17.4 18.8
26 (CaSi) 19 12.3 9.2 7.8 8.6 6.7 9.1 8.1
27 (CB) 16.4 19.9 18.3 18.6 16.1 16.2 16.1 15.5
28
(Therm) * 9.9 8.2 7.1 4 4.6 * 3.1
29 (CB) 29.1 23.1 15.4 16.5 10.6 11.9 8.8 12.4
30 (CB) 29.1 23.1 15.4 16.5 10.6 11.9 8.8 12.4
Blank3 73 40.6 62.1 85.3 71.1 105.7 91.9 130.8
31 (CB) 61.8 57.5 57 46.3 44.3 36.3 34.8 21.6
32 (CB) 61 55 54.7 45.4 36 34.9 36.7 23.1
33 (CN) 25.7 13.7 13.9 14.6 10.3 6.2 7.7 5.9
34 (CB) 36.6 52.8 41.1 44 46.4 39.5 36.4 *
35 (CN) 16.6 27 13.1 9.5 * 4.8 9.8 6.7
36(CB)
2.6 * 11 6.7 8.9 5.4 4.6 5.9

37(CN)
6.1 5.7 1.6 3.9 4 5.4 20 1.7

38(CB)
8.9 11.2 * 9.8 7.2 7.5 5.1 4.2

39 (CN) 47.2 38.6 26.5 12.7 20.9 9.3 11.5 6.5
40(CN)
8.8 8.6 6.6 6.9 5.8 7.5 6.8 4.8

Blank4
23.5 6.9 4.5 3.8 3.9 3.1 3 7.2


168
Table 6.7: raw voltammetric analyses of lead in leachates first replicates (g/l)

Sample

Extracts

Time 0.25 1 2 4 9 16 36 64
1 (CN) ** ** ** ** ** <2 <2 <2
2 (CN) ** ** ** ** ** 2.5 <2 <2
3 (CB) ** ** ** ** ** <2 <2 <2
4 (CN) ** ** ** ** ** 2.4 <2 <2
5 (CB) ** ** ** ** ** <2 <2 <2
6 (CN) ** ** ** ** ** <2 <2 <2
7 (CB) ** ** ** ** ** <2 <2 <2
8 (CN) ** ** ** ** <2 <2 <2 <2
9 (CB) ** ** ** ** <2 <2 <2 <2
10 (CB) ** ** ** ** <2 <2 <2 <2
Blank1 20.4 5.3 <2 14.1 <2 <2 <2 <2
11 (CB) <2 <2 <2 <2 <2 <2 <2 <2
12 (CB) <2 <2 <2 <2 <2 <2 <2 <2
13 (CN) <2 <2 <2 <2 <2 <2 <2 <2
14 (CB) <2 <2 <2 <2 <2 <2 * <2
15 (CN) <2 <2 <2 <2 <2 <2 * <2
16 (CB) <2 <2 * <2 <2 <2 <2 <2
17 (CaSi) <2 <2 <2 <2 <2 <2 <2 *
18 (CB) <2 <2 <2 <2 <2 <2 <2 <2
19 (CN) <2 <2 <2 <2 <2 <2 <2 <2
20 (CB) <2 <2 <2 <2 <2 <2 <2 <2
Blank2 <2 <2 <2 <2 <2 <2 <2 <2
21 (CN) <2 <2 <2 <2 <2 <2 <2 <2
22 (CN) <2 <2 <2 <2 <2 <2 <2 <2
23 (CB) <2 <2 <2 <2 <2 <2 <2 <2
24 (CN) <2 <2 <2 <2 <2 <2 <2 <2
25 (CB) <2 <2 <2 <2 <2 <2 <2 <2
26 (CaSi) <2 <2 <2 <2 <2 <2 <2 <2
27 (CB) <2 <2 <2 <2 <2 <2 <2 <2
28
(Therm) <2 <2 <2 <2 <2 <2 <2 <2
29 (CB) <2 <2 <2 <2 <2 <2 <2 <2
30 (CB) <2 <2 <2 <2 <2 <2 <2 <2
Blank3 <2 <2 <2 <2 <2 <2 <2 <2
31 (CB) <2 <2 <2 <2 <2 <2 <2 <2
32 (CB) 2.9 <2 <2 <2 <2 <2 <2 <2
33 (CN) 3.4 <2 <2 <2 <2 <2 <2 <2
34 (CB) 3 <2 <2 <2 <2 <2 <2 <2
35 (CN) 2.3 <2 <2 <2 <2 <2 <2 <2
36(CB)
<2 <2 <2 <2 <2 <2 <2 <2

37(CN)
<2 <2 <2 5.1 <2 <2 2.8 <2

38(CB)
<2 <2 <2 <2 <2 <2 <2 <2

39 (CN) 2.2 <2 <2 <2 <2 <2 <2 <2
40(CN)
<2 <2 <2 <2 <2 <2 <2 <2

Blank4
<2 <2 <2 <2 <2 <2 <2 <2

* Inaccurate data on voltammetry read-out ** Earlier calibration solution produced high Pb peaks

169
Table 6.8: raw voltammetric analyses of lead in leachates second replicates (g/l)

Sample

Extracts

Time 0.25 1 2 4 9 16 36 64
1 (CN) 2.1 <2 <2 <2 <2 <2 <2 <2
2 (CN) <2 <2 <2 <2 <2 <2 <2 <2
3 (CB) <2 <2 <2 <2 <2 <2 <2 <2
4 (CN) <2 <2 <2 <2 <2 <2 <2 <2
5 (CB) <2 <2 <2 <2 3.4 <2 <2 <2
6 (CN) <2 <2 <2 <2 <2 2.1 <2 <2
7 (CB) <2 <2 <2 <2 <2 <2 <2 <2
8 (CN) <2 <2 <2 <2 <2 <2 <2 <2
9 (CB) <2 <2 <2 <2 <2 <2 <2 <2
10 (CB) <2 <2 <2 <2 <2 4.6 <2 <2
Blank1 <2 <2 <2 <2 <2 2.6 <2 <2
11 (CB) <2 <2 <2 <2 <2 <2 <2 <2
12 (CB) <2 <2 <2 <2 <2 <2 2 <2
13 (CN) <2 <2 <2 <2 <2 <2 <2 <2
14 (CB) <2 <2 <2 <2 <2 <2 <2 <2
15 (CN) <2 <2 <2 <2 <2 <2 <2 <2
16 (CB) <2 <2 <2 <2 <2 <2 <2 <2
17 (CaSi) <2 <2 <2 <2 <2 <2 <2 <2
18 (CB) <2 <2 <2 <2 <2 <2 2.5 <2
19 (CN) <2 <2 2.8 2.8 <2 <2 <2 <2
20 (CB) <2 <2 <2 <2 <2 <2 <2 <2
Blank2 <2 <2 2.4 4.7 <2 <2 <2 <2
21 (CN) <2 <2 <2 <2 <2 <2 <2 <2
22 (CN) 2 <2 <2 <2 <2 <2 <2 <2
23 (CB) <2 <2 <2 <2 <2 <2 <2 <2
24 (CN) <2 <2 <2 <2 <2 <2 <2 <2
25 (CB) <2 <2 <2 <2 2.4 <2 <2 <2
26 (CaSi) <2 <2 <2 <2 <2 <2 <2 <2
27 (CB) <2 <2 <2 <2 <2 <2 <2 <2
28
(Therm) <2 <2 <2 <2 <2 <2 <2 <2
29 (CB) <2 2.9 <2 <2 <2 <2 <2 <2
30 (CB) <2 <2 <2 <2 <2 <2 <2 <2
Blank3 <2 <2 <2 4.1 3.5 5 2.2 <2
31 (CB) <2 <2 <2 <2 <2 <2 <2 <2
32 (CB) <2 <2 <2 <2 <2 <2 <2 <2
33 (CN) <2 <2 <2 <2 <2 <2 <2 <2
34 (CB) <2 <2 <2 <2 <2 <2 <2 <2
35 (CN) <2 <2 <2 <2 <2 <2 <2 <2
36(CB)
<2 <2 <2 <2 <2 <2 <2 <2

37(CN)
<2 <2 <2 <2 <2 <2 <2 2.1

38(CB)
<2 <2 <2 <2 <2 <2 <2 <2

39 (CN) <2 <2 <2 <2 <2 <2 <2 <2
40(CN)
<2 <2 <2 <2 <2 <2 <2 <2

Blank4
<2 <2 <2 <2 <2 <2 <2 <2


170
Table 6.9: raw voltammetric analyses of zinc in leachates first replicates (g/l)

Sample

Extracts

Time 0.25 1 2 4 9 16 36 64
1 (CN) 32 46 97 40 34 4 6 13
2 (CN) 27 43 67 37 26 11 2 13
3 (CB) 41 * 66 40 37 14 11 21
4 (CN) 69 19 41 26 11 14 14
5 (CB) 107 19 30 48 38 19 14 15
6 (CN) 55 35 41 36 28 17 15 25
7 (CB) 72 * 85 104 33 12 10 18
8 (CN) 37 30 33 37 9 4 7 21
9 (CB) 30 64 94 24 44 27 29 26
10 (CB) 32 64 46 29 25 14 34 22
Blank1 56 41 28 56 15 38 22 72
11 (CB) 16 10 15 18 16 14 12 25
12 (CB) 13 17 17 18 17 21 21 28
13 (CN) 7 5 9 7 5 6 4 14
14 (CB) 10 13 3 * 16 9 * 30
15 (CN) 6 5 2 3 5 4 * 17
16 (CB) 6 6 * * 8 3 3 17
17 (CaSi) 9 12 6 12 10 7 3 *
18 (CB) 22 4 7 8 8 5 4 73
19 (CN) 5 2 13 16 * 5 3 57
20 (CB) 11 13 219 14 * 11 13 88
Blank2 19 11 44 349 44 16 44 130
21 (CN) 3 3 3 3 2 4 2 999
22 (CN) 3 2 4 <2 <2 <2 3 52
23 (CB) 2 2 3 2 11 2 3 1193
24 (CN) 2 <2 <2 <2 <2 2 4 146
25 (CB) * <2 3 <2 <2 4 5 47
26 (CaSi) <2 <2 2 5 <2 2 3 56
27 (CB) 3 3 2 4 3 3 5 17
28
(Therm) 3 2 <2 2 3 2 3 46
29 (CB) 3 <2 <2 3 * 4 3 30
30 (CB) 4 10 <2 5 3 4 4 25
Blank3 9 7 2 5 5 21 13 42
31 (CB) 56 44 25 67 43 34 24 43
32 (CB) 63 36 391 20 28 22 22 58
33 (CN) 62 31 43 14 19 6 19 75
34 (CB) 55 46 21 30 42 42 48 86
35 (CN) 49 13 14 20 14 22 52
36(CB)
19 13 23 20 19 19 18 19
37(CN)
20 13 48 23 39 17 43 17
38(CB)
35 19 25 57 73 22 18 30
39 (CN) 35 21 26 18 67 10 17 64
40(CN)
42 40 19 27 24 18 21 81
Blank4
63 44 413 21 18 28 33 32

171
Table 6.10: raw voltammetric analyses of zinc in leachates second replicates (g/l)

Sample

Extracts

Time 0.25 1 2 4 9 16 36 64
1 (CN) 34 34 19 * 34 16 19 *
2 (CN) 47 17 21 25 27 25 24 18
3 (CB) 28 27 24 43 14 29 18 19
4 (CN) 15 39 25 26 15 12 17 12
5 (CB) 28 23 30 49 64 30 20 11
6 (CN) 18 17 18 13 10 20 * 16
7 (CB) 44 26 21 223 25 933 16 17
8 (CN) 26 21 24 21 22 24 24 21
9 (CB) 46 45 29 21 45 55 35 28
10 (CB) 34 19 35 22 43 89 42 25
Blank1 41 23 33 35 29 64 37 43
11 (CB) 30 23 25 26 32 47 26 26
12 (CB) 23 33 23 35 35 37 51 29
13 (CN) 25 25 16 24 39 16 15 19
14 (CB) 31 32 33 40 * 33 29 32
15 (CN) * 36 2735 18 23 22 16 21
16 (CB) 25 21 26 141 19 30 20 25
17 (CaSi) 19 26 20 24 14 25 26 *
18 (CB) 19 16 20 31 23 17 15 21
19 (CN) 13 15 27 39 23 130 24 29
20 (CB) 21 24 47 31 24 48 14 40
Blank2 43 26 56 80 44 62 33 163
21 (CN) 20 13 16 28 25 19 33 1078
22 (CN) 17 21 30 50 21 28 34 147
23 (CB) 25 58 36 34 22 90 33 277
24 (CN) 22 33 30 24 37 30 545 213
25 (CB) 32 19 32 23 27 24 24 134
26 (CaSi) 481 20 22 11 31 19 19 101
27 (CB) 29 39 41 65 23 64 33 62
28
(Therm) 23 30 116 19 19 * 57
29 (CB) 24 37 33 45 14 21 15 43
30 (CB) 20 19 12 12 23 22 21 39
Blank3 55 26 23 40 31 88 179 47
31 (CB) 21 42 41 30 50 24 25 33
32 (CB) 50 26 428 26 20 17 22 25
33 (CN) 40 19 15 23 16 12 12 25
34 (CB) 41 29 36 35 44 46 43 *
35 (CN) 40 12 22 17 * 14 15 13
36(CB)
11 * 38 26 27 30 26 32
37(CN)
35 43 49 15 15 15 18 14
38(CB)
22 24 * 21 18 17 16 23
39 (CN) 25 6 31 11 27 13 19 16
40(CN)
31 20 29 15 17 26 24 16
Blank4
33 56 411 28 23 22 24 39

172
-20
-18
-16
-14
-12
-10
-8
-6
-4
-2
0
2
4
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
s2 ii
s4 ii
s6 i
s8 i
s8 ii
s13 i
s13 ii
s17 ii
s19 ii
s21 ii
s22 ii
s24 ii
s26 ii
s33 i
s33 ii
s37 I
s37 ii
s39 i
s39 ii
s40 i
s40 ii

Figure 6.10: leaching of copper from UK survey samples: cementitious samples (concrete, calcium silicate, aircrete)
173
-20
-18
-16
-14
-12
-10
-8
-6
-4
-2
0
2
4
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
s3 ii
s5 i
s5 ii
s7 ii
s9 i
s9 ii
s10 i
s10 ii
s11 i
s11 ii
s12 i
s12 ii
s16 ii
s18 i
s18 ii
s20 ii
s23 i
s23 ii
s25 ii
s27 i
s27 ii
s29 i
s29 ii
s30 i
s30 ii
s31 i
s31 ii
s32 i
s32 ii
s34 i
s38 i

Figure 6.11: leaching of copper from UK survey samples: clay bricks
174
-20
-18
-16
-14
-12
-10
-8
-6
-4
-2
0
2
4
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
s1 i
s2 i
s2 ii
s4 i
s4 ii
s6 i
s6 ii
s8 i
s8 ii
s13 i
s13 ii
s15 i
s17 i
s17 ii
s19 ii
s21 i
s21 ii
s22 ii
s28 ii
s33 i
s33 ii
s35 i
s37 i
s37 ii
s39 i
s39 ii
s40 i
s40 ii

Figure 6.12: leaching of zinc from UK survey samples: cementitious samples (concrete, calcium silicate, aircrete)
175
-20
-18
-16
-14
-12
-10
-8
-6
-4
-2
0
2
4
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
s3 i
s3 ii
s5 i
s5 ii
s7 i
s9 i
s9 ii
s10 i
s10 ii
s11 i
s11 ii
s12 i
s12 ii
s16 ii
s18 i
s18 ii
s20 ii
s25 ii
s27 i
s27 ii
s29 ii
s30 ii
s31 i
s31 ii
s34 i
s34 ii
s36 i
s38 i

Figure 6.13: leaching of zinc from UK survey samples: clay bricks
172
-20
-18
-16
-14
-12
-10
-8
-6
-4
-2
0
2
4
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
) s33 i
s33 ii
s37 I
s37 ii
s39 i
s39 ii
s40 i
s40 ii

Figure 6.14: leaching of copper from cementitious samples
(from Samples 31 - 40 group - see Table 6.2)
-20
-18
-16
-14
-12
-10
-8
-6
-4
-2
0
2
4
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
s31 i
s31 ii
s32 i
s32 ii
s34 i
s38 i

Figure 6.15: leaching of copper from clay brick samples
(from Samples 31 - 40 group - see Table 6.2)

173

-20
-18
-16
-14
-12
-10
-8
-6
-4
-2
0
2
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
s33 i
s33 ii
s35 i
s37 i
s37 ii
s39 i
s39 ii
s40 i
s40 ii

Figure 6.16: leaching of zinc from cementitious samples
(from Samples 31- 40 group - see Table 6.2)

-20
-18
-16
-14
-12
-10
-8
-6
-4
-2
0
2
4
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
s31 i
s31 ii
s34 i
s34 ii
s36 i
s38 i

Figure 6.17: leaching of zinc from clay brick samples
(from Samples 31 - 40 group - see Table 6.

174

7 LEACHING OF CADMIUM, COPPER, LEAD AND ZINC
USING ACCELERATED LEACHING METHODS

7.1 INTRODUCTION

Several monolith leaching tests reported in the literature (refer back to Table 2.14, Chapter 2)
endure for several weeks, and some researchers have studied the leaching of samples over
several months or even a few years. Such tests may be impractical for general use by industry
or by environmental regulatory agencies. A series of shortened leaching methods were
developed and tested (largely on Samples A to J (see Table 3.4, Chapter 3)). Samples were
subjected to leaching in distilled water, heating, and/or pH alteration (either by initially
adjusting the leachant at pH4, or maintaining constant pH of 6.0 ( 0.1)).

Duplicates of Samples A to J were subjected to leaching with tap-water over 64 days (same
experiment as that used for the UK survey samples discussed in Chapter 6). Duplicates of
Samples A to J were then heated to 60C inside the Soxtherm glass beakers, immersed in
phosphate buffer set at pH6.0; this experiment was repeated, but at room temperature. Single
monoliths of Samples A to J (but without Samples B and E) were immersed in distilled water
acidified to pH4 (using nitric acid): this was conducted at room temperature, and at 60C and
100C using the Soxtherm unit. These last experiments were preceded by heating the CB and
CN samples to 60C, 100C and 150C using the Soxtherm unit.

7.2 STANDARD LEACHING TEST (NEN7375) USING TAPWATER LEACHANT
7.21 Details of samples tested

10 samples (1 aircrete, 7 concrete and 2 clay brick samples) were subjected to the same
leaching test method used for the UK survey samples described in Chapter 6. The details and
dimensions of duplicates of each sample are listed in Table 7.1. Samples A through J were
processed between 17
th
October and 27
th
December 2005. Due to air intrusion (and resulting
pH depletion) in the first duplicates, single cubes of samples F H and J were subjected to
further tests between 9
th
January and 14
th
March 2006. All plastic boxes were doubly sealed
with lids and sellotape, in order to prevent air intrusion. Duplicate extracts of all samples
were analysed using voltammetry during 8
th
14
th
May 2006, most within the acceptable limit
of 180 days after processing.

175

Table 7.1: details of Samples A J tested using NEN7345 method
Sample

Details Dimensions
(cm)
Dimensions
(cm)
A Aircrete block (West Highland HA site) 3 3 9 3 3 8.5
B Concrete block (Cairn HA site) 9.5 3 2 9.5 3 2
C Clay brick (Ibstock, red-facing) 4.5 6 3.5 4.5 6 3.5
D GGBS-concrete (sample JC GGBS1) 8 3 3 8.5 3 3
E Recycled (clay brick) aggregate-based concrete 7.5 3 3.5 7.5 3 3.5
F Silica fume-concrete (sample JC BK SF-3) 4 4 4 n.a
G Ordinary concrete (sample JC BK 12-2 25/11) 4 4 4 n.a
H Sewage sludge ash-concrete (400NA BT30) 4 4 4 n.a
I Clay brick (Red Scotland) 4.5 4.5 6.5 4.5 4.5 6.5
J PFA-concrete PFA-1 3.5 4 5.5 3 3.5 6

7.2.2 Results from standard leaching tests

The extracts generated from the tests were initially analysed using AAS for copper and lead,
before being analysed using voltammetry. The data generated using AAS is provided in
Tables 7.2 and 7.3, whilst the voltammetry data is provided in Tables 7.4 to 7.7. In addition,
pH data for the sample leachates is presented in Figure 7.1.

The concentrations observed using voltammetry were generally below 100g/l for copper and
zinc, whilst copper was seldom detected using AAS, and lead was not at all detected using
AAS. Cadmium and lead were seldom detected using voltammetry (Tables 6.4 and 6.6,
respectively), although traces of both cadmium and lead were detected for the Cairn HA
concrete block (Sample 2), and trace of cadmium were detected from extracts of Sample 6
(concrete with silica fume). Copper and zinc were detected in almost all sample extracts, and
cumulative release data is provided in Figures 7.2 and 7.3, respectively.

In contrast with the cumulative release charts presented in Chapter 6 for the UK survey
samples (Figures 7.10 to 7.13), several sets of sample leachates discussed in this section
contained copper and zinc concentrations exceeding those detected in the blank (tapwater)
extracts. Interestingly, the lowest cumulative release of zinc in Figure 7.2 occurs between -6
and -8 mg.m
-2
, similar to the value for the lowest cumulative release of zinc recorded amongst
the UK survey samples. Another peculiar trend is the tendency for second replicate
cumulative results for copper to be higher than for first replicate results, whilst the opposite
trend is seen with the zinc results. One possible trend was the comparatively greater release
of Cu and Zn from Sample J (containing PFA). This may be due to the weaker influence of
Portlandite due to the pozzolanic nature of the PFA, which therefore resulted in a slightly
176
lower pH (Halliday, 2003). Nevertheless, this pattern is at odds with the contrast between the
copper and zinc cumulative release data for the Sample A (thermalite block) replicates.
The negligible release of metals from Samples D to F (containing GGBS, recycled clay brick,
and silica fume, respectively) might indicate the strong adsorptive properties of their
secondary materials. GGBS is an effective absorber of Pb and Zn (Morrison et al, 2003),
whilst concrete containing silica fume accommodates more precipitation of Pb (Geysen et al,
2003). Overall, the release of Cd, Cu, Pb and Zn from standard clay bricks, ordinary concrete
and concrete containing GGBS, PFA, SSA or silica fume may be considered to be
insignificant, and likewise with the UK survey samples, metals may have been transferred
from the solution to the sample surface (via precipitation), although there were some
indications of copper and zinc release into solution (as reflected by cumulative release results
occurring above zero mg.m
-2
).

Table 7.2: AAS analyses of Copper in Samples A to J leachates raw data (g/l)

Sample

Leaching stages (no. of days after commencing experiment)

0.25 1 2 4 9 16 36 64
(1
st
replicates)
A 54.6 <8.3 18.2 11.9 23.0 14.5 17.0 13.3
B 46.5 11.4 17.4 16.9 16.9 <8.3 21.8 18.3
C 69.6 12.1 14.1 9.7 12.1 <8.3 12.1 4.9
D 41.9 10.8 9.6 <8.3 12.1 18.5 7.3 <8.3
E 12.2 <8.3 <8.3 8.5 12.0 9.7 9.7 <8.3
F 32 18.7 12.1 20.3 19.3 <8.3 12.1 15.1
G 11.3 16.5 10.6 10.6 <8.3 8.5 <8.3 13.7
H 16.7 14.9 15.2 10.5 <8.3 17.4 19.2 <8.3
I 9.7 19.5 8.6 13.8 <8.3 16.2 16.4 10.1
J 20.0 9.5 <8.3 <8.3 14.6 11.6 <8.3 <8.3
Blank <8.3 <8.3 <8.3 <8.3 <8.3 <8.3 <8.3 <8.3

Table 7.3: AAS analyses of Lead in Samples A to J leachates raw data (g/L)

Sample

Leaching stages (no. of days after commencing experiment)

0.25 1 2 4 9 16 36 64
(1
st
replicates)
A <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7
B <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7
C <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7
D <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7
E <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7
F <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7
G <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7
H <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7
I <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7
177
J <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7
Blank <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7 <46.7

Table 7.4: voltammetric analyses of Cadmium in Samples A to J leachates raw data (g/l)

Sample

Extracts
(bold figures indicate no. of days extract was obtained after start of
experiment)

0.25 1 2 4 9 16 36 64

(1
st
replicates)

A 0.6 <0.1 <0.1 <0.1 <0.1 0.8 0.7 <0.1
B 1.4 0.9 0.4 0.4 <0.1 0.5 <0.1 0.3
C <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
D <0.1 0.3 3.9 <0.1 <0.1 <0.1 <0.1 <0.1
E <0.1 0.2 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
F
0.2
0.4
1.2
2.0
0.5
<0.1
0.4
0.2
0.4
0.2
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
G <0.1 0.2 0.2 0.2 0.3 <0.1 <0.1 <0.1
H <0.1 <0.1 <0.1 0.2 <0.1 <0.1 <0.1 <0.1
I <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
J <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
Blank <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

(2
nd
replicates)

A <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
B 0.3 0.3 0.5 0.2 0.3 0.2 0.3 1.1
C <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
D <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
E <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
F
G
H
I <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1
J <0.1 <0.1 * * <0.1 * * <0.1

* Inaccurate results
No replicate samples were subjected to leaching (leachate analyses of the silica fume-containing
concrete were duplicated)

178

Table 7.5: voltammetric analyses of Copper in Samples A to J leachates raw data (g/l)

Sample

Extracts
experiment)

0.25 1 2 4 9 16 36 64

(1
st
replicates)

A 10.2 8.4 17.2 8.4 9.9 10.8 7.6 9.6
B 42.8 22.3 16.0 28.0 24.0 23.6 39.1 23.4
C 17.7 26.3 10.3 <2 14.2 21.8 16.6 11.7
D 21.4 9.6 12.5 10.0 20.1 17.9 12.6 14.4
E 13.3 11.6 12.1 10.9 15.4 20.3 14.0 10.1
F
13.9
16.6
13.1
27.6
5.0
5.3
30.9
20.5
7.0
6.0
16.5
14.1
19.2
14.6
16.8
24.2
G 16.0 5.9 5.2 9.1 7.6 17.2 22.2 21.6
H 8.3 8.9 15.3 11.9 9.3 17.9 14.4 31.8
I 21.9 24.0 22.7 26.2 18.3 15.9 22.8 18.7
J 17.9 23.0 19.3 14.5 12.5 81.3 66.0 60.1
Blank 12.4 9.3 13.4 10.5 22.8 19.0 25.6 13.0

(2
nd
replicates)

A 13.0 10.8 15.0 12.6 8.2 6.3 5.5 8.0
B 27.5 20.0 17.3 14.1 17.9 4.6 52.7 32.1
C 13.2 5.7 11.2 9.6 8.4 10.4 7.9 8.3
D 11.9 11.8 7.9 5.2 4.2 10.2 10.0 6.6
E 12.6 8.6 7.3 7.5 6.3 6.0 9.5 7.5
F
G
H
I 11.5 8.9 10.8 12.8 10.7 7.7 8.2 9.5
J 10.8 6.4 * * 10.9 * * 4.4


179

Table 7.6: voltammetric analyses of lead in Samples A to J leachates raw data (g/l)

Sample

Extracts
experiment)

0.25 1 2 4 9 16 36 64

(1
st
replicates)

A <2 <2 <2 <2 <2 <2 <2 <2
B <2 <2 2.1 2.0 <2 <2 <2 <2
C <2 6.1 <2 <2 <2 <2 <2 <2
D <2 <2 2.4 <2 <2 <2 <2 <2
E <2 <2 <2 <2 <2 <2 <2 <2
F
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
<2
G <2 <2 <2 <2 <2 <2 <2 <2
H <2 <2 <2 <2 <2 <2 <2 <2
I <2 <2 <2 <2 <2 <2 <2 <2
J <2 4.1 <2 <2 <2 <2 <2 <2
Blank <2 <2 <2 <2 <2 <2 <2 <2

(2
nd
replicates)

A <2 <2 <2 <2 <2 <2 <2 <2
B <2 <2 <2 <2 <2 <2 <2 <2
C <2 <2 <2 <2 <2 <2 <2 <2
D <2 <2 <2 <2 <2 <2 <2 <2
E <2 <2 <2 <2 <2 <2 <2 <2
F
G
H
I <2 <2 <2 <2 <2 <2 <2 <2
J <2 <2 * * <2 * * <2


180

Table 7.7: voltammetric analyses of zinc in Samples A to J leachates raw data (g/l)

Sample

Extracts
experiment)

0.25 1 2 4 9 16 36 64

(1
st
replicates)

A 58 46 50 58 39 55 53 65
B 60 57 34 65 172 28 30 31
C 71 71 30 67 62 34 36 46
D 24 58 23 26 47 32 31 33
E 30 26 21 23 33 33 26 28
F
20
39
40
8
17
16
23
17
27
23
24
19
51
6
21
18
G 64 18 45 18 18 21 18 20
H 27 30 34 28 28 32 20 30
I 44 41 50 149 29 29 52 37
J 25 35 38 75 17 113 63 60
Blank 42 22 27 31 27 51 40 56

(2
nd
replicates)

A 38 12 24 20 13 53 18 24
B 26 18 17 18 15 3 15 15
C 21 23 21 27 14 18 15 23
D 10 15 12 9 13 10 15 13
E 16 12 21 10 11 13 22 13
F
G
H
I 17 23 28 25 36 34 39 31
J 23 21 * * 43 * * 20


176
6
7
8
9
10
11
12
0.1 1 10 100
Time (days)
p
H
A i
A ii
B i
B ii
C i
C ii
D i
D ii
E i
E ii
F
G
H
I i
I ii
J i
J ii
Blank

Figure 7.1: pH of sample leachates under standard NEN7345 test
178
-8
-6
-4
-2
0
2
4
6
8
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
A i
A ii
B i
B ii
C i
D i
D ii
E i
E ii
F
F ii
G
H
I i
I ii
J

Figure 7.2: leaching of copper from samples under NEN7345 test (refer back to Table 7.1)
179
-8
-6
-4
-2
0
2
4
6
8
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
A i
A ii
B i
B ii
C
D i
D ii
E i
E ii
F i
F ii
G
H
I i
I ii
J

Figure 7.3: leaching of zinc from samples under NEN7345 test (refer back to Table 7.1)
180
7.3 TREATMENT OF CLAY BRICK AND PFA-LADEN CONCRETE SAMPLES
(CB, CN) USING pH4-ACIDIFIED DISTILLED WATER AND RAISED
TEMPERATURE

7.3.1 pH data

Figures 7.4 and 7.5 illustrate the pH changes observed with clay brick and concrete samples
(details provided in Chapter 3, Table 3.10). As expected, the pH of clay brick leachate
occurred near the neutral range. The pH of the concrete leachate was typically between pH10
and pH11.

2
3
4
5
6
7
8
9
10
11
12
0 50 100 150 200
Time (hours)
p
H
CB 20C i
CB 20C ii
CB 60C i
CB 60C ii
CB 100C i
CB 100C ii
CB 150C i
CB 150C ii

Figure 7.4: pH data for the clay brick (CB) leachates
2
3
4
5
6
7
8
9
10
11
12
0 50 100 150 200
Time (hours)
p
H
CN 20C i
CN 20C ii
CN 60C i
CN 60C ii
CN 100C i
CN 100C ii
CN 150C i
CN 150C ii

Figure 7.5: pH data for the concrete (CN) leachates

181
7.3.2 Cumulative release data

All extracts were acidified and refrigerated prior to voltammetry analysis, which was conducted
during May June 2006. However, some of the VA results were characterised by uneven
background noise, imbalanced peaks and shrunken peak heights. The results for sample
extracts produced at 150C were particularly prone to these problems, and none have been
reproduced in the tables or figures provided. Tables 7.8 to 7.11 detail the raw voltammetric
data produced from the CB and CN sample extracts. As expected, Cd and Pb were undetected.
The concentrations of copper and zinc were also particularly low, often occurring below the
detection limit (less so with copper). The data does not suggest greater leaching of copper and
zinc from the PFA-laden concrete (CN) sample, compared with the data for the clay brick (CB)
sample.
Table 7.8: raw leachate data (voltammetry analyses) (g/l): cadmium

Leaching stage (time, days)

Sample
0.25 1 2.25 4 7
CB 20C 0.3 0.4 <0.1 0.1 <0.1
CB 20C <0.1 0.2 <0.1 0.3 <0.1
CN 20C <0.1 1.0 <0.1 <0.1 <0.1
CN 20C <0.1 <0.1 <0.1 <0.1 <0.1
CB 60C 0.3 <0.1 <0.1 <0.1 <0.1
CB 60C <0.1 <0.1 <0.1 <0.1 <0.1
CN 60C 0.6 <0.1 <0.1 <0.1 <0.1
CN 60C 0.8 <0.1 <0.1 <0.1 <0.1
Blanks <0.1, <0.1 <0.1, 0.2 <0.1, <0.1 0.1, 0.3 <0.1, 0.3
CB 100C <0.1 <0.1 <0.1 <0.1 -
CB 100C <0.1 <0.1 <0.1 <0.1 -
CN 100C <0.1 <0.1 <0.1 <0.1 -
CN 100C <0.1 <0.1 <0.1 <0.1 -
Blank 0.2 0.2 <0.1 <0.1 -

Table 7.9: raw leachate data (voltammetry analyses) (g/l): copper

Leaching stage (time, days)

Sample
0.25 1 2.25 4 7
CB 20C 20.8 44 9.6 9 14.2
CB 20C 20.5 25 8.4 5 7.5
CB 60C 6.4 7.5 9.1 9.7 8.8
CB 60C 10.1 4.3 8.2 14.9 6.2
CN 20C 113.4 22.1 10.4 7.1 7.8
CN 20C 50.4 12.7 4.3 3 4.4
CN 60C <2 22.6 9.8 10.3 12.4
CN 60C 9.1 19.1 27 7.2 12.4
Blanks <2, 5.9 <2, 3.7 <2, 5.1 <2, 3.0 <2, 2.1
CB 100C 8.5 11.1 <2 4.3 -
CB 100C 3.3 5.9 <2 <2 -
CN 100C 14.2 16.2 11.6 9.7 -
CN 100C 15.8 16.8 15.1 12.1 -
Blank 2.4 2.0 3.0 <2 -
182
Table 7.10: raw leachate data (voltammetry analyses) (g/l): lead

Sample
0.25 1 2.25 4 7
CB 20C <2 <2 <2 <2 <2
CB 20C <2 <2 <2 <2 <2
CB 60C <2 <2 <2 <2 <2
CB 60C <2 <2 <2 <2 <2
CN 20C <2 <2 <2 <2 <2
CN 20C <2 <2 <2 <2 <2
CN 60C <2 <2 <2 <2 <2
CN 60C <2 <2 <2 <2 <2
Blanks <2, 3.1 <2, <2 <2, <2 <2, <2 <2, <2
CB 100C <2 <2 <2 <2 -
CB 100C <2 <2 <2 <2 -
CN 100C <2 <2 <2 <2 -
CN 100C <2 <2 <2 <2 -
Blank <2 <2 <2 <2 -

Table 7.11: raw leachate data (voltammetry analyses) (g/l): zinc

Sample
0.25 1 2.25 4 7
CB 20C 36 34 5 12 9
CB 20C 21 31 20 6 4
CB 60C 85 48 5 9 3
CB 60C 16 10 7 0 11
CN 20C 60 18 4 6 8
CN 20C <2 * <2 4 3
CN 60C 71 2 5 12 10
CN 60C <2 6 2 <2 <2
Blanks 23, 13 16, 9 14, 16 7, 12 9, 8
CB 100C 5 6 <2 6 -
CB 100C 9 6 <2 4 -
CN 100C <2 3 <2 3 -
CN 100C <2 <2 <2 <2 -
Blank 19 18 15 11 -

Furthermore, the cumulative release trends for copper and zinc (indicated in Figures 7.6 and
7.7) do not indicate that the rate of copper or zinc leaching correlated with temperature on the
contrary, the results for copper in extracts of samples heated at 60C and 100C tended to
suggest that the leaching may have been suppressed. Due to zinc concentrations in several
extracts occurring below the detection limit, the data presented in Figure 7.6 is considerably
limited, and no relationship between leaching and temperature could be discerned. The
recorded cumulative release of copper and zinc from the CB and CN samples might have been
too insignificant (generally less than 3mg.m
-2
), for any influences of temperature to be
exhibited by the data.
183
0.01
0.1
1
10
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
CB 20C
CB 20C ii
CB 60C
CB 60C ii
CB 100C
CB 100C ii
CN 20C
CN 20C ii
CN 60C
CN 60C ii
CN 100C
CN 100C ii

Figure 7.6: CB/CN tests: cumulative release data (copper)
0.01
0.1
1
10
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
CB 20C
CB 20C ii
CB 60C
CB 60C ii
CB 100C
CB 100C ii
CN 20C
CN 20C ii
CN 60C
CN 60C ii
CN 100C
CN 100C ii

Figure 7.7: CB CN Tests: cumulative release data (zinc)

During heating of the concrete (CN) samples, it was noticed that small crystals precipitated
around the Soxtherm beaker glass interior. Andac and Glasser (1999) reported that trace metals
may be re-absorbed into precipitates or onto the container walls, especially at a moderately
alkaline pH. Once the experiment for heating concrete replicates at 100C (CN100C) was
complete, the leachate was discarded, and dilute nitric acid was slowly poured into the beakers
to dissolve the crystals.

184
Since the cumulative release data for Pb, Cd, and Zn were insignificant for the CN duplicates
treated at 100C, only the proportions of leachate and re-precipitated copper were studied.
Based on raw voltammetric data (without blank values subtracted), it was estimated that
between 10% and 20% of Cu initially in the leachate may have re-precipitated on the Soxtherm
glass beaker surface.

7.3.3 Comparison with XRF data

Portions of the CB and CN bricks were crushed following the leaching tests. Most replicates
contained undetectable quantities of copper and lead; only zinc was detected in all samples
(Figure 7.8; Tables 7.35 to 7.37). The zinc concentrations in the clay bricks were consistently
higher (~150 200ppm) compared with the concentrations in the test PFA-concrete
(<100ppm). Nevertheless, this contrast was not translated into consistently higher cumulative
releases of zinc from the CN samples, compared with the CB samples. The data for copper
concentrations analysed using XRF was too limited to compare with cumulative release data.
0
20
40
60
80
100
120
140
160
180
200
C
B

2
0
C

i
C
B

2
0
C

ii
C
B

6
0
C

i
C
B

6
0
C

ii
C
B

1
0
0
C

i
C
B

1
0
0
C

i
i
C
B

1
5
0
C

i
C
B

1
5
0
C

i
i
C
N

2
0
C

i
C
N

2
0
C

i
i
C
N

6
0
C

i
C
N

6
0
C

i
i
C
N

1
0
0
C

i
C
N

1
0
0
C

ii
C
N

1
5
0
C

i
C
N

1
5
0
C

ii
p
p
m
Cd
Cu
Pb
Zn

Figure 7.8: XRF analysis of CB and CN replicates

7.4 INVESTIGATION INTO THE INFLUENCE OF TEMPERATURE ON
LEACHING OF METALS FROM SAMPLES A J USING DISTILLED
WATER ACIDIFIED TO pH4

Further investigation into the influence of temperature was undertaken, using Samples A to J,
and employing the same experimental conditions used upon the CB and CN samples.

185
7.4.1 Materials and Methods

Due to limited remaining sample quantities, three single blocks of samples A-J (excluding
samples B and E) were tested, at room temperature (using plastic containers), and at 60C and
100C (using the Soxtherm units). These were approximately 2cm 2cm 5cm dimensions,
which were cut and prepared using the same methods as with previous blocks mentioned in
Chapter 3 (see Table 3.11), and subjected to leaching for 1 week. AAS was used for analysis.
Unfortunately, the pH meter produced inaccurate readings, although the leachate pH of
Samples A to J was recorded for the standard NEN735 leaching test (refer back to Figure 7.1).

7.4.2 Proportions of Dissolved and Re-precipitated Metals

After completion of the leaching experiments, some further investigation was conducted into
the trace metal content within the precipitated crystals around the Soxtherm glass beakers.
20ml of dilute nitric acid was added to the Soxtherm beakers, in order to wash off any
precipitated compounds from the container walls.

The proportions of dissolved (total cumulative release) and re-precipitated metals are illustrated
in Figures 7.9 and 7.10. Although this is based on raw data without the AAS detection limit
values having been subtracted, there are indications that the proportions of metals being
absorbed into the precipitated crystals could have been significant, particularly for copper and
zinc. However, no precipitates were present inside the (plastic) containers used for leaching the
samples at room temperature, and neither copper nor zinc were detected in any rinses from
these containers (to check for precipitated metals).

-50
0
50
100
150
200
T
o
t
a
l

Z
n

(
g
/
l
)
precip
leached

Figure 7.9: Proportions of leached and re-precipitated Zn
186
-100
0
100
200
300
400
500
T
o
t
a
l

C
u

(
g
/
l
)
precip
leachate

Figure 7.10: Proportions of leached and re-precipitated Cu

7.4.3 Cumulative release of copper, lead and zinc

Tables 7.11 to 7.20 detail the corrected sample analyses of copper, lead and zinc, as analysed
using AAS. All lead and most zinc results occurred below the limit of detection, hence only the
cumulative release of copper was calculated (as shown in Figure 7.13). Few comparisons can
be due to undetectable concentrations of copper within several extracts. For sample G
(ordinary concrete), the occurrence of leachate concentrations is greater for treatment at 60C
(compared with treatment at room temperature), and greater for treatment at 100C (compared
with treatment at 60C). However, the same pattern is not repeated with the data sets for
samples D, F or H. Conclusions cannot therefore be drawn regarding the influence of
temperature on the leaching of copper (or for cadmium, lead and zinc) from Samples A to J,
mainly since the concentrations in extracts were either minor or below the limit of detection.
0.1
1
10
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
C (20C)
D (60C)
D (100C)
F (20C)
F (60C)
F (100C)
G (20C)
G (60C)
G (100C)
H (20C)
H (60C)
I (100C)

Figure 7.11: cumulative release of copper from samples treated at pH4

187
Table 7.12: copper in sample leachates (pH4-acidified distilled water at room temperature)

Time Sample
0.25 1 2.25 4 7
A 13.3 <8.3 11.1 <8.3 10.0
C 31.1 11.1 11.1 <8.3 10.0
D 30.0 <8.3 <8.3 <8.3 <8.3
F 41.1 12.21 12.2 <8.3 10.0
G 20.0 8.9 13.3 <8.3 15.5
H 79.9 14.4 17.8 <8.3 11.1
I 26.6 <8.3 <8.3 <8.3 <8.3
J 27.8 <8.3 <8.3 <8.3 <8.3
Blank <8.3 <8.3 <8.3 <8.3 <8.3

Table 7.13: copper in sample leachates (pH4-acidified distilled water at 60C)

Time Sample
0.25 1 2.25 4 7
A <8.3 <8.3 14.2 11.8 13.0
C 30.7 18.88 <8.3 <8.3 <8.3
D 36.6 18.9 31.9 29.5 <8.3
F 30.7 24.8 31.9 29.5 27.1
G 40.0 23.3 18.9 16.7 17.8
H 45.5 28.9 13.3 11.1 6.7
I 28.9 34.4 <8.3 11.1 12.2
J 12.21 <8.3 <8.3 <8.3 34.4
Blank <8.3 <8.3 <8.3 <8.3 <8.3

Table 7.14: copper in sample leachates (pH4-acidified distilled water at 100C)

Time Sample
0.25 1 2.25 4 7
A <8.3 1.11 7.77 <8.3 <8.3
C <8.3 3.33 79.92 <8.3 <8.3
D 34.4 17.76 13.32 <8.3 17.76
F 34.4 23.31 25.53 22.2 12.21
G 132.0 82 64 40 72
H <8.3 15 <8.3 <8.3 <8.3
I 147 108 66 45 42
J 86.58 36.63 <8.3 <8.3 <8.3
Blank <8.3 <8.3 <8.3 <8.3 <8.3

Table 7.15: lead in sample leachates (pH4-acidified distilled water at room temperature)

Time Sample
0.25 1 2.25 4 7
A <46.7 <46.7 <46.7 <46.7 <46.7
C <46.7 <46.7 <46.7 <46.7 <46.7
D <46.7 <46.7 <46.7 <46.7 <46.7
F <46.7 <46.7 <46.7 <46.7 <46.7
G <46.7 <46.7 <46.7 <46.7 <46.7
H <46.7 <46.7 <46.7 <46.7 <46.7
I <46.7 <46.7 <46.7 <46.7 <46.7
J <46.7 <46.7 <46.7 <46.7 <46.7
Blank <46.7 <46.7 <46.7 <46.7 <46.7
188
Table 7.16: lead in sample leachates (pH4-acidified distilled water at 60C)

Leaching time (days) Sample
0.25 1 2.25 4 7
A <46.7 <46.7 <46.7 <46.7 <46.7
C <46.7 <46.7 <46.7 <46.7 <46.7
D <46.7 <46.7 <46.7 <46.7 <46.7
F <46.7 <46.7 <46.7 <46.7 <46.7
G <46.7 <46.7 <46.7 <46.7 <46.7
H <46.7 <46.7 <46.7 <46.7 <46.7
I <46.7 <46.7 <46.7 <46.7 <46.7
J <46.7 <46.7 <46.7 <46.7 <46.7
Blank <46.7 <46.7 <46.7 <46.7 <46.7

Table 7.17: lead in sample leachates (pH4-acidified distilled water at 100C)

Time Sample
0.25 1 2.25 4 7
A <46.7 <46.7 <46.7 <46.7 <46.7
C <46.7 <46.7 <46.7 <46.7 <46.7
D <46.7 <46.7 <46.7 <46.7 <46.7
F <46.7 <46.7 <46.7 <46.7 <46.7
G <46.7 <46.7 <46.7 <46.7 <46.7
H <46.7 <46.7 <46.7 <46.7 <46.7
I <46.7 <46.7 <46.7 <46.7 <46.7
J <46.7 <46.7 <46.7 <46.7 <46.7
Blank <46.7 <46.7 <46.7 <46.7 <46.7

Table 7.18: zinc in sample leachates (pH4-acidified distilled water at room temperature)

Time Sample
0.25 1 2.25 4 7
A <19.6 <19.6 <19.6 <19.6 22
C <19.6 <19.6 <19.6 <19.6 <19.6
D <19.6 36 <19.6 <19.6 <19.6
F
G <19.6 <19.6 <19.6 <19.6 <19.6
H <19.6 38 28 <19.6 24
I <19.6 <19.6 <19.6 <19.6 <19.6
J <19.6 <19.6 <19.6 <19.6 <19.6
Blank <19.6 <19.6 <19.6 <19.6 <19.6

Table 7.19: zinc in sample leachates (pH4-acidified distilled water at 60C)

Time Sample
0.25 1 2.25 4 7
A <19.6 <19.6 <19.6 <19.6 <19.6
C <19.6 22 <19.6 <19.6 <19.6
D 30 26 40 <19.6 <19.6
F <19.6 26 <19.6 <19.6 24
G <19.6 46.875 <19.6 -22.5 <19.6
H <19.6 <19.6 <19.6 -24.375 <19.6
I <19.6 <19.6 <19.6 -24.375 <19.6
J <19.6 <19.6 <19.6 <19.6 <19.6
Blank
<19.6 <19.6 <19.6 <19.6 <19.6
189
Table 7.20: zinc in sample leachates (pH4-acidified distilled water at 100C)

Time Sample
0.25 1 2.25 4 7
A 100 <19.6 <19.6 <19.6 <19.6
C 30 <19.6 <19.6 <19.6 50
D <19.6 <19.6 <19.6 <19.6 <19.6
F <19.6 <19.6 <19.6 <19.6 <19.6
G <19.6 <19.6 <19.6 <19.6 50.625
H <19.6 <19.6 <19.6 <19.6 <19.6
I <19.6 <19.6 <19.6 <19.6 <19.6
J <19.6 <19.6 <19.6 <19.6 <19.6
Blank <19.6 <19.6 <19.6 <19.6 <19.6

7.5 TREATMENT OF SAMPLES A TO J USING pH6 PHOSPHATE BUFFER

Three series of experiments were conducted, using phosphate buffer solution set at pH6.0
(0.1). Extracts of samples subjected to Soxtherm heating at 60C were produced between
November 2005 and January 2006. Extracts of samples subjected to room temperature were
produced during March 2006, and extracts of samples heated in an oven at 60C were produced
in April 2006. All extracts were analysed using either AAS or voltammetry, and were therefore
studied within the recommended limit of 180 days after production.

7.5.1 AAS Results

Extracts of samples heated to 60C using the Soxtherm units produced were initially analysed
using AAS. AAS analysis of Pb proved difficult, since the concentrations of the extracts were
mostly below the limit of detection. Only the results for Cu and Zn are therefore presented
(Tables 7.21 and 7.22, and Figures 7.12 and 7.13). The data is tempered with few
consistencies, although the leaching of copper and zinc were lowest from the aircrete sample
(Sample A), and tended to be comparatively higher from the clay brick samples (Samples 3 and
9). Cumulative release of copper ranged from approximately 2 to 10 mg.m
-2
, whilst the
cumulative release of zinc ranged from approximately 0.8 to 8 mg
-2
. Plotted on logarithmic
scales, the data plots for nearly all samples appear perfectly linear. This may indicate that the
prime leaching mechanism was diffusion, in obedience of Ficks 1
st
Law.

7.5.2 Voltammetry results

Extracts of samples treated with pH6 buffer at room temperature, and heated to 60C using the
Soxtherm units were analysed using voltammetry. Raw data is presented in Tables 7.23 to
7.30, and cumulative release results for cadmium, copper and zinc are presented in Figures 7.15
190
Table 7.21: leaching of copper (pH6 buffer, 60C using Soxtherm heating) (g/l)

0.25 1 2.25 4 7
A 29.1 19.1 25.1 27.9 0
B 67.8 54.6 57.5 52.4 53.7
C 105 78.1 79.9 62.1 59.1
D 38.8 26.8 32.3 17 19.1
E 40.3 27.3 35.3 28.2 28.4
F 93.7 68.4 84.2 55.2 57.5
G 57 45.9 42.4 40.1 45.9
H 36.8 15.8 29.5 17.3 19.4
I 113.6 60.7 61.1 47 47.4
J 146 101.5 99.7 88.6 83.9
Blank <2 <2 <2 <2 <2

Table 7.22: leaching of zinc (pH6 buffer, 60C using Soxtherm heating) (g/l)

0.25 1 2.25 4 7
A 18.5 <2 <2 <2 27.8
B 27.6 18.4 18.4 9.2 18.4
C 91.9 55.1 46.0 36.8 46.0
D 54.6 36.4 36.4 18.2 18.2
E 27.7 27.7 27.7 27.7 18.5
F 7.3 45.5 36.4 27.3 18.2
G 55.7 37.1 27.8 22.3 18.6
H 27.5 22.0 22.0 11.0 9.2
I 54.8 36.5 45.7 27.4 3.7
J 45.4 27.2 27.2 18.2 18.2
Blank <2 <2 <2 <2 <2
0.1
1
10
100
0.1 1 10
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
A
B
C
D
E
F
G
H
I
J

Figure 7.12: leaching of copper from samples treated with phosphate buffer at 60C
(AAS results)
191
0.1
1
10
100
0.1 1 10
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
A
B
C
D
E
F
G
H
I
J

Figure 7.13: leaching of zinc from samples treated with phosphate buffer at 60C
(AAS results)

to 7.17. Regular analyses of phosphate buffer solution were conducted alongside analyses of
sample extracts, and the former analyses were treated as blanks. Blank values have been
subtracted from the data presented in Tables 7.23 to 7.30.

Within Figures 7.14 to 7.16, data plots for samples leached at room temperature are connected
with broad lines, whilst those of samples leached at 60C are connected with dotted lines. It
was not evident that raising the temperature led to increased cumulative release of either
cadmium, copper or zinc. The sparse data for cadmium leaching (Figure 7.14) suggests slight
increases in leaching under increased temperature from samples F and I, although no clear
conclusions can be drawn here. The data regarding copper and zinc leaching is even less
convincing.

The copper leaching results for heated samples tend to be concentrated towards the centre of the
range of cumulative release results (Figure 7.15), hence the cumulative release of copper from
unheated samples often exceeded that of heated samples. Similar findings are presented in
Figure 7.16 for the cumulative release of zinc.

Two Sample F (silica fume-laden concrete) leachate extracts (from experiments set at 60C)
contained anomalously high concentrations of lead (Table 7.29). This was not repeated with
any other extracts, so this may have been due to contamination in the voltammetry cell.
192
Table 7.23: raw voltammetric data of extracts of samples leached at room temperature using
pH6 buffer (Cadmium)

0.25 1 2.25 4 7
First replicates
A 9 <0.1 <0.1 7.0 4.7
B - - - - -
C <0.1 <0.1 <0.1 <0.1 <0.1
D <0.1 <0.1 <0.1 <0.1 <0.1
E - - - - -
F <0.1 19.4 2.8 2.6 5.6
G <0.1 <0.1 <0.1 <0.1 <0.1
H <0.1 <0.1 <0.1 <0.1 <0.1
I <0.1 <0.1 <0.1 <0.1 <0.1
J 5.3 <0.1 <0.1 <0.1 <0.1
Second replicates
A <0.1 1.0 0.6 0.6 0.6
B <0.1 <0.1 <0.1 <0.1 0.4
C 0.5 0.6 0.6 0.6 0.9
D <0.1 <0.1 <0.1 0.6 0.4
E <0.1 <0.1 <0.1 <0.1 <0.1
F 1.1 0.4 1.3 0.6 0.1
G <0.1 <0.1 0.5 <0.1 <0.1
H <0.1 0.5 <0.1 0.4 0.3
I 0.3 0.2 0.8 0.4 0.3
J - - - - -

pH6 buffer (Copper)

0.25 1 2.25 4 7
First replicates
A 54.2 72.5 49.3 48.2 70.8
B - - - - -
C 191.8 171.5 107 86.7 100.1
D 155.2 109.7 91.1 84 87.7
E - - - - -
F 96.9 170.6 70.6 70.2 81.9
G 118 112.9 85.6 81.5 90
H 116 153 84 82 86
I 116 153 84 82 86
J 130 139 67 69.6 84.6
Second replicates
A 20.5 16.7 23.8 24.3 25.8
B 56 50.7 47.7 44.3 49.5
C 87.7 73.2 75.8 54.3 47.8
D 29.1 22.2 24 16.9 25
E 34.5 25.5 26.2 28.5 26.8
F 87.5 64.5 81.5 58.4 59.3
G 53.1 45.1 47.3 41.9 46.7
H 35.9 16.7 29.9 18.8 20.5
I 109.5 71.2 70.2 51.8 50.3
J - - - - -
193
pH6 buffer (Lead)

0.25 1 2.25 4 7
First replicates
A <2 <2 12 3.4 4.1
B - - - - -
C <2 <2 <2 4.6 1.9
D <2 <2 <2 4.7 5.6
E - - - - -
F <2 19.4 2.8 2.6 5.6
G <2 <2 <2 4.4 6.5
H <2 10.8 4.4 4.7 2.6
I <2 10.8 4.4 4.7 2.6
J <2 9.9 5.5 4.7 6
Second replicates
A <2 <2 <2 <2 <2
B <2 <2 <2 <2 <2
C <2 <2 <2 <2 <2
D <2 <2 <2 <2
E <2 <2 <2 <2 <2
F <2 <2 <2 <2 <2
G <2 <2 <2 <2 <2
H 3.7 <2 <2 <2 <2
I <2 <2 <2 <2 <2
J - - - - -

pH6 buffer (Zinc)

0.25 1 2.25 4 7
First replicates
A 23 9 24 46 <2
B
C 26 15 11 16 20
D 155 110 91 84 88
E
F 12 23 <2 5 15
G 18 6 7 6 13
H <2 6 <2 <2 15
I <2 6 <2 <2 15
J 46 <2 3 11 15
Second replicates
A 10 23 10 3 31
B 10 23 10 3 31
C 74 49 36 27 34
D 29 22 24 17 25
E 30 16 17 11 10
F 69 40 24 12 101
G 29 25 13 7 13
H 28 10 15 5 12
I 50 28 26 18 26
J
194
Table 7.27: raw voltammetric data of extracts of samples leached at 60C using pH6 buffer
(Cadmium)

Leaching time (days)
Sample

0.25 1 2.25 4 7
A <0.1 <0.1 <0.1 <0.1 <0.1
B 0.8 <0.1 0.6 0.9 <0.1
C <0.1 1.1 1.5 1 1.8
D 0.3 <0.1 0.3 <0.1 <0.1
E 0.2 <0.1 <0.1 <0.1 <0.1
F 0.3 0.7 0.4 15.8 23.5
G 0.4 <0.1 <0.1 <0.1 <0.1
H 0.6 0.3 0.2 0.3 0.8
I 0.4 0.5 0.6 1.8 0.6
J <0.1 <0.1 <0.1 <0.1 <0.1

(Copper)

Sample

0.25 1 2.25 4 7
A 97.5 22.3 18.3 27.3 18.5
B 96.1 61.1 70.1 17.3 52.2
C 65.6 38.0 18.6 20.0 17.5
D 54.6 41.3 42.3 35.5 55.8
E 55.9 49.3 28.6 48.3 62.2
F 35.8 37.3 36.6 41.6 40.0
G 24.4 35.6 27.5 41.8 29.2
H 26.1 23.4 21.4 21.1 21.2
I 32.5 45.6 27.8 21.4 20.4
J 14.6 117.1 100.4 83.9 63.5

(Lead)

Sample

0.25 1 2.25 4 7
A <2 <2 <2 <2 <2
B <2 <2 <2 <2 <2
C <2 <2 <2 <2 <2
D <2 <2 <2 <2 <2
E <2 <2 <2 <2 <2
F <2 <2 <2 15.8 23.5
G <2 <2 <2 <2 <2
H <2 <2 <2 <2 <2
I <2 <2 <2 <2 <2
J <2 <2 <2 <2 <2

195
Table 7.30: raw voltammetric data of extracts of samples leached 60C using pH6 buffer (Zinc)

Sample

0.25 1 2.25 4 7
A 37 27 12 60 12
B 32 22 50 31 15
C 125 75 61 43 29
D 54 41 42 36 56
E 28 19 15 19 26
F 25 34 20 38 30
G 25 31 16 33 20
H 40 30 23 24 31
I 51 49 37 41 40
J 21 35 26 20 20

0.001
0.01
0.1
1
0.1 1 10
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
C roomT ii
F roomT ii
F 60C
H 60C
I roomT ii
I 60C

Figure 7.14: cumulative release of cadmium from samples leached with pH6 buffer at room
temperature and at 60C
196
0.01
0.1
1
10
100
0.1 1 10
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
A roomT i
A roomT ii
A 60C
B buffer roomT ii
B 60C
C room T i
C roomT ii
C 60C
D roomT i
D roomT ii
D 60C
E roomT ii
E 60C
F roomT i
F roomT ii
F 60C (VA)
G roomT i
G roomT ii
G 60C
H roomT i
H roomT ii
H 60C
I roomT i
I roomT ii
I 60C
J roomT i
J 60C

Figure 7.15: leaching of copper from Samples A J treated with pH6 buffer at room temperature, and at 60C
197

0.01
0.1
1
10
100
0.1 1 10
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
A roomT i
A roomT ii
A 60C
B roomT ii
B 60C
C roomT i
C roomT ii
C 60C
D roomT i
D roomT ii
D 60C
E roomT ii
E 60C
F roomT i
F roomT ii
F 60C
G roomT i
G roomT ii
G 60C
H room T i
H roomT ii
H 60C
I room T i
I roomT ii
I 60C
J roomT i
J 60C

Figure 7.16: leaching of zinc from samples treated with pH6 buffer at room temperature, and at 60C
198
7.5.3 XRF Analysis of Samples

The XRF results for samples produced alongside the Soxtherm (60C), room temperature and
oven heating (60C) tests are illustrated in Figures 7.17 - 7.19 (also see Tables 7.35 to 7.37).
Concentrations of each metal amongst the samples were similar, although Samples 1 and 8
contained comparatively higher concentrations. Anderson and Skerratt (2003) reported that
sewage sludge contains elevated heavy metal concentrations (compared with standard
construction materials, e.g. ordinary (Portland cement-based) concrete). During XRF
analysis, it was noticed that noticeable quantities of phosphate were present in the crushed
pellets of Samples A-J after Soxtherm treatment. During Soxtherm leaching, small white
crystals were formed on the concrete samples. It may be possible that phosphate compounds
derived from the buffer solution precipitated out onto and within the pores of the samples.
Further research is required in order to investigate whether or not significant proportions of
leached metals were absorbed by these crystals.
0
50
100
150
200
250
300
350
400
450
500
A B C D E F G H I J
p
p
m
60C i
60C ii
25C
20C
60C oven

Figure 7.17: Copper content of samples leached with pH6 buffer
0
50
100
150
200
250
300
350
400
450
500
A B C D E F G H I J
p
p
m
60C i
60C ii
25C
20C
60C oven

Figure 7.18: Lead content of samples leached with pH6 buffer

199
0
50
100
150
200
250
300
350
400
450
500
A B C D E F G H I J
p
p
m
60C i
60C ii
25C
20C
60C oven

Figure 7.19: Zinc content of samples leached with pH6 buffer

7.6 OVEN HEATING OF SAMPLES AT 60C

Samples A to J (excluding samples 2 and 5) were also heated within plastic containers under
oven heating at 60C, in order to compare these conditions with those within the Soxtherm
units. Raw data is presented in Tables 7.31 to 7.34, and cumulative release of copper and zinc
are presented in Figures 7.20 and 7.21, respectively. It is interesting to note that overall, these
releases of copper and zinc are comparatively lower with the general range of cumulative
releases of copper and zinc portrayed (for Soxtherm-heated samples) in Figures 7.16 and 7.17.
As anticipated, most cadmium and lead concentrations in extracts were negligible.

Table 7.31: cumulative release of cadmium from samples oven-heated to 60C


Sample
0.25 1 2.25 4 7
A <0.1 <0.1 <0.1 0.2 <0.1
C 0.3 0.9 <0.1 <0.1 <0.1
D <0.1 <0.1 <0.1 <0.1 <0.1
F <0.1 <0.1 <0.1 <0.1 <0.1
G <0.1 0.5 <0.1 <0.1 <0.1
H <0.1 <0.1 <0.1 <0.1 <0.1
I 0.9 0.5 1.4 <0.1 <0.1
J <0.1 <0.1 0.9 <0.1 <0.1
Blank <0.1 <0.1 <0.1 <0.1 <0.1

200
Table 7.32: cumulative release of copper from samples oven-heated to 60C


Sample
0.25 1 2.25 4 7
A 24.8 22.6 22.9 19.3 9.1
C 53.2 48.1 35.5 19 29.7
D 58 26.3 30.8 6.1 16.7
F 67.4 41.1 38.8 16.7 26.2
G 66.4 44.1 47.6 27.4 32.5
H 52.5 42.5 43.2 21.5 22.5
I 63.3 34.2 41 10.3 12.2
J 50.7 29.6 43.6 12.7 14.4
Blank 4.8 3.5 2.8 <2 2.5

Table 7.33: cumulative release of lead from samples oven-heated to 60C


Sample
0.25 1 2.25 4 7
A <2 <2 <2 <2 <2
C <2 <2 <2 <2 <2
D 3.1 <2 <2 <2 <2
F <2 <2 <2 <2 <2
G <2 <2 <2 <2 <2
H <2 <2 <2 <2 <2
I <2 <2 2 <2 <2
J 3 <2 <2 <2 <2
Blank <2 <2 <2 <2 <2

Table 7.34: cumulative release of zinc from samples oven-heated to 60C


Sample
0.25 1 2.25 4 7
A 20 12 5 5 4
C 20 3 11 8 18
D 30 8 8 <2 4
F 1 6 14 2 6
G 27 9 9 2 6
H 26 18 18 43 5
I 35 13 26 12 9
J 26 5 36 14 7
Blank 4.8 3.5 2.8 <2 2.5

201
0.1
1
10
0.1 1 10
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
A
C
D
F
G
H
I
J

Figure 7.20: cumulative release of copper from samples oven-heated to 60C

0.01
0.1
1
10
0.1 1 10
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
A
C
D
F
G
H
I
J

Figure 7.21: cumulative release of copper from samples oven-heated to 60C

7.7 COLLATION OF RESULTS FROM DIFFERENT LEACHING METHODS

Comparisons between different leaching methods addressed in this chapter are illustrated for
the cumulative release of copper and zinc (Figures 7.22 to 7.41). (Note: 60C implies
heating at 60C; VA indicates voltammetry analysis of leachates.) XRF data for copper, lead
and zinc in Samples 1 to 10 is also provided in Tables 7.35 to 7.37. (Aliquots of Samples A
to J were taken and processed for XRF analysis alongside different leaching experiments.)
202
7.7.1 Influence of altered parameters on leaching

The evidence provided in Figures 7.22 to 7.41 indicate that either the influence of temperature
on the recorded cumulative release data was marginal, or that the cumulative release of
copper and zinc from the samples was too insignificant for the influence of temperature to be
deduced. In general, the setting of the pH using phosphate buffer or nitric acid did not
significantly alter the rate of leaching either. The phosphate buffer tended to enable higher
release of metals into solution, especially with the first run of Cu analyses of extracts of
samples processed at room temperature. In relation to the pH6 leaching tests, the
concentration of zinc and copper in leachate extracts were consistently higher compared with
those in blank extracts. One prominent feature is the very high Cu concentration in Sample B
leachates produced at room temperature using pH6 buffer treatment. These high results were
the first produced after the voltametry machine was repaired after several months of being
inoperative.

With regards to the samples leached using pH4-acidified distilled water, copper was regularly
detected, although the higher limits of detection associated with AAS mostly prevented the
detection of lead and zinc. It is interesting to note that the cumulative release of copper was
typically higher amongst several of the samples, compared with that of zinc. This contrasts
somewhat with the regular detection of often higher concentrations of zinc compared with
copper, in solid samples using XRF analysis.

-4
-2
0
2
4
6
8
10
12
14
16
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater I (VA)
NEN7345 tapwater ii (VA)
pH6 buff er roomT i
pH6 buff er roomT ii
pH6 buff er 60C (VA)
pH6 buff er 60C (AAS)
pH6 buff er 60C (oven)

Figure 7.22: cumulative release of copper from sample A under different leaching conditions
203
-10
-5
0
5
10
15
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater i
NEN7345 tapwater ii
pH6 buff er roomT i

Figure 7.23: cumulative release of zinc from sample A under different leaching conditions

-2
0
2
4
6
8
10
12
14
16
18
20
22
24
26
28
30
32
34
36
38
40
42
44
46
48
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater i
NEN7345 tapwater ii

Figure 7.24: cumulative release of copper from sample B under different leaching conditions
204
-10
-5
0
5
10
15
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater i
NEN7345 tapwater ii

Figure 7.25: cumulative release of zinc from sample B under different leaching conditions

-2
0
2
4
6
8
10
12
14
16
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater ii
RoomT pH4 dist.wtr
pH6 buff er roomT i

Figure 7.26: cumulative release of copper from sample C under different leaching conditions
205
-10
-5
0
5
10
15
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater ii
pH6 buff er roomT i

Figure 7.27: cumulative release of zinc from sample C under different leaching conditions

-2
0
2
4
6
8
10
12
14
16
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
) NEN7345 tapwater i
NEN7345 tapwater ii
60C pH4 dist.wtr
100C pH4 dist.wtr
pH6 buff er roomT i

Figure 7.28: cumulative release of copper from sample D under different leaching conditions
206
-10
-5
0
5
10
15
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater i
NEN7345 tapwater ii
pH6 buff er roomT i

Figure 7.29: cumulative release of zinc from sample D under different leaching conditions

-2
0
2
4
6
8
10
12
14
16
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater i
NEN7345 tapwater ii

Figure 7.30: cumulative release of copper from sample E under different leaching conditions
207
-10
-5
0
5
10
15
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater i
NEN7345 tapwater ii

Figure 7.31: cumulative release of zinc from sample E under different leaching conditions

-2
0
2
4
6
8
10
12
14
16
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater i
NEN7345 tapwater ii
RoomT pH4 dist.wtr
60C pH4 dist.wtr
100C pH4 dist.wtr
pH6 buff er roomT i

Figure 7.32: cumulative release of copper from sample F under different leaching conditions
208
-10
-5
0
5
10
15
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater i
NEN7345 tapwater ii
pH6 buff er roomT i

Figure 7.33: cumulative release of zinc from sample F under different leaching conditions

-2
0
2
4
6
8
10
12
14
16
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
) NEN7345 tapwater i
RoomT pH4 dist.wtr
60C pH4 dist.wtr
100C pH4 dist.wtr
pH6 buff er roomT i

Figure 7.34: cumulative release of copper from sample G under different leaching conditions
209
-10
-5
0
5
10
15
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater i
pH6 buff er roomT i

Figure 7.35: cumulative release of zinc from sample G under different leaching conditions

-2
0
2
4
6
8
10
12
14
16
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater i
RoomT pH4 dist.wtr
60C pH4 dist.wtr
pH6 buff er roomT i

Figure 7.36: cumulative release of copper from sample H under different leaching conditions
210
-10
-5
0
5
10
15
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater i
pH6 buff er roomT i

Figure 7.37: cumulative release of zinc from sample H under different leaching conditions

-2
0
2
4
6
8
10
12
14
16
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater i
NEN7345 tapwater ii
100C pH4 dist.wtr
pH6 buff er roomT i

Figure 7.38: cumulative release of copper from sample I under different leaching conditions
211
-10
-5
0
5
10
15
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater i
NEN7345 tapwater ii
pH6 buff er roomT i

Figure 7.39: cumulative release of zinc from sample I under different leaching conditions

-2
0
2
4
6
8
10
12
14
16
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater i
pH6 buff er roomT i

Figure 7.40: cumulative release of copper from sample J under different leaching conditions
212
-10
-5
0
5
10
15
0.1 1 10 100
Time (days)
C
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
NEN7345 tapwater i
pH6 buff er roomT i

Figure 7.41: cumulative release of zinc from sample J under different leaching conditions

7.7.2 Correlation between cumulative release and XRF data

Tables 7.35 to 7.37 provide raw XRF analysis data for the sample replicates analysed
alongside the leaching experiments. With many samples (among Samples A to J), the
concentrations of copper and lead were detected in some replicates, but not in others. Tables
7.38 and 7.39 detail the averaged concentrations of copper and zinc determined using XRF for
samples, alongside the averaged cumulative release of these metals under the various leaching
tests. The data used for studying the relationship between XRF and cumulative release could
only be conducted with copper and zinc, and only where both XRF and cumulative release
values were produced in relation to the same accelerated leaching test. As shown in Tables
7.35 and 7.36, copper and zinc were often either detected, or undetectable in replicates of the
same samples. As shown in Figures 7.23 to 7.42, the cumulative release of copper or zinc
was sometimes undetectable, particularly when samples were treated using pH4 dilute nitric
acid. As a result, some cumulative release and XRF data is omitted from this study.

The relationship between the averaged XRF and leachate data is illustrated in Figures 7.42
and 7.43. Overall, there was neither a positive nor a negative correlation between average
metal concentrations in the samples with cumulative leaching of the metal although the
concentrations in replicates and leachate were possibly so low that such a correlation cannot
be disproved. Another interesting feature is the regular detection of lead in sample replicates
(Table 7.36), even though lead was almost never detected in sample leachates.

213
Table 7.35: XRF analyses of copper (mg/kg)
Samples Leaching experiment
A B C D E F G H I J
Room temperature, pH6 buffer (i) 136 66 n.d. n.d. n.d. n.d. 154 97 61 68
Room temperature, pH6 buffer (ii)
257

n.d. 80

n.d. n.d. n.d. n.d. n.d.
60C (Soxtherm), pH6 buffer (i) 75 n.d. n.d. n.d. n.d. n.d. n.d. 185 n.d. n.d.
60C (Soxtherm), pH6 buffer (ii) 99 n.d. n.d. n.d. n.d. n.d. n.d. 147 n.d. n.d.
60C (Oven heating), pH6 buffer 116 n.d. 77 n.d. n.d. 125 n.d. n.d.
Room temperature, pH4-acidified
water 182 n.d. n.d. 98 n.d. 139 n.d. 61
60C, pH4-acidified water 199 83 n.d. n.d. n.d. 166 n.d. 94
100C, pH4-acidified water 205 81 n.d. 77 n.d. 178 n.d. 68

Table 7.36: XRF analyses of lead (mg/kg)
A B C D E F G H I J
Room temperature, pH6 buffer
(i) 104 n.d. 48 n.d. n.d. n.d. 97 n.d. 68 n.d.
Room temperature, pH6 buffer
(ii)

98

69 n.d.

n.d n.d n.d n.d n.d
60C (Soxtherm),
pH6 buffer (i) n.d. n.d. n.d. n.d. 79 n.d. n.d. 119 n.d. 69
60C (Soxtherm),
pH6 buffer (ii) 87 n.d. 48 n.d. 77 n.d. n.d. 87 n.d. n.d.
60C (Oven heating), pH6 buffer 93 80 n.d. n.d. n.d. 74 n.d. n.d.
Room temperature,
pH4-acidified water 228 55 n.d. n.d. n.d. 59 n.d. n.d.
60C,
pH4-acidified water 146 63 n.d. n.d. n.d. 70 76 n.d.
100C,
pH4-acidified water 202 62 n.d. n.d. n.d. 158 n.d. n.d.

Table 7.37: XRF analyses of zinc (mg/kg)
A B C D E F G H I J
Room temperature, pH6
buffer (i) 198 79 106 68 134 62 238 85 134 54
Room temperature, pH6
buffer (ii)

381

154 73

72 57 90 67 n.d.
60C (Soxtherm), pH6 buffer
(i) 117 65 165 68 101 43 73 276 80 62
60C (Soxtherm), pH6 buffer
(ii) 139 61 121 79 112 94 82 341 77 43
60C (Oven heating), pH6
buffer 147 152 69 66 74 209 92 66
Room temperature,
pH4-acidified water 174 121 160 68 113 350 78 161
60C, pH4-acidified water 171 140 74 137 132 298 108 130
100C, pH4-acidified water 220 173 236 134 145 345 98 178

214
Table 7.38: averaged concentrations of copper

Sample

Average cumulative
release*
(mg.m
-2
)

Average concentration
in sample* (XRF
analysis)
(ppm)

Sample population (n)

(No. of different leaching experiments
whereby metal was detected in both
leachate and XRF replicates)

A 3 136.6 5
B ** ** 0
C ** ** 0
D 2.8 78.5 2
E ** ** 0
F 1.5 77.0 1
G 10.5 154.0 1
H 4.3 144.0 5
I 12 61.0 1
J 10.9 68.0 1
* Based on data from leaching experiments whereby copper was detected in both leachates and in
samples processed for XRF analysis
** Copper not detected using XRF in any sample replicates

Table 7.39: averaged concentrations of zinc

Sample

Average cumulative
release*
(mg.m
-2
)

Average concentration
in sample* (XRF
analysis)
(ppm)

Sample population (n)

(No. of different leaching experiments
whereby metal was detected in both
leachate and XRF replicates)

A 1.5 196.4 5
B 2.3 63.0 2
C 4.5 139.6 5
D 5.1 71.4 5
E 3.0 106.5 2
F 2.6 67.4 5
G 2.6 104.8 5
H 1.8 200.2 5
I 3.0 90.0 5
J 2.2 56.3 4
* Based on data from leaching experiments whereby copper was detected in both leachates and in
samples processed for XRF analysis
** Copper not detected using XRF in any sample replicates

7.8 DISCUSSION

It has been said that as the pH decreases from approximately pH8, the quantities of transition
metal released via diffusion increase exponentially (Van der Sloot, 2001). Van der Sloot
(2001) also noted that the rate of release of cations into solution generally increases with
temperature. (However, certain cement hydration products become less soluble with
increasing temperature. For example, Jooss (2001) reported that the leaching rate of calcium
ions into solution could decrease from approximately 60C upwards.)
215
0
2
4
6
8
10
12
14
0 50 100 150 200 250
Average concentration in sample (ppm)
A
v
e
r
a
g
e

c
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
Aircrete
Clay bricks
Concrete

Figure 7.42: correlation between averaged XRF and cumulative release data: copper

0
2
4
6
8
10
12
14
0 50 100 150 200 250
Average concentration in sample (ppm)
A
v
e
r
a
g
e

c
u
m
u
l
a
t
i
v
e

r
e
l
e
a
s
e

(
m
g
.
m
-
2
)
Series1
Series2
Series3

Figure 7.43: correlation between averaged XRF and cumulative release data: zinc

The NEN7345 leaching test prescribed immersion of monolithic samples in distilled or
weakly acidic (pH4) water, in order to reflect exposure of structures to acidic soil or rainwater
(Van der Sloot et al, 2001). Nevertheless, the standard did not require that pH4 conditions be
maintained throughout the experiment. Surface water and soil water are also exposed to
ingress of carbon dioxide, allowing carbonic acid to be produced. Other acids (e.g. sulphuric
and nitric acid in acid rain; e.g. biogenic acids in soil water) will also react with building
materials (Andac and Glasser, 1999). Natural soil water typically has a pH of approximately
216
pH4.5 to pH8, whilst rainwater typically has a pH of approximately pH3.5 to pH7 (Van der
Sloot, 2003).

Andac and Glasser (1999) subjected concrete samples to pH6 conditions by injecting carbon
dioxide gas into the surrounding water. Some other researchers (e.g. Moudilou et al, 2002)
have used similar pH control methods using nitric acid. These require automated injection
and monitoring equipment - neither of which were available for this project. An alternative
approach is to use a buffer solution. Nagataki et al (2002) used dilute acetic-acetate buffer
(pH5.2), although the pH of their leachates were typically above pH6. Phosphate buffer was
therefore, whereby the imposed pH of the solution surrounding the samples was 6.0 (0.1).
Occasional injections of buffer salts were required to retain this pH.

Later tests involved heating solutions containing Samples A-J using distilled water acidified
to pH4. For those tests, the pH was not kept constant as such pH control would have been
highly demanding (requiring additions of nitric acid on an hourly or more regular basis). It
would have been desirable to have had these extracts analysed using voltammetry, in order to
make direct comparisons with leachate data produced from the other experiments (except for
the extracts produced over 64 days).

With all the extracts produced, there were some general patterns. In general, Cd and Pb were
never detected (again, the absence of Pb was unexpected, and contrasts with the literature
review findings in Figures 2.25 and 2.26). The concentrations of Cu in extracts of samples
treated with tap-water over 64 days were consistently the lowest, compared with results from
other experiments. A similar pattern was found with regards to Zn concentrations, with the
exception of high Zn concentrations in extracts of Samples B and I (concrete, clay brick,
respectively) treated over 64 days with tap-water.

Some individual patterns were identified. One possible trend was the comparatively greater
release of Cu and Zn from Sample J (containing PFA) compared with the other samples,
based on the 64-day leaching test using tap-water. This may have been due to the weaker
influence of Portlandite due to the pozzolanic nature of the PFA, which therefore resulted in a
slightly lower pH (Halliday, 2003). Nevertheless, this pattern was at odds with the contrast
between the copper and zinc cumulative release data for the Sample A (thermalite block)
replicates using the same test (Figures 7.2 and 7.3).

The negligible release of metals from Samples D to F (containing GGBS, recycled clay brick,
and silica fume, respectively) using the 64-day test might have been an indication of the
217
strong adsorptive properties of their secondary materials. GGBS is an effective absorber of
Pb and Zn (Morrison et al, 2003), whilst concrete containing silica fume accommodates more
precipitation of Pb (Geysen et al, 2003). As mentioned in the last chapter, the iron and
aluminium minerals in clay brick are also reported to strongly absorb trace metals (Karius et
al, 2002).

Nevertheless, the patterns observed using the 64-day leaching test with tap-water were not
repeated with extracts produced using the shortened leaching tests using altered pH or
temperatures. One reason for this may have been that none of the samples (Samples A to J)
contained significant quantities of trace metals. According to several literature sources,
leaching tests have been conducted using concrete containing incinerator fly ashes, which
release considerably higher quantities of trace metals into solution. Based on the data
provided in this chapter, the influence of heating could not be deduced. It is more probable
that the stronger influence of the pH6 phosphate buffer on leaching of Cu and Zn owed to the
chelating effect of the buffer complex, as well as the pH being constantly maintained at
around 6.0.

However, other factors can affect the mobilisation of trace metals, including sample porosity,
as well as any micro-cracks induced by mechanical wear (e.g. when cutting the samples), both
of which are characterised by additional exposed sample surface area from which more metals
may be released (Achternbosch et al, 2003). The extent of carbonation of concrete samples is
another factor, mainly due to the changes in capillary porosity of concrete due to calcite
precipitation. The concrete samples containing GGBS, silica fume, recycled aggregate, SSA,
PFA and (PFA + SSA) (Samples D, E, F, H, J and CN, respectively) were wrapped in cling
film immediately after being cured, in order to restrict air ingress. However, further research
using larger samples, as well as carbonation tests (using phenolphatalein indicator (Guteirrez
et al, 1996)) and porosity tests (e.g. hydrostatic testing (Aubert et al, 2004)) are required in
order to try and relate leaching of trace metals with carbonation and porosity of concrete
samples. Results for Cu and Zn in extracts of Samples A to J (except B and E) processed
using pH4-acidified water at various temperatures may have been considerably different, had
it been possible to use voltammetry. Future research using the same tests should therefore
entail voltammetry analysis.

7.9 CONCLUSIONS

Monoliths of Samples A to J, as well as of the CB and CN samples, were subjected to
accelerated leaching tests, as well as being leached using the NEN7345 for comparison.
218
Alterations used to accelerate the leaching process included pH control, and temperature
increase. All samples subjected to leaching under altered conditions were immersed in
distilled water, in order to isolate and investigate the leached metals released from the
samples (as opposed to the metals dissolved in tap-water).

Regardless of the testing method employed, cadmium was never detected, and lead was rarely
detected in the extracts. With regards to Samples A to J, the leaching of copper and zinc did
not generally appear to have increased under higher temperatures (with the exception of
Sample 7), when pH4-acidified distilled water leachant was used. Leaching of zinc using
phosphate buffer tended to be similar at both room temperature and at 60C, whereas leaching
of copper using phosphate buffer tended to be greater at room temperature. However, this
pattern may have owed to higher peaks and background noise during voltammetry analysis of
the first set of extracts produced from samples treated with phosphate buffer at 60C.

Overall, the release of cadmium and lead using these tests was determined to be insignificant,
whilst minor quantities of copper and zinc were usually detected in extracts (typically a few
tens of micrograms per litre), even when the pH and the temperature was controlled. It may
be concluded that there would normally be insignificant leaching of Cd, Cu, Pb and Zn into
the environment from clay bricks, ordinary Portland cement-based concrete, or concrete
containing GGBS, silica fume, SSA or PFA.
237
8 CONCLUSIONS AND RECOMMENDATIONS

The aims of this PhD project were (1) to investigate the content of dioxins and furans in a
range of inorganic, non-metallic building materials for British housing, and (2) to assess their
potential for leaching of Cd, Cu, Pb and Zn into the environment (specifically into water).
The null hypothesis underlying these aims was to prove that their dioxin and furan content,
and the leaching of the aforementioned trace metals from building materials is not a cause for
concern.

8.1 LITERATURE REVIEW

An investigation was conducted into the occurrence of dioxins and furans, and the potential
release of Cd, Cu, Pb and Zn from inorganic, non-metallic building materials for housing.
Information was collected on the manufacture, use and chemical composition of mortar, clay
bricks, concrete bricks/blocks, calcium silicate bricks and plasterboard, as well as the
materials used in these products. Information was also collected on the production and
potential applications of secondary materials (namely GGBS, silica fume, PFA, FBA), as well
as on waste materials (including SSA, cement kiln dust and incinerator fly ash).

The sources and formation of dioxins and furans, as well as their concentrations in soils and
building materials were investigated. Dioxins and furans originate from two main
anthropogenic sources: combustion (especially of organic matter), and as by-products of the
pesticides (organochlorine) industry. There has been considerable debate on the exact
mechanisms of dioxin and furan formation during the past 3 decades, and much of this has
focussed specifically on their formation in MSW incinerator flue gases. In general there has
been less interest on their occurrence in cement kilns, coal-fired power stations (which
produce PFA and FBA) or iron smelting (although iron ore sintering is a reported source).
Consequently, plentiful data exists on the dioxin and furan content of soils, sediment and
MSW incinerator fly ash. Limited data exists on the dioxin and furan content of PFA and
MSW incinerator bottom ash (IBA), and almost none exists on that in standard building
products or Portland cement. Concentrations of dioxins and furans reported within this
restricted data pool are very minor (only a few ng I-TEQ kg or less), in contrast with the wide
variation of concentrations reported for MSW incinerator fly ash (ranging from around 70 up
to 70,000 ng I-TEQ kg).

238
Cd, Cu, Pb and Zn are ubiquitous elements, occurring often in trace concentrations in soils,
sediment, as well as in cement and concrete. Intact solid materials (termed, monolithic)
may leach these metals into surrounding water, and research has been conducted into the
release of trace metals, particularly from concrete-encapsulated incinerator ashes. A common
method used for monolithic samples is the NEN7345 test (now superceded by the NEN7375
test in the UK), whereby a cubic sample of dimensions >40mm is immersed in distilled water
(often acidified to pH4 using nitric acid) and leached for 8 successively longer periods (from
6 hours to 28 days), lasting 64 days in total. Results on leaching tests conducted on concrete
comprising Ordinary Portland cement, blast furnace slag, incinerator (IFA, IBA) ashes or
PFA have been published by some researchers. In contrast, no literature was found regarding
leaching of metals from clay bricks, nor was any found regarding leaching of metals from
monolithic samples containing silica fume or SSA. There was some evidence that the
inclusion of MSW fly ash in concrete may produce greater leaching of Cu, Pb and Zn
compared with that emanating from ordinary concrete or cement mortar - although a few
results for Cd, Pb and Zn leaching from ordinary samples exceeded those for waste-
encapsulating mortars or concrete.

8.2 COLLECTION OF SAMPLES

A large collection of building material/product samples representative of British housing was
assembled, along with some demolition waste samples and PFA samples, plus some concrete
samples containing secondary or waste materials (GGBS, silica fume, PFA or SSA). Samples
of commercial clay bricks, mortar, Portland cement, plasterboard, concrete and calcium
silicate bricks were collected from new housing sites from 12 broad regions in the UK:
Scotland, Northern Ireland, Wales, London and another 8 regions in England. Particular
emphasis was made on targeting new and existing housing sites in heavily urbanised regions.
The collection of building material samples (as well as soils which would represent
background environmental dioxin and furan levels) from new housing construction sites
was a success over 200 samples comprising all six types (aforementioned) were obtained.

Obtaining samples (drillings) from existing housing was more difficult, mainly because these
were collected by tradesmen and posted via courier - only 16 were assembled. A limited
number of PFA, demolition waste, and concrete blocks containing secondary/waste materials
were provided within the department. At least one drilled sample from existing housing was
sourced from each of the 12 targeted UK regions. Concrete blocks comprising GGBS, silica
fume, PFA or SSA were assembled.

239
8.3 EXTRACTION AND ANALYSIS OF DIOXINS AND FURANS

Over 150 (new housing) construction material samples, 15 existing housing, 13 demolition
waste, 8 PFA and 22 soil samples were subjected to Soxtherm extraction, extract filtration,
extract concentration and GC-MS/MS analysis. No evidence of any dioxin and furan content
was forthcoming in any of the samples analysed with the possible exception of some minor
hepta-chlorinated furan congener peaks found in two soil sample extract chromatographs.

It was originally intended to process all the samples which had been assembled, as well as
analysing GGBS, silica fume, MSW incinerator fly ash and SSA. However, when the first
(approx.) 40 samples (mostly from Scottish new housing construction sites) were processed
using the EPA 1613 cleanup filter, the chromatograph results were unsatisfactory, and sample
processing was delayed for several weeks until a more suitable (altered) cleanup filter was
developed. Once this problem was overcome, access to the GC-MS/MS instrument at the
consultancy was very limited, and not all samples could be processed as a result. Indeed,
processing soil, demolition waste and PFA samples produced contaminated extracts which
obscured the
13
C-dioxin and furan peaks on the resulting chromatographs. Further alterations
to the clean-up method would have been required in order to analyse other substances such as
these, as well as other secondary/waste materials including GGBS, SSA and silica fume. This
was not possible as access to the GC-MS/MS instrument was no longer possible once the soil
samples had been processed.

The recovery of dioxins and furans during sample processing using the altered clean-up filter
was either moderate or low (generally less than 50%, often lower). As a result, it cannot be
categorically proven that dioxins and furans did not exist in the samples. The concentrations
were, however, likely to have occurred below the recommended limit of 50ng I-TEQ/kg.
This is in agreement with the small data pool found in the literature, which reported very
minor quantities of dioxins and furans in construction materials.

Further research is needed to confirm that the concentrations in construction materials,
namely those containing secondary by-products (e.g. GGBS-laden concrete or thermalite
blocks), is indeed insignificant. Data regarding dioxins and furans in demolition waste and a
wide range of secondary by-products for concrete does not exist in the literature at present,
and ought to be a priority for future research. It may be speculated that clay bricks, concrete,
plasterboard (as well as secondary materials such as GGBS, silica fume or SSA) contain very
minor quantities of dioxins and furans. One recommendation may be to use larger sample
aliquots (perhaps 20g or more), and if necessary, reverting to using HR (high resolution)
240
GCMS which embodies lower limits of detection (down to 3fg, or 3 10
-15
grams), compared
with GC-MS/MS (characterised with an LOD of approximately 100 300fg) (Petrovic et al,
2002).

8.4 LEACHING OF CADMIUM, COPPER, LEAD AND ZINC FROM A
SELECTION OF BUILDING MATERIALS USING THE 64-DAY TEST

13 concrete, 2 calcium silicate, 20 clay brick samples and one aircrete sample taken from the
UK survey samples were cut into 40 monoliths in total, and subjected to leaching using an
altered NEN7345 method, whereby tap-water was the leachant, and many samples comprised
dimensions of under 40mm. 36 monoliths were immersed in tap-water, whilst another 4 were
immersed in distilled water, in order to investigate the leaching of metals from the samples,
and the influence of dissolved metals in tap-water, respectively.

It was found that the concentrations of zinc and copper in tap-water-based leachates tended to
range from around 10g/l to over 100g/l, and the concentration of lead in tap-water was
sometimes detectable (occurring at or below 10g/l). With samples immersed in distilled
water, it was found that the leaching of copper and zinc from concrete and clay brick samples
was minimal, whilst the leaching of lead and cadmium could not be detected. In contrast,
copper and zinc were regularly detected in tap-water leachates from the other samples,
although at lower concentrations compared with tap-water blank extracts.

The copper and zinc detected in the tap-water extracts probably originated mostly from the
tap-water itself. In addition, proportions of dissolved copper and zinc may have precipitated
out of solution during the leaching tests. It may be concluded that the leaching of cadmium,
copper, lead and zinc from concrete, clay bricks, calcium silicate bricks and demolition
(housing) materials, is generally insignificant, and probably would not warrant any further
H&S investigation under most circumstances. However, other factors need to be considered,
including possible contamination within the voltammetry cell by traces of metals left behind
from calibration solutions. Secondly, the peaks on the voltammetry readout seemed to
decline prior to the machine breaking down as the first sample extracts were being analysed.

The precipitation of trace metals out of solution onto sample surfaces could be further
examined using methods detailed by Coleman et al (2005), whereby (1) concrete samples
were placed in distilled water solutions characterised by set concentration of 1000ppm (mg/l)
of copper, lead and zinc nitrate; (2) electron microscopy was used to examine the precipitate
crystals on sample surfaces; and, (3) concrete samples were treated using nitric acid in order
241
to extract metal compounds which had precipitated out of solution. Another recommendation
might be to analyse all extracts from further construction material samples as soon as they are
obtained, as well as following the NEN7375 method more closely (i.e. use glass sample
containers, use samples with dimensions exceeding 4mm, and use distilled water leachant). A
third suggestion is that sample extracts processed according to the NEN7375 method could be
evaporated to a smaller volume, in order to augment the concentrations of leached metals. In
addition, the sides of sample containers should be flushed with dilute nitric acid at the end of
leaching tests, and these wash-offs should also be analysed.

8.5 ACCELERATED LEACHING OF CADMIUM, COPPER, LEAD AND ZINC

A selection of commercial concrete and clay brick, plus concrete samples laden with
secondary/waste materials (Samples A to J, CB, CN) were subjected to a range of
leaching tests, including the 64-day leaching test used for the UK survey samples, and also a
number of shortened tests (7 days) under altered temperature and/or pH conditions. This was
conducted in order to investigate leaching under lower pH conditions, and also to shorten the
lengthly 64-day leaching test.

It was anticipated that lower pH and higher temperatures would have led to increased
leaching of Cd, Cu, Pb and Zn. In spite of these alterations, there was no significant increase
in leaching of any of these metals from any particular sample, except when some samples
were immersed in dilute phosphate buffer solution constantly set at pH6 (0.1). With all tests
conducted, trace quantities of copper and zinc were present in extracts (usually between 10
and 150g/l); lead was seldom detected, and occurred at very small quantities (seldom above
10g/l). Cadmium was never detected in relation to any samples processed.

There was no observable influence of temperature on the rate of leaching, not even with
samples treated with phosphate buffer solution. Nevertheless, the data detailed throughout
Chapter 7 can only be interpreted with great caution, mainly because most samples comprised
dimensions less than 40mm, and they could not always be analysed in duplicate. This was
due to limited time, the limited quantities of each sample, as well as the small dimensions of
samples (as the Soxtherm machine glass beakers could only accommodate samples with sides
less than 25mm).

Recommendations for further research include the following:

242
- Reducing sample extract volume using evaporation in order to increase dissolved
metal concentrations;

- Using larger glass containers, in order to accommodate more suitably sized samples
(in contrast with the small Soxtherm glass beakers);

- Constantly monitoring temperature and pH throughout leaching experiments
(although pH monitoring might become difficult if the temperature is significantly
raised above room temperature);

- Doping samples with metal oxides (e.g. lead or cadmium oxide) in order to
exacerbate the quantities of metals leached into solution. This approach has been
taken previously by researchers such as Barna et al (2005). However, Andac and
Glasser (1999) have warned against this practice stating that the leaching behaviour
from a doped sample is likely to be considerably different to leaching from a real
specimen. Another approach may be to conduct tests on concrete containing MSW
incinerator fly ash, which has been widely studied by other researchers in the field.

243
REFERENCES

Abad, E; Adrados, M A; Caixach, J; Fabrellas, B; Rivera, J. Dioxin Mass Balance in a
Municipal Waste Incinerator. Chemosphere 40 (2000) 1143-1147

Acternbosch, M; Brautigam, K R; Hartlieb, N; Kupsch, C; Richers, U; Stemmerman, P.
Heavy Metals in Cement and Concrete Resulting from the Co-incineration of Wastes in
Cement Kilns with Regard to the Legitimacy of Waste Utilisation. Published by
Umweltbundesamt, 2003 (Forschungszentrum Karlsruhe in der Helmholtz-Gemeinschaft)

Addink, R; Glovers, H A J; Olie, K. Isomer Distributions of Polychlorinated Dibenzo-p-
dioxins / Dibenzofurans Formed During De Nvo Synthesis on Incinerator Fly Ash.
Environmental Science and Technology 32 (1998) 1888-1893

Ahlborg, U. G.; Brouwer, A.; Fingerhut, M. A.; Jacobson, J. L. Assessment: Impact of
PCDDs, PCDFs and Biphenyls on Human and Environmental Health, with Special Emphasis
on Application of the Toxic Equivalency Factor Concept. European Journal of
Pharmacology 228 (1992) 179-199

Amptek, 2004. X-Ray Fluorescence (XRF). Available from:
http://www.amptek.com/pdf/xrf.pdf [Accessed 07/04/2005]

Andac, M; Glasser, F P. Long-term Leaching Mechanisms of Portland Cement-stabilised
Municipal Solid Waste Fly Ash in Carbonated Water. Cement and Concrete Research 29
(1999) 179 - 186

Anderson, M; Skerratt, R G. Variability Study of Incinerated Sewage Sludge Ash in Relation
to Future Use in Ceramic Brick Manufacture. British Ceramic Transactions 102 (2003) 109-
113

Anderson, S. MSc thesis: The Use of Municipal Solid Waste and Sewage Sludge Ash as a
Binder Material. Chapter 2: Literature Review; pages 12-13. (Completed in 2002)

Appleby Group Ltd, 2005. GGBS: General Utilisation. (CD provided by Caledonian Slag
Cement & Appleby Group Ltd. Refer to http://www.ggbs.co.uk for further information)

Ashurst, J. The Technology and Use of Hydraulic Lime. Available from:
http://www.buildingconservation.com/articles/lime/hylime.html [Accessed 03/12/03]

Agency for Toxic Substances and Disease Registry (ATSDR), 1998. Toxicological Profile
for Chlorinated Dibenzo-para-dioxins (CDDs).
Available from: http://www.atsdr.cdc.gov/toxprofiles/tp104.html [Accessed 03/05/04]

Agency for Toxic Substances and Disease Registry (ATSDR), 1994. Toxicological Profile
for Chlorinated Dibenzofurans (CDFs). Available from:
http://www.atsdr.cdc.gov/toxprofiles/tp32.html [Accessed 03/05/04]

Agency for Toxic Substances and Disease Registry (ATSDR), 1993. ToxFAQs for Zinc.
Available from:
http://www.atsdr.cdc.gov/tfacts60.html [Accessed 04/09/2005]

Aubert, J E; Husson, B; Vaquier, A. Use of Municipal Solid Waste Incineration Fly Ash in
Concrete. Cement and Concrete Research 34 (2004) 957 963
244
Barna, R; Rethy, Z; Tiruta-Barna, L. Release Dynamic Process Identification for a Cement-
based Material in Various Leaching Conditions. Part I: Influence of Leaching Conditions on
the Release Amount. Journal of Environmental Management 74 (2005) 141 151

Bates, R. What Risk? Science, Politics and Health. Chapter 9: The Risk of Dioxin to Human
Health; pages 201-204. Copyright 1999 Butterworth-Heinemann Ltd

BBC, 2001. Newsnight: Why has Contaminated Ash Been Used to Build Homes? Available
from: http://news.bbc.co.uk/1/hi/events/newsnight/1426196.stm
[Accessed 09/06/03]

Brick Development Association (BDA), 1994. The BDA Guide to Successful Brickwork.
Section 6.10: Brick Manufacture; pages 194-200. Copyright 1994 BDA

Brindle, J H. PhD thesis: Physical and Chemical Impact of Co-fuelling on Fly Ash for Use in
Concrete. University of Dundee, 2005

Beall, L. Masonry and Concrete Real Answers Contractors Need. Chapter 2:
Understanding Concrete. Pages 13-15, 16. Chapter 4: Understanding Masonry. Pages 83,
87, 115. Copyright 2001 McGraw-Hill Books Ltd

Building Research Establishment (BRE) Ltd, 2003. Construction and Demolition Waste:
GBG 57 Part 2. Available from: http://www.info4education.com [Accessed 02/10/05]

1
British Cement Association (BCA), 2002. Letter: Energy Policy Review. Available from:
http://www.dti.gov.uk/energy/developop/british_cement_association.pdf [Accessed 08/08/03]

2
British Cement Association (BCA), 2002. Environmental Benefits of Using Alternative
Fuels in Cement Production. Available from:
http://www.wbcsd.org/web/projects/cement/tf2/CEMBUREAU.pdf [Accessed 03/03/2007]

British Geological Survey, 2004. General Planning Fact-sheet: Limestone. Available from:
http://www.mineralsuk.com/britmin/mpfmiscellaneous.pdf [Accessed 23/12/2005]

BS 1199: Building Sands from Natural Sources. Copyright 1976 British Standards
Institution, London, UK

BS 8500-2: 2002. Concrete Complementary British Standard to BS EN 206-1: Part 2:
Specification for Constituent Materials and Concrete. Copyright 2002 British Standards
Institution, London, UK

Buekens, A; Huang, H. Review: Comparative Evaluation of Techniques used for Controlling
the Formation and Emissions of Chlroinated Dioxins/Furans in Municipal Incineration.
Journal of Hazardous Materials 62 (1998) 1-33

Cai, Z; Bager, D H; Christensen, T H. Leaching from Solid Waste Incineration Ashes Used
in Cement-Treated Base Layers for Pavements. Waste Management 24 (2004) 603-612

Cains, P W; Dyke, P. Chlorinated Dibenzo-p-dioxins and Dibenzofurans in Waste
Combustion: Formation Mechanisms and Analysis of UK Plant Measurements. Pages 12, 19-
20. Copyright 1993 ETSU

1: Castle Cement, 2003. Agricultural Waste-derived Fuel at Ribblesdale. Available from:
http://www.castlecement.co.uk/ [Accessed 14/11/03]
(File: file://D:\DOCUMENT\ADMINI~1\LOCALS~1\Temp\triHKLBB.htm)
245
2: Castle Cement, 2003. Alternative Fuels. Available from:
http://www.castlecement.co.uk/env_alt.htm [Accessed 14/11/03]

CERAM, 2005. Waste/secondary Raw Material Usage Opportunities in the UK Brick
Industry. Available from:
http://www.ceram.com/downloads/waste-utilisation-uk-brick.pdf [Accessed 28/03/07]

Chandra, S. Waste Materials used in Concrete Manufacturing. Chapter 2: Production and
Use of By-Product Gypsum in the Construction Industry; pages 72, 83. Chapter 5: Blast
Furnace Slag the Ultimate Binder; page 237. Chapter 9: Use of Silica Fume in Concrete.
Copyright 1997 Noyes Publications

Cheriminisoff P N. Waste Incineration Handbook. Chapter 3: Incinerator Types; pages 54-
57. Copyright 1992 Butterworth-Heinemann

Christensen, T H; Cai, Z; Bager, D H; Mosbk, H. Leaching from Cement-treated Base
Layers containing Solid Waste Incineration Bottom and Fly Ashes. Pages 71-80. WASCON
2003: Progress on the Road to Sustainability proceedings of the 5
th
International
Conference on the Environmental and Technical Implications of Construction with
Alternative Materials (edited by De Urbina, G; Houmans, H)

CIRIA, 1999. The Reclaimed and Recycled Construction Materials Handbook. Chapter
25: Sewage Sludge; pp152 153

Collivignarelli, C; Sorlini, S. Reuse of Municipal Solid Wastes in Incineration Fly Ashes in
Concrete Mixes. Waste Management 22 (2002) 909-912

Coleman, N J; Lee, W E; Slipper, I J. Interactions of Aqueous Cu2+, Zn2+ and Pb2+ Ions
with Crushed Concrete Fines. Journal of Hazardous Materials B121 (2005) 203 - 213

Concrete Society, 1980. Technical Report No.18: Admixtures.

Concrete Society, 2001. Concrete and the Environment (leaflet)

Day, K W. Concrete Mix Design, Quality Control and Specification. Chapter 7: Aggregates
for Concrete; page 232. Chapter 8: Cementitious and Pozzolanic Materials; pages 240-243,
249. Copyright 1995 E & FN Spon

Danish Environmental Protection Agency (Danish EPA), 1997. Working Document: Dioxins
Sources, Levels and Exposures in Denmark.
Available from: http://chem.unep.ch/pops/DENDIOX.html [Accessed 17/08/03]

Dawy, C W. Review Article: Legislation with Respect to Dioxins in the Workplace.
Environment International 30 (2004) 219-233

DEFRA, 2000. Dioxins and Dioxin-like PCBs in the UK Environment Consultation
Document. Available from: http://www.scotland.gov.uk/library5/environment/dpcb.pdf
[Accessed 11/11/03]

Department of Statistics, 2002. Product Sales and Trade. PRA 26400: Bricks, Tiles &
Construction Products in Baked Clay. Available from:
http://www.statistics.gov.uk/downloads/theme_commerce/PRA-20030/PRA26400_20030.pdf
[Accessed 11/11/2003]

246
Department of Statistics, 2004. Government Office Regions (GORs). Available from:
http://www.statistics.gov.uk/geography/gor.asp [Accessed 20/01/04]

Dhir, R K; Paine, K; Caliskan, S. Research Information Digest 6: Incinerator Ashes.
Concrete 39 (No.11) (2005) pp90-92 (The Concrete Society)

Dhir, R K; Dyer, T; Paine, K. Appropriate Use of Sustainable Construction Materials.
Concrete, October 2006, pp20 24

Dionex, 1999. Extraction of Polychlorinated Dibenzo-p-dioxins and Polychlorinated
Dibenzofurans from Environmental Samples using Accelerated Solvent Solvent Extraction.
(Application Note 323) Available from:
http://www1.dionex.com/en-
us/webdocs/application/industry/environmental/extraction/an323.pdf [Accessed 26/05/04]

Dodson, V. Concrete Admixtures Structural Engineering Series. Chapter 2: Admixtures
General Concepts; page 23. Chapter 4: Accelerators; page 73. Chapter 5: Retarders; pages
103-107. Chapter 6: Air-entrainers; pages 130-131. Copyright 1990 Van Norstrand
Reinhold

Doran, D K. Construction Materials Reference Book. Chapter 15: Admixtures and
Polymers; page 15-3, 15-6, 15-14, 15-21. Copyright 1994 Butterworth-Heinemann Ltd

Drinking Water Inspectorate, 2005. Sample Preservation and Preparation for Metals
Analysis of Drinking Water. Available from:
http://www.dwi.gov.uk/regs/infolett/2005/1205sample2guidance.pdf [Accessed 06/02/2006]

DTI, 2003. UK Capability: Instrumentation and Control for Conventional Coal-fired Power
Plant. Available from: http://www.dti.gov.uk/files/file18243.pdf [Accessed 15/06/2003]

Dunster, A. Blast Furnace Slag and Steel Slag: Their Use as Aggregates (Report IP 18/01);
pp1-2, 5. Copyright BRE 2001. Available from: http://www.info4education.com

Dyke, P H; Foan, C; Wenborn, M; Coleman, P J. A Review of Dioxin Releases to Land and
Water in the UK. The Science of the Total Environment 207 (2003) 469-480

Dyke, P H; Foan, C; Wenborn, M; Coleman, P J. A Review of Dioxin Relases to Land and
Water in the UK. The Science of the Total Environment 207 (1997) 119-131

ENDS Report, 2002 (Issue 328, May 2002). Agency on the Rack in Row over Health Impacts
of Tyre Burning.

Entec, 2004. Appendix H: Notes on Scenarios of Environmental Impacts Associated with
Construction and Occupation of Homes. Available from:
http://statistics.defra.gov.uk/esg/reports/housing/appendh.pdf [Accessed 30/11/04]

Eduljee, G. Waste Disposal in Cement Kilns: a Review of Dioxin Formation and Control.
Environmental and Waste Management 2 (1) 1999 45 - 54

Eduljee, G H; Dyke, P; Cains, P W. The Effect of Changing Waste Management Practise on
PCDD/PCDF Releases from Household Waste Recycling and Disposal Practises.
Chemosphere 34 (1997) 1615-1622

247
Eljarrat, E; Barcelo, D. Priority Lists for Persistent Organic Pollutants and Emerging
Contaminants Based on their Relative Toxic Potency in Environmental Samples. TrAC
Trends in Analytical Chemistry 22 (2003) 655 665

Environment Agency, 2006. Capacity of Incineration Facilities Operating under Permits
issued by the Environment Agency: 2005. Available from:
http://www.environment-agency.gov.uk/commondata/103601/ew_incin_cap_1769513.xls
[Accessed 14/04/2008]

Environment Agency, 2005. EA NEN 7375: 2004. Leaching Characteristics of Moulded or
Monolithic Building and Waste Materials Determination of Leaching of Inorganic
Components with the Diffusion Test, The Tank Test. Available from:
http://www.environment-
agency.gov.uk/commondata/acrobat/ea_nen_7375__2004_1026071.pdf
[Accessed 20 November 2006]

Environment Agency, 2002. Solid Residues from Municiapl Waste Incinerators in England
and Wales a Report on an Investigation by the Environment Agency. Available from:
http://www.environment-agency.gov.uk/dcommondata/105385/ash_pdf4.pdf
[Accessed 15/06/04]
Environment Agency, 1998. Tyres in the Environment. Section 4.4: Material Recovery and
Energy Recovery. Available from [CHECK]:
http://www.environment-agency.gov.uk/commondata/105385/ea_tyres_report.pdf

Environment Australia, 2003. Incineration and Dioxins: Review of Formation Processes.
Available from:http://www.ea.gov.au/industry/chemicals/dioxins/pubs/review.pdf [Accessed
15/10/03]

European Cement Association, 1995. Use of Non-ferrous Slag in Cement and the Leaching of
Concrete in Drinking Water. BSI Document 95/106424

European Commission, 2000. Management of Construction and Demolition Waste: Working
Document No.1; page 3. Available from:
http://ec.europa.eu/enterprise/environment/index_home/waste_management/constr_dem_wast
e_000404.pdf [Accessed 23/03/07]

European Commission, 2001. Integrated Pollution Prevention and Control: Reference
Document on Best Available Techniques in the Cement and Lime Manufacturing Industries.
Chapter 1: Cement; pp4-6. Chapter 2: Lime; pp62-73.

European Commission, 2001. Integrated Pollution Prevention and Control (IPPC), Best
Available Techniques Reference Document for Production of Iron and Steel. Available from:
http://www.sepa.org.uk/ppc/brefs/PDFs/iron_and_steel.pdf [Accessed 28/08/2003]

Everett, A. Mitchells Materials (5
th
Ed.). Chapter 6: Bricks and Blocks; pages 96-97.
Chapter 7: Limes and Cements. Pages 115-116. Copyright 1994 Longman Scientific &
Technical

Fell, H J; Tuczek, M. Removal of Dioxins and Furans from Flue Gases by Non-flammable
Adsorbants in a Fixed Bed. Chemosphere 37 (1998) 2327 - 2334

248
Flor, M V; Barra, M; Pardo, P; Vazquez, E; Josa, A. Laboratory and Field Study on Leaching
and Properties of Gravel-Cement-Bound and Roller-Compacted Concrete using MSWI
Bottom Ash as Aggregates. Pages 155-164. WASCON 2003: Progress on the Road to
Sustainability proceedings of the 5
th
International Conference on the Environmental and
Technical Implications of Construction with Alternative Materials (edited by De Urbina, G;
Houmans, H)

Focant, J F; Eppe, G; Pauw, E. Optimisation and Use of Tandem-in-time Mass Spectrometry
in Comparison with Immunoassay and HRGC-HRMS for PCDD/F Screening. Chemosphere
43 (2001) 417-424

Friends of the Earth (FOE). Briefing Sheets: Gone to Blazes, Burning Hazardous Waste in
Cement Kilns, 1997. Available from:
http://www.foe.co.uk/pubsinfo/briefings/html/19971215145335.html [Accessed 04/09/2003]
Gan, S; Goh, R; Clarkson, P J; Parracho, A; Nasserzadeh, V; Swithenbank, J. Formation and
Elimination of PCDDs and PCDFs from Municipal Solid Waste Incinerators. Combustion
Science and Technology 175 (2003) 103-124
Gerhardt, 2001. Soxtherm Applications Extraction of Dioxines from Soil. C. Gerhardt
GmbH & Co. KG
Geysen, D; Van Gerven, T; Vandecasteele, C. Immobilisation of Heavy Metals in Fly Ashes
and Flue Gas Cleaning Residues from MSW Incineration a Comparison of the
Immobilisation with Cement and with Silicate-containing Materials. Pages 873 876.
WASCON 2003: Progress on the Road to Sustainability proceedings of the 5
th
International
Conference on the Environmental and Technical Implications of Construction with
Alternative Materials (edited by De Urbina, G; Houmans, H)

Gossman, D; Black, M; Ward, M. The Fate of Trace Metals in the Wet Process Cement Kiln.
(Produced in 1990) Available from:
http://gcisolutions.com/MTLFATE.htm [Accessed 19/04/2005]

Gregory, R J; Hughes, T G; Kwan, A S K. Brick recycling and re-use. Proceedings of the
Institution of Civil Engineers (2004) 155 - 161

The Guardian (8
th
March 2001). House Calls. Available from:
http://society.guardian.co.uk/housing/story/0.7890,448604,00.html [Accessed 09/11/03]

Gutierrez, N; Bin-Shafique, M D S; Walton, J; Tarquin, A; Smith, R; Sheeley, P; Rodriguez,
M; Andrade, R. Effects of Carbonation on the Long-term Leaching Performance of
Cementitious Wasteforms. Proceedings of the HSRC/WERC Joint Conference on the
Environment, May 1996. Published by the Great Plains/Rocky Mountain Hazardous
Substance Research Centre.
Available from: http://hsrc.ksu.edu/96Proceed/home.html [Accessed 10/08/2006]

Halliday, J E. PhD thesis: The Potential for Re-using Wastes from Thermal Sources as a
Constituent in Blended Cements. Chapter 2: Literature Review; pages 13-20. University of
Dundee, 2002

Harrex, R M. Recycled Building Products. Recycling and Re-use of Waste Materials
(Proceedings of the International Symposium held at the University of Dundee, Scotland, UK
on 9-11 September 2003) Pages 527-542

Harrison, R M. Pollution: Causes, Effects and Control (4
th
Ed.). Chapter 4: Soil Pollution
and Land Contamination; pp360 362. Copyright 1999 Royal Society of Chemistry
249
Habaux, A; Vos, G. Decision and Detection Limits for Linear Calibration Curves. Analytical
Chemistry 42 (1970) 849 - 855

Helen, C; Lemasle, M; Laplanche, A; Genin, E. Determination of PCDDs and PCDFs by Gas
Chromatography / Tandem Mass Spectrometry and GC / Triple Mass Spectrometry in a
Quadruple Ion Trap. Journal of Mass Spectrometry 36 (2001) 546-554

Hendry, A W. Review Article: Masonry Walls - Materials and Construction. Construction
and Building Materials 15 (2001) 323-330

Hewitt, P C. LEA Chemistry of Cement and Concrete (4
th
Ed.). Chapter 2: Portland Cement.
Page 62. Chapter 11: Cements Made from (GGBS) Blast Furnace Slag; pages 633-634.
Chapter 16: Concrete Aggregates; pages 987-988. Copyright 1998 Arnold Publishers

Hillier, S R; Sangha, C M; Plunkett, B A; Walden, P J. Long-term Leaching of Toxic Trace
Metals from Portland Cement Concrete. Cement and Concrete Research 29 (1999) 515-521

Hohberg, I; de Groot, G J; de Veen, A M H; Wassing, W. Development of a Leaching
Protocol for Concrete. Waste Management 20 (2000) 177-184

Hsu, M S; Ling, Y C. Experimental Evaluation of PCDD/Fs in Cement Samples from Kilns
Using Waste Tyres. Organohalogen Compounds 46 (2000) 366-368

Hunsinger, H; Vehlow, J I. Formation and Destruction of PCDD/F inside a Grate Furnace.
Chemosphere 46 (2002) 1263-1272

Jooss, M. Leaching of Concrete under Thermal Influence. Otto-Graf Journal 12 (2001) 51 -
68

Joshi, R C; Lohtia, R P. Fly Ash in Concrete: Production, Properties and Use. Chapter 1:
Introduction; pages 1-11. Copyright 1997 Overseas Publishers Association

Jyothi, N V V; Mouli, P C; Reddy, S R J. Determination of Zinc, Copper, Lead and
Cadmium in some Medicinally Important Leaves by Differential Pulse Anodic Stripping
Analysis. Journal of Trace Medicinal Biology 17 (2003) 79 - 83

Kamali, S; Gerard, B; Moranville, M. Modelling the Leaching Kinetics of Cement-based
Materials Influence of Materials and Environment. Cement & Concrete Composites 25
(2003) 451-458

Karius, V; Hamer, K; Lager, T. Reaction Fronts ain Brick-sand Layers: Column Experiments
and Modelling. Environmental Science and Technology 36 (2002) 2875 - 2883

Karius, V; Hamer, K. pH and Grain-size Variation in Leaching Tests with Bricks Made of
Harbour Sediments Compared to Commercial Bricks. The Science of the Total Environment
278 (2001) 73 85

Kemp, W. Organic Spectroscopy (3
rd
Ed.). Chapter 5: Mass Spectrometry; pages 286-294,
323, 328. 1991 McMillan Press Ltd.
Kjeller, L; Rappe, C. Time Trends in Levels, Patterns and Profiles for Polychlorinated
Dibenzo-p-Dioxins, Dibenzofurans and Biphenyls in a Sediment Core from the Baltic Proper.
Environmental Science and Technology 29 (1995) 346-365

250
Krauss, T; Braga, M C B; Marins, E R; Carvalhaes, G; Brooks, P. PCDD/F Concentrations in
the Surroundings of a Cement Kiln/CoProcessing Waste Plant in Rio de Janeiro, Brazil.
Organohalogen Compounds 46 (2000) 366-368

La-Farge (Blue Circle) Cement, 2003. Alternative Cement-making Fuels Recycled Liquid
Fuel (RLF). Available from:
http://www.cement.bleucircle.co.uk/alt-rlf.htm [Accessed 15/11/03]

Landesumweltamt Nordrhein-Westfalen (LUA-NRW). Materialien No.43: Identification of
Relevant Industrial Sources of Dioxins and Furans in Europe Final Report. Section
030312: Lime; page 119. Published 1997 by LUA-NRW

Lewin, K. Leaching Tests for Waste Compliance and Characterisation: Recent Practical
Experiences. The Science of the Total Environment 178 (1996) 85 94

Livesay, P. A Cement Makers View of Cements and their Performance. Euro-cements:
Impact of ENV 197 on Concrete Construction. (Proceedings of the National Seminar held at
the University of Dundee, 15
th
September 1994. Copyright 1994 E & FN Spon Ltd) pages
217-228.

Lorber, M; Pinsky, P; Gehring, P; Braverman, C; Winters, D; Sovocol, W. Relationships
Between Dioxins in Soil, Air, and Emissions from a Municipal Solid Waste Incinerator
Emitting Large Amounts of Dioxins. Chemosphere 37 (1998) 2173-2197

Malhotra, V M; Mehta, P K. High Performance High Volume Fly Ash Concrete: Materials,
Mixture Proportioning, Properties, Construction Practise and Case Studies. Chapter 2: What
is Fly Ash? Pages 19-21. Copyright 2002 Supplementary Cementing Materials for SD Inc.,
Ottawa Canada

Marion, A M; De Laneve, M; De Grauw, A. Study of the Leaching Behaviour of Paving
Concretes: Quantification of Heavy Metal Content in Leachates Issued from Tank Test using
Demineralised Water. Cement and Concrete Research 35 (2004) 951 957

Markiewicz-Patkowska, J; Hursthouse, A; Przybyla-Kij, H. The Interaction of Heavy Metals
with Urban Soils: Sorption Behaviour of Cd, Cu, Cr, Pb and Zn with a Typical Mixed
Brownfield Deposit. Environment International 31 (2005) 513 - 521

Marshall, D; Worthing, D. The Construction of Houses (2
nd
Ed.). Chapter 2: External Load-
bearing Walls; pages 24-26. Chapter 4: Plastering; pages 136-138, 165. Copyright 1995
Lavenham Press Ltd.

McKay, G. Dioxin Characterisation, Formation and Minimisation during Municipal Solid
Waste (MSW) Incineration: Review. Chemical Engineering Journal 86 (2002) 343-368

Metrohm, 2006. Trace analysis and metal speciation with voltammetry. Available from:
http://www.metrohm.com/products/06/va_tech.html [Accessed 07/03/2007]

Mokrzycki, E; Uliasz-Bochenczyk, A; Sarna, M. Use of Alternative Fuels in the Polish
Cement Industry. Applied Energy 74 (2003) 101 111

Morrison, C; Hooper, R; Lardner, K. The Use of Ferro-Silicate Slag from ISF Zinc
Production as a Sand Replacement in Concrete. Cement and Concrete Research 33 (2003)
2085-2089

251
Moudilou, E; Beletto, M; Defosse, C; Seclerate, I; Baillif, P; Touray, J C. A Dynamic
Leaching Method for the Assessment of Trace Metals Release from Hydraulic Binders.
Waste Management (2002) 153 157

Nagataki, S; Yu, Q; Hisidam M. Effect of Leaching Conditions and Curing Time on the
Leaching of Heavy Metals in Fly Ash Cement Mortars. Advances in Concrete Research 14
(2002) 71-83

National Centre for Diversity, 2004. [Home page] Available from:
http://www.nationalcentrefordiversity.com/design/images/uk_regions_map.gif
[Accessed 20/01/04]

Nawy, 1995. Concrete Construction Engineering Handbook. Chapter 1: Concrete
Constituent Materials. Pages (1-6); (1-12); (1-16). Chapter 2: Mineral Admixtures; page
(2-3). Copyright 1997 CRC Press LLC

Neville, A M. Properties of Concrete (4
th
Ed.). Chapter 1: Portland Cement. Pages 3, 5-7.
Chapter 2: Cementitious Materials of Different Types. Pages 69-82, 84-85, 89. Chapter 3:
Properties of Aggregate. Pages 111, 136-140. Copyright 1995 A M Neville

Nishida, K; Nagayoshi, Y; Ota, H; Nagasawa, H. Melting and Stone Production using MSW
Incinerated Ash. Waste Management 21 (2001) 443-449

Office of Public Sector Information, 2005. Statutory Instrument 2005 No. 1640: the Landfill
(England and Wales) (Amendment) Regulations 2005. Available from:
http://www.opsi.gov.uk/SI/si2005/20051640.htm [Accessed 07/02/2007]

Paillere, A M. RILEM Report No. 10: Application of Admixtures in Concrete. Volume 1:
pages 18, 34-35. Chapter 4: Retarders; page 49. Chapter 8: page 95. (Published 1979
DETAILS)
Petrovic, M; Eljarrat, E; Lopez de Alda, M.J.; Barcelo, D. Review: recent advances in the
mass spectrometric analysis related to endocrine disrupting compounds in aquatic
environmental samples. Journal of Chromatography A 974 (2002) pages 23-51
Plomley, J B; Lausevic, M; March, R E. Determination of Dioxins/Furans and PCBs by
Quadruple Ion-Trap Gas Chromatography - Mass Spectrometry. Mass Spectrometry Reviews
19 (2000) 305-365

Porteous, A. Dictionary of Environmental Science and Technology (2
nd
Ed.). Page 59:
Cadmium. Pages 114 115: Copper. Pages 324 325: Lead. Copyright 1996 John Wiley
& Sons Ltd

Powell, M J V. House-builders Reference Manual (Vol.1). Chapter 27: Concrete
Technology. Pages (27-4); (27-5). Chapter 32: Brickwork and Blockwork. Pages (32-2),
(32-9), (32-14), (32-16). Copyright (FIND!), 1979

Radojevic, M; Bashkin, V N. Practical Environmental Analysis. Chapter 5: Soil, Sediment,
Sludge and Dust Analysis; p357. Copyright 1998 the Royal Society of Chemistry

Reid, P. Bricks and the Environment. International Ceramics Issue 1 (2000). Available from
http://www.international-ceramics.com/pages/2000/12000/reid.pdf [Accessed 10/11/2003]

Rose, C L; Rose, N L; Harlock, S; Fernades, A. A Historical Record of PCDD and PCDF
Deposition to a Remote Lake in North-west Scotland, UK. The Science of the Total
Environment 198 (1997) 161-173
252
Rugby Cement (RMC), 2003. Waste Minimisation UK. Available from:
http://www.rmc-group.con/rmc/environment/issues/waste/uk [Accessed 30/11/03]

Sakanakura, H; Mizutani, S; Osako, M; Kida, A; Tasaki, T; Sakai, S. Evaulation of Grains
and Mortars of Waste Molten Slag by Diffusion Test. Pages 281-290. WASCON 2003:
Progress on the Road to Sustainability proceedings of the 5
th
International Conference on
the Environmental and Technical Implications of Construction with Alternative Materials
(edited by De Urbina, G; Houmans, H)

Samarin, A. Wastes in Concrete: Exploiting Wastes in Concrete; pages 3-6. Exploiting
Wastes in Concrete proceedings of the International Seminar held at the University of
Dundee, 1999 (editors: Dhir, R K; Jappy, T G)

Sear, L K. The Properties and Use of Coal Fly Ash. Chapter 1: The Production and
Properties of Fly Ash.; pages 6-9, 19-20, 23, 25. Chapter 7: Manufactured Lightweight
Aggregates from Fly Ash; pages 196-206. Copyright 2001 Thomas Telford Ltd

Scottish Environment Protection Agency (SEPA), 2008. Waste Data Digest 4: Waste
Disposal. Available from: http://www.sepa.org.uk/publications/wds/html/wdd04/4.html
[Accessed 14/04/2008]

Serclerat, I; Moszkowicz, P; Pollet, B. Retention Mechanisms in Mortars of the Trace Metals
Contained in Portland Cement Clinkers. Waste Management 20 (2000) 259-264

Sewert, A; Harrad, S J; McLachlan, M S; McGrath, S P; Jones, K C. PCDD/Fs and non-o-
PCBs in Digested Sewage Sludges. Chemosphere 30 (1995) 51-67

Sidhu, S; Kasti, N; Edwards, P; Dellinger, B. Hazardous Air Pollutants Formation from
Reactions of Raw Meal Organics in Cement Kilns. Chemosphere 42 (2001) 499-506

Silica Fume Asociation, 2005. General Information: What is Silica Fume? Available from:
http://www.silicafume.org/general-silicafume.html [Accessed 20/12/05]

Simmons, H L; Olin, H B. Construction; Principles, Materials and Methods (7
th
Ed.).
Chapter 3: Concrete; pages 127-128, 229-230. (Published 2001)

Sincich, T; Levine, D M; Stephan, D. Practical Statistics by Example Using Microsoft Excel.
Chapter 10: Regression Analysis; pp560 566. Copyright 1999 Pentice-Hall, Inc

Smith, W F. Foundations of Material Science and Engineering (2
nd
Ed.). Chapter 11:
Composite Materials; page 614. Copyright 1993 McGraw-Hill Inc

Socioeconomic Data & Applications Center, 2004. [Home page] Available from:
http://sedac.ciesin.org/gpw/country.jsp?iso=GBR [Accessed 20/01/04]

Stanmore, B R. Review: The Formation of Dioxins in Combustion Systems.
(Published in the Combustion & Flame journal for early 2004 find reference)

Tanna, B; Schipholt, B. Waste-derived Fuel in Cement Kilns. (Produced in 1998.) Available
from: http://www.eratech.com/papers/wdf.htm [Accessed 20/04/2005]

Teychenne, D C; Franklin, R E; Nicholls, J C; Hobbs, D W; Marsh, B K. Design of Normal
Concrete Mixes (2
nd
Ed.). Pages13-14. Copyright Building Research Establishment (BRE)
Ltd, 1988

253
Thomas, K. Masonry Walls: Specification and Design. Chapter 1: Bricks and Blocks. Pages
1, 7-8. Chapter 2: Mortars. Pages 27-28, 30, 35, 41-43. Chapter 8: Wall Finishes; pages
160-161. Copyright 1996 Butterworth & Heinemann Ltd

UKQAA, 2003. Assessment of the Leaching Risk to the Environment from the Use of
Pulverised Fuel Ash (PFA). Available from:
http://www.ukqaa.org.uk/Environment/Environmental%20Risk%20Assessment%20January%
20January%202003.pdf [Accessed 28/07/03] CHECK

UKQAA, 2002. The Production and Applications of Pulverised Fuel Ash (PFA).
Available from:
http://www.ukqaa.org.uk/Environment/Production%20and%Applications%20January%20200
3.pdf [Accessed 28/07/03]

United States Environment Protection Agency (USEPA), 2001. Dioxin Reassessment: an
SAB Review of the Office of Research and Developments Assessment of Dioxin. Available
from: http://www.pea.gov/sab [Accessed 20/05/04]

United States Environment Protection Agency (USEPA), 1994. Method 1613: Tetra- through
Octa-chlorinated Dioxins and Furans by Isotope Dilution HRGC/HRMS. Pages 2-3, 12-13,
36

United States Environment Protection Agency (USEPA), 1995. Regulatory Determination on
Cement Kiln Dust. Part IV: Final Rule. (40 CFR Part 261) Available from:
http://www.epa.gov/fedgstr/EPA-WASTE/1995/February/Day-07/pr-134.html
[Accessed 19/04/2005]

Valls, S; Vazquez, E. Accelerated Carbonation of Sewage-Cement-Sand Mortars and its
Environmental Impact. Cement and Concrete Research 31 (2001) 1271-1276

Van der Sloot; vandersloot@ecn.nl, 2006. RE: Tank leaching test: sample size message to
M Sutherland (m.a.z.sutherland@dundee.ac.uk) [Sent Saturday 22 October]

Van der Sloot, H A; Dijstra, J J. Development of Horizontally Standardised Leaching Tests
for Construction Materials: a Material-based or Release-based Approach? ECN-C-04-060
(published 2004).

Van der Sloot, H A; Kosson, D S. A Unified Approach for the Judgement of Environmental
Properties of Construction Materials (Cement-based, Asphaltic, Unbound Aggregates, Soil)
in Different Stages of their Lifecycle. (Published 2003). Available from:
http://www.ecn.nl.docs/library/report/2003/rxc03032.pdf [08/06/05]

Van der Sloot, H A; Hoede, D; Cresswell, D J F; Barton, J R. Leaching Behaviour of
Synthetic Aggregates. Waste Management 21 (2001) 221-228

Vite-Torres, J; Diaz-Calva, A; Leon, C.C.D. Appplication of Coupled Thermostatted
Columns in Civil Engineering and for Leaching Heavy Metals of Wastes from Foundry Sands
and Mining Industry. International Journal of Environment and Pollution 19 (2003) 46-67

Watson, A. Comments on the Report of the Analysis of PCDD/PCDF and Heavy Metals in
Soil and Egg Samples Related to the Byker Incinerator. Available from:
http://www.tcpublications.freeserve.co.uk/Reports/Byker%20Rep%20Final%20Watson.pdf
[Accessed 10/09/2003]

254
Willard, H H; Merritt, L L; Dean, J A; Settle, F A. Instrumental Methods of Analysis (7
th
Ed).
Chapter 13: X-ray Methods; pp371 373. Copyright 1988 Wadsworth, Inc (USA)

Wunderli, S; Zennegg, M; Dolezal, I S; Gujer, E; Moser, U; Wolfensberger, M; Hasler, P;
Noger, D; Studer, C; Karlaganis, G. Determination of PCDDs and PCDFs in Solid Residues
from Wood Combustion by HRGC/HRMS. Chemosphere 40 (2000) 641-649

255
APPENDIX 1: dioxin and furan concentrations in materials cited from the literature

(Concentrations in ng I-TEQ kg)

(Most data is directly extrapolated from an MS Excel spreadsheet; spaces between numbers
do not indicate decimal points or any correlation)

256
MATERIALS

Raw Materials

CEMENT

Reference Recorded Levels

Environment Agency, 2002 0.5, 1.0
Hsu & Ling, 2000 0.094, 0.8
Krauss et al, 1999 0.35

AGGREGATE

Reference Recorded Levels

Hsu & Ling, 2000 0.37

1
Secondary Materials

PFA

Reference Levels

Environment Agency, 2002 6.7 2.8 2 65
UKQAA, 2002 25 210 270 0.049 2.4
LUA NRW, 1997 0.321
Danish EPA, 1997 60000 80000
Dyke et al, 1997 0.23 8.7

FBA

Reference Levels

Dyke et al, 1997 0.02 13.5

IBA (continued over page)

Reference Levels

Dawy, 2004 5 26 0.64 23 150
Abad et al, 2003 20 30
Dyke et al, 2003 6 2.5
Environment Australia, 2003 10 30 140
Gan et al, 2003 60 120
McKay, 2002 20000 20
Hunsinger & Vehlow, 2002 45
Abad et al, 2000 60 130
Danish EPA, 1997 5 50 0.77
Dyke et al, 1997 12 71
Eduljee et al, 1997 20
Swithenbank et al, 1996 0.8 2

GGBS

Environment Agency 1

Waste Materials

SOOT

Reference Levels

Dyke et al, 1997 1.6 52.6 53 10065 584

CEMENT KILN DUST

2
Reference Levels

Hsu & Ling, 2000 0.011 0.0026
Eduljee, 1999 0.52 34.61 0.77 6.9 1.46
Krauss et al, 1999 7.7 8.3
Dyke et al, 1997 0.001 30

OTHER INDUSTRIAL ASH

Reference Type Levels

McKay, 2002 Waste wood incineration 549 6587

Wunderli et al, 2000 Waste wood incineration 2000 2500

Freshwood incineration 7.1 6.3

Danish EPA, 1997 Steel recycling 1200 3200
Steel arc 53

Dyke et al, 1997 Wood burning
IFA 584 1090 722
7620
IBA 891 1070 22.3
Steel arc FA 900
Al foundry dust 3 4 480
3000
Cu foundry dust 12000

MUNICIPAL SOLID WASTE (continued over page)


European Commission, 2003 MSW average 3.1 13 10 250
Inert 8.8 11
Fine dust 5.6 70
McKay, 2002 MSW average 50
Abad et al, 2000 Paper 6.26
Plastic 21.77
Textile 157.55
Wood 2.71
Organic 2.71
RDF average 15.82
Hsu & Ling, 2000 Waste tyres 8.91
Danish EPA, 1997 Paper 1 450 120
Putrescibles 40
3
Plastics 340
Dyke et al, 1997 MSW 11.5
Eduljee et al, 1997 Paper 4.5
Plastics 8.9
Textiles 7.9
Glass + inert 3.4
Putrescibles 9.5
Fine dust 14.7
MSW average 6.3

MUNICIPAL SOLID WASTE ASH

Fly Ash


Abad et al, 2003 ESP 78700 16300
Fabric filter 790
Mixed 8700 1070 1310
1630 3120
Dyke et al, 2003 ESP 20000

ESP + FF mixed 840

Environment Australia, 2003 ESP 1000 4000 28000
2000
Fabric filter 1875 31250 6000

Gan et al, 2003 Superheater ash 70 100 110 160

Heat exchanger ash 80

Economizer ash 120 480

FF ash 1620 1550 2810
3000
Evaporator ash 110

McKay, 2002 Fly ash 130 21000 5000
20000 300 13000
Nishida et al, 2001 Fly ash 11000

Wunderli et al, 2000 ESP dust 1600 810

Abad et al, 2000 Fly ash 650 370

Dionex, 1999 Fly ash (Soxhlet) 7600

Fly ash (fast extract) 8900

4
Lorber et al, 1998 Fly ash 28800

Danish EPA, 1997 ESP dust 1000 28000

Fly ash 7000 250000

Copenhagen incin 240

Dyke et al, 1997 ESP ash pre-1997 6600 31000

FGD spray drier ash 810 1800

Eduljee et al, 1997 Average 300

LUA NRW, 1997 Fly ash 26000 5000 31000 530
2400

Boiler Ash

Environment Australia, 2003 100 857 200

McKay, 2002 50 1000 5000

Danish EPA, 1997 100 800

Eduljee et al, 1997 50

Mixed IFA and IBA

McKay, 2002 106 466 258

SEWAGE SLUDGE

Reference Levels

European Commission, 2003 23.3 42.5 42.3 52.8

Danish EPA, 1997 60 18 23 33 23 53

Dyke et al, 1997 20 80

LUA NRW, 1997 50 60

Sewart et al, 1995 23 79 41 133 79 41 133
142 37 776 341 64 1560 28 14

5
SEWAGE SLUDGE ASH

Halliday, 2002 0.3 1.2 3 3.1

Danish EPA, 1997 6.3

PRODUCTS

CONCRETE

Reference Levels

(Normal)

Environment Agency, 2002 3 2

(With IBA)

Environment Agency, 2002 4
Friends of the Earth, 1997 4 23

(With IFA)

Friends of the Earth, 1997 117 390

(With mixed IFA and IBA)

Environment Agency, 2002 117 390

(Aircrete)

Environment Agency, 2002 1.5 12 10
6

CLAY BRICKS

Environment Agency, 2002 1.4 1.7 0.9

Dionex, 1999 (Former chimney brick) 540

ENVIRONMENTAL MATERIALS

SOIL


European Commission, 2003 Rural soil 0.78 17 5.2
2.5 14 5.8
Urban soil 4.9 87 28 3 20 8
Near
incinerator 1 35 209 2.4 160 19 13.3 1535 230 3.3
680 29 5.8 90
Environment Agency, 2002 Rural German soils 10

Urban German soils 10 30
7
Ind.
German soils 30 300
UKQAA, 2002 Upper normal limit 290

Bates, 1999 Agricultural soil 2 8 7 14

Natural soil 20 30
Soil beside motorway 2800

Seveso soil 7 25 79 360
1900 45000
Times Beach soil 50 100 404000

Outside Dynamit Nobel: 3800000

Krauss et al, 1999 Near cement kiln 0.03 6.91

Lorber et al, 1998 Near incinerator 458

Watson, 1998 Near incinerator 9500

Danish EPA, 1997 Rural soils 3

Urban Soils 20 30 60 150

Near industrial plant 2400

SEDIMENT


Rose et al, 1997 Lacustrine 3.4

Fluvial 130 275

REGULATION (soil)

European Commission, 2003 Residential land 10

Other land 250

Agricultural 500 1000 10
40
8
Public soil 100 10

Industrial 10000 250

Hsu & Ling, 2000 Centre of Disease Control
Recommended Limit: 1

Watson, 1998 Soil Target Value 5

Garden Soil 40

Other natural soil 100

Public remed. Soil
1000
Residential (remediation) Soil
1000

Dawy, 2004 Construction Materials 50

9
APPENDIX 2: Referenced Trace Metal Content in Construction Materials

10
Reference Material Cd Cu Pb Zn
Raw Materials and Fuel
Raw Meal 0.3 21 20 53
Aggregate 0.2 10 10 11
Basalt 1.0 44 10 102
Achternbosch et al, 2003
BF Slag 1.0 150 20 250
Vite-Torres et al, 2003 Foundry sand - - 8.65 -
Gypsum 0.3 6.5 2.9 9.8 Chandra, 1997
FGD Gypsum 0.5, 0.4 7, 9 5.8, 3.3 19.4, 12.5
Coal N.D. - 2-225 10-130 Gossman, 1990
Hazardous waste 6.5-71 - 350-1800 500-1300
Clinker
Achternbosch et al, 2003 Clinker 0.8 40 41 159
Clinker
1
3 11 <10 57
Clinker
2
4 21 <10 187
Mokrzycki et al, 2001
Clinker
3
3 55 <10 62
Gossman et al, 1990 Clinker N.D. - 5.3, 5, 43 20.4, 9.7,
34.5, 18.1
Cement Brands
CEM I cement 0.51,1.5 22, 60 12, 145 91, 514 Marion et al, 2004
CEM III cement 0.53,
0.89
15, 30 15, 56 75, 199
Seclerat et al, 2004 Portland cement - - 32, 6, 2,
13,24,14
200, 192,
224, 228,
246, 248
ERA-Tech, 2004 Acceptable levels
in cement
1000 - 5000 -
Portland cement 0.8 39 40 153
Blast F cement 0.7 12 13 59
Slag cement 0.7 29 30 115
Pozzolanic cmnt 0.7 28 43 144
Shale cement 1.0 46 39 163
Limestone cmnt 0.6 32 34 115
German cement* 0.4 25 27 140
Halliday, 2002 Portland cement 0.34 - 12 -
Hillier et al, 1999 Portland cement ND - - -
1975 P Cement 1.1 125 59 430 Chandra, 1997
1992 P Cement 1.6 138 40 550
Cement Kiln Dust
Halliday, 2002 CKD 0.66 - 12 -
USEPA, 1995 CKD Av 9.7 - Av 287 -
1: Clinker produced by kiln burning coal
2: Clinker produced by kiln co-incinerating mostly municipal solid waste
3: Clinker produced by kiln co-incinerating industrial liquid and solid waste
* Average German VDZ Cement concentrations

11
Levels in Clay Brick

Karius & Hamer, 2001 Commercial
bricks
0.7,
0.01,
0.1, 0.3,
0.7, 0.2,
0.01,
0.01,
0.01
- 21, 24,
25,
6400,
28, 34,
20, 22,
19
73, 75, 93,
94, 100,
95, 370,
73, 80

Levels in Concrete

CEM I concrete 0.14,0.2 18, 30 11, 27 56, 94 Marion et al, 2004
CEM III concrete 0.08,
0.17
9.3, 12 8.6, 12 30, 38
Concrete
1
0.3 15 15 28
Concrete
2
0.3 19 19 41
Concrete
3
0.9 81 19 153
Concrete
4
0.9 84 22 165
Concrete
5
0.3 28 22 311
Concrete
6
0.65 118 142 334
Hohberg et al, 2000
Concrete
7
0.11 178 187 2190

1: blast furnace cement + natural aggregate
2: Portland cement + natural aggregate
3: Blast furnace cement + BFS aggregate
4: Portland cement + BFS aggregate
5: Portland cement concrete
6: (Dry ash disposal) IBA ash-containing concrete
7: (Wet ash disposal) IBA ash-containing concrete

12
APPENDIX 3: samples collected during the UK Survey

13
Samples collected from EAST ANGLIA

HOUSING
ASSOCIATION

LOCATION
AND OS
REFERENCE
DATE
OF
VISIT
SAMPLE
TYPE
MANUFACTURER REFERENCE
ID
Clay
brick
Walman Reds N180
Aircrete Topbloc N181
Bellway Homes Nacton Rd,
Ipswich airport
(620750,
214250) Soil N187, N203
Mortar Euromix N178
Clay
brick
Halli Bazbarmoti N182
Concrete RMC N185
Clay
brick
Hanson N186
Wimpey Homes Havers Road,
Norwich
(621936,
310148)

Soil N213

Samples collected from EAST MIDLANDS

HOUSING
ASSOCIATION

LOCATION
AND OS
REFERENCE
DATE OF
VISIT
SAMPLE
TYPE
ID

Persimmon
Homes
Hampton
Hargate,
Peterborough
(Extensive
housing estate:
obtained
materials at
entrance)
Lime
cement
Buxton Lime
Industries
N124
Plasterboard British Gypsum N30
Mortar Tilcon Aggregates N123
Bovis Homes Glen Parva,
Leicester
(456250,
298750)
Aircrete Thermalite N176
Derwent
Housing
Association
Manchester
St., Derby
(433750,
336750)
29/09/2004
Clay brick (No details given) N125

14
Samples collected from LONDON

HOUSING
ASSOCIATION

LOCATION
AND OS
REFERENCE
DATE OF
VISIT
SAMPLE
TYPE
ID
Clay brick Taylor Maxwell (red) N85
Cement La Farge N86
Charlton
Triangle Homes
Ltd
Warren estate,
Charlton
Church Lane,
Charlton
(SE7), East
London
(541250,
177750)
Plaster N18 Network HA Wilton Road,
Victoria
(SW1), Central
London
(529250,
178750)
05/07/2004

Plasterboard
British Gypsum
N23
Mortar Euromix N20
Clay brick Leicester Red Facing
Brick
N64
7N/mm
block
Lignacite N87
Patchwork
Community HA
210 Green
Lanes, Palmers
Green, Enfield
(N13), North
London
(531250,
192750)
Received
25/06/2004
Concrete
brick
Smead Dean Kent
Yellow
N89

Samples collected from NORTHEAST ENGLAND

HOUSING
ASSOCIATION

LOCATION
AND OS
REFERENCE
DATE OF
VISIT
SAMPLE
TYPE
ID

Mortar RMC Readymix N34
Clay brick Baggeridge N35, N60
Station Road,
Wallend,
Newcastle
(429250,
566750)
Concrete Redland N44
Concrete
block
James Burrels N29
Plasterboard British Gypsum
(stnd. Board)
N36
Clay brick James Burrels N58
Johnnie Johnson
HA
Bell View/West
Street, Belford,
Northumberland
(410750,
633750)
Mortar (Contains La Farge
cement)
N130
Concrete
block
N37 Tees Valley HA Lewis Crescent,
Hendon,
Sunderland
(440750,
18/05/2004
Concrete
brick
Archibald
N59
15
Clay brick The Brick Business N61 556250)
Mortar Archibald N88

16
Samples collected from NORTHWEST ENGLAND

HOUSING
ASSOCIATION

LOCATION
AND OS
REFERENCE
DATE OF
VISIT
SAMPLE
TYPE
ID
Clay brick Ibstock N53
Concrete (Unknown) N55
CDS Housing Gwent St.,
Liverpool
(336250,
388750)
Calcium
silica. brick
Ibstock N73
Clay brick Phoenix N39
Concrete William Rianford N69
Clay brick Manchester Brick N74
Olive Mount
Heights,
Liverpool
(339750,
389750)
Soil N218
Calcium
silicate
(Unknown) N56
Clay brick The Brick Business N63
Mortar (Unknown) N129
Cosmopolitan
Housing
Shireley
Avenue,
Kirkby
(341750,
397250)
09/06/2004
Soil N195
Cement Blue Circle N42
Clay brick Furness Brick N50
Clay brick Reclaimed (Cheshire
Spire)
N51
Johnnie Johnson
HA
Crowther St.,
Stockport
(390250,
390250)
10/06/2004
Concrete
brick
Plasmor Stranlight N57
Clay brick Baggaridge Brick N38, N72
Concrete Plasmor Lightweight N40
Cement BLI Limebound N83
Mosscare HA Old Lane,
Openshaw,
Manchester
(338750,
397250)
08/06/2004

17
Samples collected from SOUTH COAST

HOUSING
ASSOCIATION

LOCATION
AND OS
REFERENCE
DATE OF
VISIT
SAMPLE
TYPE MANUFACTURER
REFERENCE
ID
Plasterboard Knauf N105 Bromyard
Crescent/Ludlow
Road, north
Portsmouth
(464750,
106250)
Cement Rugby Cement N175
Cement Rugby Cement N96
Aircrete Topbloc Tarmac N101
Portsmouth HA
Crenden Hill
Road, north
Portsmouth
(464250,
106250)
Clay brick Ibstock (red brick) N108
Clay brick (Recycled from
original barracks)
N103 Berkeley Homes Royal Clarence
(former navy
barracks)
housing estate,
Gosport
(4651250,
100250)
Plaster British Gypsum N106
Plasterboard Knauf (moisture
board)
N97
Plasterboard Knauf (sound
insulation)
N98
Pavillon HA Fleet Road,
Fleet, N
Hampshire
(480750,
153750)
20/04/2004
Plasterboard Knauf (19mm
standard)
N99

Table 4.8 Samples collected from SOUTHWEST ENGLAND

HOUSING
ASSOCIATION
LOCATION
AND OS
REFERENCE
DATE OF
VISIT
SAMPLE
TYPE
MANUFACTURER
REFERENCE
ID
Concrete Masterblock N177 Magna Homes Hendford Hill,
Yeovil,
Somerset
(355153,
115360)
Soil N201
Western
Challenge
Housing
Seldown
estate,
Walking Field
Lane, Poole,
Dorset
(401810,
907130)
07/09/2004
Concrete Manarpen N179

18
Samples collected from WEST MIDLANDS

HOUSING
ASSOCIATION
LOCATION
AND OS
REFERENCE
DATE OF
VISIT
SAMPLE
TYPE
ID
Concrete Master Block N15, N33
Clay Brick Cattybrook
Brunswick
Farmhouse
N24
Plasterboard Sheffield Insulations N32
Jephson HA 134-152
Coventry
Road,
Bedworth
(435750,
286250)
12/05/2004
Soil N217
Concrete La Farge N16
Plasterboard Gyproc N19
Mortar (contains La Farge
cement)
N25
Clay brick Ibstock (Lime
colour)
N26
Clay brick Ibstock (Red colour) N27
Mercian HA Moxley Road,
Darleston
(297250,
296250)
12/05/2004
Clay brick Ibstock (Grey colour) N28
Concrete White lightweight
concrete (Tarmac)
N17
Concrete Grey concrete
(Tarmac)
N22
Optima HA Bath Road
(near Cregoe
St.), central
Birmingham
(406250,
286250)
12/05/2004

Soil N199

19
Samples collected from YORKSHIRE

HOUSING
ASSOCIATION

LOCATION
AND OS
REFERENCE
DATE OF
VISIT
SAMPLE
TYPE
ID
Ibstock (red) N70 Clay brick
Ibstock
(Staffordshire blue)
N71
Concrete
brick
(Unknown) N76
Leeds Federated
HA
Lincoln Green
Rd., Leeds
(431250,
434250)
09/06/2004
Soil N211
Calton Brick (red) N45 Clay brick
Calton Brick (orange
colour)
N75
Plasterboard Knauf N82
20 Burngreave
Rd., Sheffield
(436250,
388250)
Clay brick Butterly Bricks N78 Henry St.,
Parkgate
Rotherham
(443750,
392750)
Soil N188
Concrete Durox N77
Plasterboard Knauf N79
(Redwall
Contractors)
Delmar Way,
Wickersley
Rotherham
(447750,
392750)
11/06/2004
Clay brick Hanson Butterly N80

20
Samples collected from SCOTLAND

HOUSING
ASSOCIATION

LOCATION
AND OS
REFERENCE
DATE OF
VISIT
SAMPLE
TYPE
ID
Concrete (Made on-site) D1
Clay brick Ibstock D3
Plasterboard Jewson D4
Plasterboard Jewson N10
Ardenglen HA Ardencraig
Road,
Castlemilk,
Glasgow
(260750,
658750)
02/03/2004
Mortar Euromix D25
Concrete
block
Laird Brothers Ns6
Cement Castle Cement D33
Concrete
brick
Laird Brothers D34
Angus HA Ness
Drive/Prosen
Drive, Arbroath
(365250,
741750)
22/04/2004
Mortar (Unknown) D37
Cement La Farge D39 Berwickshire
HA
Station
Road/Station
Avenue, Duns
(378750,
653250)
13/03/2004
Mortar (Contains above
cement)
D40
Mortar Bodychell Recycling Ns11 Cairn HA Huntly
Street/Dunaggan
Road, Inverness
(266250,
845750)
11/03/2004
Cement La Farge Ns12
Canmore HA 419 Gorgie
Road,
Edinburgh
(323250,
672250)
03/03/2004 Cement Castle Cement D8
Cement Mastercrete Original Ns5
Clay brick Hanson Butterly D21
Cube HA Hardridge Road,
Corkerhill,
Glasgow
(253750,
662750)
02/03/2004
Mortar (Unknown) D26
Concrete
brick
PJ Edenhall D28
Concrete
block
Laird Brothers D30
Clay brick Ibstock D27
Fairfield HA Fairfield
Avenue, Perth
(310250,
724750)
27/04/2004

Concrete
brick
Pattersons of Airdrie Ns3
Mortar Silomix Ns7
Link HA Minchway
Estate, Airdrie
(277750,
664250)
12/03/2004
Concrete
block
Pattersons of Airdrie N9
Masonry Tudorstone Ns1 Stewart Milne
Homes
Braehead,
Stonehaven
15/03/2004
Cement La Farge D36
21
Mortar (Made on-site) D29 (386750,
787750)

Concrete
block
Gordon & Sons
Concrete Block
Manufacturing
D35

Cement La Farge Ns2
Concrete
block
PJ Edenhall Ns4
Mortar (Made on-site) D23
West Highland
HA
Soroba Road
housing estate,
south Oban
(185250,
728250)
05/03/2004
Soil N215

22
Samples collected from NORTHERN IRELAND

HOUSING
ASSOCIATION

LOCATION
AND OS
REFERENCE
DATE OF
VISIT
SAMPLE
TYPE
ID
Concrete
block
? N142 NIHE Dungannon
Mortar ? N144
Mortar
cement
? N132
Concrete
block
? N135
Mortar ? N136
Pre-cast
concrete
? N139
NIHE Newry
27/05/2004
(Sent by
Brenden
Morgan)
Plasterboard ? N140

Samples collected from WALES

HOUSING
ASSOCIATION

LOCATION
AND OS
REFERENCE
DATE OF
VISIT
SAMPLE
TYPE
ID
Concrete
block
N109 Ysgol St., St
Thomas,
Swansea
(267750,
193250)
Concrete
brick
Keyline
D51
Clay brick The Brick Business N111
Plasterboard Sneff (fireline board) N112
Sneff (impact board) D52 Plasterboard
Sneff (sound
insulation)
D50
Soil N200
Ty Gwalia
Swansea
University
campus,
Swansea
(263250,
192250)
05/05/2004
Concrete CCP Ltd N120; D16

23
Samples collected from drillings from existing housing

ORGANISATION ORIGIN AND
APPROXIMATE
AGE OF SAMPLES
DATE
(RECEIVED/OBTAINED)
REFERENCE
ID

AWL Plumbing &
Heating
19
th
century housing,
Kirkcaldy
21/08/2004 N156
(N/A) (Lindon Sears house,
West Midlands)
03/10/2004 N157
ENHAM Housing
Association
1950s housing, Enham
Alamein
06/08/2004 N153
Caernarven Court
estate, Kent
N149 EPS Projects Ltd
Carrisbrook Court,
London
13/09/2004
N150
Linx Homes 1950s housing, Louth,
Lincolnshire
26/08/2004 N154
Salford, Manchester N160 Miller Crompton
Ltd Wallsall, Liverpool
13/09/2004
N161
SLD Architects &
Surveyors
1960s housing,
Thamesend, London
(Calcium silicate)
02/08/2004 N151
South Lanarkshire
Council
1980s housing, Kildare
Place, Lanark
23/09/2004 (Bathroom
drilling)
N158
West Lothian
Council
1970s housing,
Durware Drive,
Livingston
24/09/2004 N152

Demolition waste samples

DEMOLITION
WASTE
REFERENCE ID

Mike George Company N164
Fulton Building concrete
(From CTU department)
N165
Fulton Building granite
(From CTU department)
N166
Munroe Light Aggregate
Block
N167
Greyhound N168
Belmont (Material 5) N171
AM Lawson (Material
10)
N172

Owing to reasons of confidentiality, Appendix 4 has been withdrawn from public view.
24

Dioxin and Furan Extraction and Trace Metal Leaching From Selected Building Materials For Housing

Hochgeladen von

Dokumentinformationen

Originaltitel

Copyright

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Dioxin and Furan Extraction and Trace Metal Leaching From Selected Building Materials For Housing

Hochgeladen von

Copyright:

DIOXIN AND FURAN EXTRACTION, AND TRACE METAL LEACHING

FROM SELECTED BUILDING MATERIALS FOR HOUSING

1.7 * 1.4 0.4 <0.1 <0.1 <0.1 <0.1

1.2 0.7 1.0 0.6 <0.1 0.3 <0.1 1.9

1.7 1.7 <0.1 * 0.8 <0.1 <0.1 1.8

1.7 1.5 1.8 <0.1 <0.1 <0.1 <0.1 4.2

2.4 2.2 1.1 2.3 <0.1 <0.1 0.8 1.4

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

1.3 0.3 0.4 0.2 0.3 <0.1 <0.1 <0.1

<0.1 <0.1 * <0.1 <0.1 <0.1 <0.1 <0.1

<0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1

<0.1 <0.1 1.2 <0.1 <0.1 <0.1 <0.1 <0.1

7.9 * 11.9 7.7 9 4.4 4.6 10.9

5 4.5 4.3 5.6 8 4.4 6.5 20.9

13.2 12.3 10 30 15 9.7 6.7 14.1

12.1 9.5 7.3 11.4 5.5 5.9 5 15.2

33 9.2 8 7 19.1 2.2 5.4 24.8

2.6 * 11 6.7 8.9 5.4 4.6 5.9

6.1 5.7 1.6 3.9 4 5.4 20 1.7

8.9 11.2 * 9.8 7.2 7.5 5.1 4.2

8.8 8.6 6.6 6.9 5.8 7.5 6.8 4.8

23.5 6.9 4.5 3.8 3.9 3.1 3 7.2

<2 <2 <2 <2 <2 <2 <2 <2

<2 <2 <2 5.1 <2 <2 2.8 <2

<2 <2 <2 <2 <2 <2 <2 <2

<2 <2 <2 <2 <2 <2 <2 <2

<2 <2 <2 <2 <2 <2 <2 <2

<2 <2 <2 <2 <2 <2 <2 <2

<2 <2 <2 <2 <2 <2 <2 2.1

<2 <2 <2 <2 <2 <2 <2 <2

<2 <2 <2 <2 <2 <2 <2 <2

<2 <2 <2 <2 <2 <2 <2 <2

Das könnte Ihnen auch gefallen