Southern Cross University

ePublications@SCU
Theses

2009

Reactive in-situ covers for the remediation of mine

waste rock using BAUXSOL lime and biosolids
Gregory Arthur Maddocks
Southern Cross University, gmaddocks@golder.com.au

Suggested Citation
Maddocks, GA 2009, 'Reactive in-situ covers for the remediation of mine waste rock using BAUXSOL lime and biosolids', PhD thesis,
Southern Cross University, Lismore, NSW.
Copyright GA Maddocks 2009

ePublications@SCU is an electronic repository administered by Southern Cross University Library. Its goal is to capture and preserve the intellectual
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REACTIVE IN-SITU COVERS

FOR THE REMEDIATION OF
MINE WASTE ROCK
USING
BAUXSOL
LIME AND BIOSOLIDS

GREGORY A MADDOCKS
Bachelor of Applied Science (Hons.)

Submitted in fulfilment of the degree of

Doctor of Philosophy,
Department of Environmental Resource Management
Southern Cross University
10th July 2009

Gregory A Maddocks

THESIS DECLARATION
I certify that the work presented in this thesis is, to the best of my knowledge and
belief, original, except as acknowledged in the text, and that the material has not been
submitted, either in whole or in part, for a degree at this or any other university.
I acknowledge that I have read and understood the Universitys rules, requirements,
procedures and policy relating to my higher degree research award and to my thesis. I certify
that I have complied with the rules, requirements, procedures and policy of the University.

Gregory A Maddocks

ABSTRACT
Failure to design, construct and remediate waste rock and tailings storage facilities at
mine sites leads to adverse environmental degradation and unforeseen financial costs. Typical
closure options for these facilities include barrier or store and release covers. This thesis
investigates the use of reactive in-situ covers as an alternative engineering design approach
that involves mixing reagents (e.g. BauxsolTM) with waste rock to neutralise acidity and to
immobilise major and minor metals. It was unknown whether this approach could be achieved
at a field scale, whether the use of BauxsolTM would achieve its primary objectives, whether
there would be adverse effects on the soil chemistry or whether there would be adverse
ecotoxicological problems.
Four 400 m2 field trials were conducted at a mine site and included a Control;
Bauxsol (25 kg / m2) plus biosolids (15 kg / m2); Lime (2.5 kg / m2) plus biosolids (15 kg /
m2) and a fourth site that was encapsulated with 0.3 m of compacted clay and 0.1 m of topsoil.
The results suggest that soil chemistry can be significantly improved by mixing Bauxsol
with the top 0.5 m of the waste rock profile i.e., creating a reactive in situ cover. This was
sufficient to create a root zone up to 1.6 m deep that had pH greater than 5 and lower
concentrations of metals measured using a sequential extraction procedure. Treatment of the
acid mine waste with Lime did not achieve marked improvement of soil conditions in soil
layers below the amended zone. The capping treatment created a topsoil layer with higher pH,
but the underlying mine soil remained unimproved. Leachate pH in the Control became
increasingly acidic (pH 4.57 to pH 3.95). The addition of Lime and biosolids led to an initial
increase in leachate pH, compared to the Control, however this decreased over the duration of
the study (pH 5.37 to pH 4.89). In the Bauxsol and biosolids treatment leachate pH
increased to 6.92 after the first rainfall event and continued to increase over the duration of
the study to pH 7.4. After 24 months metal leachate concentrations (mg / L) in the lysimeters
for Al, Cd, Cu, Mn and Zn were (Control: 32.6, 5.7, 12.7, 39.3, 121.8), (Bauxsol: 0.07,
0.02, 0.07, 0.57, 0.23) and (Lime: 2.19, 1.19, 2.33, 3.6, 28.4). No leachate was available for
collection from the Clay treatment indicating that this technique was functioning in terms of
minimising the infiltration of water into the mine soil.
Ecotoxicological studies of major and minor metals in eucalypt leaves from the field
trials and earthworm bioaccumulation studies were undertaken. The Bauxsol, Ca(OH)2 and
Clay treatments in the field trials allowed good tree growth of four eucalypt species,
compared to the Control. There was no statistical difference in tree growth between the
Bauxsol, Lime or Clay treatments over the two years of monitoring. However the growth of
one tree species was poor in the Bauxsol treatment.
Laboratory bioaccumulation assessments found that there was good motility and no
mortality of the earthworm species E. fetida after 28 days exposure to metal loaded
BauxsolTM. The bioaccumulation of metals in E. fetida and bioaccumulation factors were
below reported toxicity thresholds to cause mortality and below reported bioaccumulation
factors for moderately contaminated soils, indicating that the metals bound to the Bauxsol
reagents are mostly non-bioavailable E. fetida. Analyses of the 20 % treatment at 28 days
using a sequential extraction procedure showed that > 95 % of the metals are bound within the
Fe / Mn oxide fractions. However, changes occurred in metal fractionation after exposure to
E. fetida for Cd, Cr and Fe, Mn. The data also showed that the exchangeable (1M MgCl2) and
the Toxicity Characteristic Leaching Procedure extractant are useful as indicators of metal
bioavailability to E. fetida.

Gregory A Maddocks

ACKNOWLEDGEMENTS
Foremost I would like to thank my wife for her patience, ongoing encouragement and
support and my son Alec for his inspiration to complete this work. I would like to thank my
supervisor David McConchie for his ongoing support and inspiration. Thanks also go to
Malcolm Clark and Chuxia Lin. I would also like to thank the staff of the Environmental
Analysis Laboratory at Southern Cross University for their analytical assistance and Virotec
Global Solutions.

LIST OF PUBLICATIONS
I warrant that I have obtained, where necessary, permission from the copyright owners
to use any third party copyright material reproduced in the thesis or to use any of my own
published work in which the copyright is held by another party.

PRE-PhD THESIS
The following papers have been completed from previous work associated with my
Southern Cross University Honours work. The published papers are related to the PhD thesis
as the work included initial smaller scale pot trials to assess the potential for scaling up to
larger field trials. The first two papers are provided in Appendix A.

Lin, C., Maddocks, G., Lin, J., Lancaster, G. and Chu, C. 2004. "Acid neutralising
capacity of two bauxite residues and their potential applications for treating acid
sulfate soil and water", Australian Journal of Soil Research. Vol. 42, No. 5. pp. 649657

Maddocks, G., Lin, C. and McConchie, D. 2004. "Effects of BauxsolTM and biosolids
on conditions of acid-generating mine soils for plant growth", Environmental
Pollution. Vol. 127. pp. 157-167.

McConchie, D., Clark, M., Lin, C., Davies-McConchie, F., Maddocks, G., 2002.
Bauxsol - A new treatment for acid sulphate soils and sulphidic mining wastes. IN:
Sustainable Management of Acid Sulfate Soils: 5th International Acid Sulfate Soils
Conference, Tweed Heads, August 2002, Abstracts Volume, 73-74.

Lin, C., Maddocks, G., McConchie, D., Lancaster, G. and Lin, J., 2002. The uses of
Bauxsol for treating sulfidic soils: laboratory modelling and pot trials. IN:

Gregory A Maddocks

Sustainable Management of Acid Sulfate Soils: 5th International Acid Sulfate Soils
Conference, Tweed Heads, August 2002, Abstracts Volume, 157-158.

McConchie, D., Clark, M., Lin, C., Davies-McConchie, F., Maddocks, G., 2002.
Strategies for the use of Bauxsol in the management of acid sulphate soils and
sulphidic mining wastes. In: Sustainable Management of Acid Sulfate Soils: 5th
International Acid Sulfate Soils Conference, Tweed Heads, August 2002, Abstracts
Volume, 165-166.

McConchie, D., Clark, M., Maddocks, G., Davies-McConchie, F. and Biggin, T.,
2004. Controlling acid mine drainage by in situ treatment of sulphidic waste rock and
tailings. 17th. Australian Geological Convention, Hobart, February 2004. Geol. Soc.
of Aust. Abstracts V. 73, p 32.

PUBLICATIONS ASSOCIATED WITH THIS PhD THESIS

The following conference proceeding was completed from work that was principally
conducted before the commencement of this PhD. However, this publication does include
work that is directly associated with this PhD thesis. This publication is included as a chapter
of the thesis. The author of this thesis contributed to less than % 25 of the content of the
following publication.

McConchie, D., Clark, M., Maddocks, G., Pope, S. and Caldicot, W. 2003. "The use
of BauxsolTM Technology, in Mine Site Management and Remediation", In:
Proceedings of the Mining Industry Conference, Montreal, Canada. Canadian Institute
of Mining. May, 2003.

The following publications have been completed from work directly associated with this PhD
thesis and are included as chapters within this thesis. This statement is to verify that I, Greg
Maddocks, am the principal author of the following published papers. I have undertaken the
all laboratory and field work programs associated with these publications and have
contributed to greater than 95 % of the writing and submission of these papers.

Maddocks, G., Lin, C. and McConchie, D. 2008. "Field Scale Remediation of Mine
Wastes at an Abandoned Gold Mine, Australia I- Effects on Soil Characteristics",
Environmental Geology. Under Review.

Gregory A Maddocks

Maddocks, G., Lin, C. and McConchie, D. 2008. "Field Scale Remediation of Mine
Wastes at an Abandoned Gold Mine, Australia II-Effects on Plant Growth and
Groundwater", Environmental Geology. Vol 57, No. 5, pp 987-996.

Maddocks, G., Reichelt-Bruschett, A., Vangronsveld, J., and McConchie, D. 2005.

"Bioaccumulation of metals in Eisenia fetida after exposure to a metal loaded
BauxsolTM", Environmental Toxicology and Chemistry. Vol. 24, No. 3, pp. 554-563.

Appendix B provides the publication history for the papers that were accepted in 2008
by Environmental Geology. Appendix C provides the publication history and copyright
statement for the paper that was published by Environmental Toxicology and Chemistry in
2005.
The following publication had been completed from work directly associated with this
PhD thesis and is included as an abstract in the Proceedings of the Joint Conference of the 6th
International Acid Sulfate Soils and the Acid Rock Drainage Symposium. I have contributed
to greater than 90 % of the writing and submission of this publication.

Greg Maddocks, Chuxia Lin and David McConchie (2008). Characteristics of Soils
under Field Scale Remediation in an Abandoned Gold Mine (Abstract). In C. Lin, S.
Huang and Y. Li (eds.). Proceedings of the Joint Conference of the 6th International
Acid Sulfate Soils and the Acid Rock Drainage Symposium. Guangdong Science and
Technology Press, Guangzhou.

Gregory A Maddocks

TABLE OF CONTENTS
THESIS DECLARATION.......................................................................................................3
ABSTRACT...............................................................................................................................4
ACKNOWLEDGEMENTS .....................................................................................................5
LIST OF PUBLICATIONS .....................................................................................................5
PRE-PhD THESIS ................................................................................................................5
PUBLICATIONS ASSOCIATED WITH THIS PhD THESIS............................................6

CHAPTER 1
AIMS AND OBJECTIVES ....................................................................................................14

CHAPTER 2
INTRODUCTION ..................................................................................................................26
BIOAVAILABILITY, SPECIATION AND FRACTIONATION.....................................27
Bioavailability............................................................................................................27
Speciation ..................................................................................................................27
Fractionation ..............................................................................................................27
SOURCES OF METAL CONTAMINATION...................................................................28
ACID AND METALIFFEROUS DRAINAGE .................................................................29
REMEDIATION OF METAL CONTAMINATED SITES...............................................30
Global remediation problems ....................................................................................30
Remediation definitions.............................................................................................31
CURRENT PRACTICES: SOIL REMEDIATION ...........................................................32
CURRENT PRACTICES: MINE WASTE REMEDIATION ...........................................34
Aims of mine site remediation...................................................................................35
Problems associated with waste rock and tailings remediation ................................36
Processes of remediation ...........................................................................................37
Landform design ........................................................................................................37
Pedongenic reformation.............................................................................................39
Habitat development and ecosystem sustainability ...................................................41
THE STUDY SITE .................................................................................................................44
REGIONAL GEOLOGY....................................................................................................44
WASTE ROCK AND AMENDMENTS............................................................................46
Waste rock .................................................................................................................46
Biosolids ....................................................................................................................47

Gregory A Maddocks

BauxsolTM ..................................................................................................................50
Lime ...........................................................................................................................52

CHAPTER 3
THE USE OF BAUXSOLTM TECHNOLOGY IN MINE SITE MANAGEMENT AND
REMEDIATION.....................................................................................................................54
ABSTRACT ......................................................................................................................55
INTRODUCTION ..............................................................................................................56
PRODUCTION OF NEUTRALISED RED MUD (THE BASECON PROCESS) ...........57
HOW DOES THE BAUXSOLTM TECHNOLOGY WORK AND IS IT
ENVIRONMENTALLY SAFE?........................................................................................62
TREATMENT OF SULFIDIC MINE TAILINGS AND WASTE ROCK........................73

CHAPTER 4
FIELD SCALE REMEDIATION OF MINE WASTES AT AN ABANDONED GOLD
MINE, AUSTRALIA I-EFFECTS ON SOIL CHARACTERISTICS...............................78
ABSTRACT ......................................................................................................................79
INTRODUCTION ..............................................................................................................79
MATERIALS AND METHODS........................................................................................81
The study site .............................................................................................................81
Experimental design ..................................................................................................82
Analytical methods ....................................................................................................83
Soil sampling .............................................................................................................84
RESULTS

......................................................................................................................84

pH and EC..................................................................................................................87
Ammonium acetate extractable salts .........................................................................88
Operationally defined fractionation of metals ...........................................................91
Aluminium .....................................................................................................91
Cadmium

.....................................................................................................91

Copper

.....................................................................................................92

Manganese .....................................................................................................92
Zinc

.....................................................................................................92

DISCUSSION.....................................................................................................................95
CONCLUSIONS ................................................................................................................99

Gregory A Maddocks

CHAPTER 5
FIELD SCALE REMEDIATION OF MINE WASTES AT AN ABANDONED GOLD
MINE, AUSTRALIA II-EFFECTS ON PLANT GROWTH AND GROUNDWATER101
ABSTRACT ....................................................................................................................102
INTRODUCTION ............................................................................................................102
METHODS ....................................................................................................................104
Plant species.............................................................................................................104
Leaf tissue metal and major ion analysis .................................................................104
Experimental design ................................................................................................105
Ground water monitoring ........................................................................................105
Installation of lysimeters.................................................................................105
Water sample collection..................................................................................105
Water analysis.................................................................................................105
Rainfall records........................................................................................................106
RESULTS

....................................................................................................................106

Rainfall records........................................................................................................106
Plant growth.............................................................................................................106
Statisitical analysis by SPSS: Tree mortality..................................................106
Statistical analysis by SPSS: Tree Growth .....................................................107
Root development ....................................................................................................108
Leaf tissue metal concentrations..............................................................................108
Leaf tissue major ion concentrations .......................................................................110
Groundwater characteristics ....................................................................................111
pH and EC

...................................................................................................111

Soluble salts ...................................................................................................111

Heavy metals ..................................................................................................113
DISCUSSION...................................................................................................................113
Control .....................................................................................................................113
Bauxsol treatment ................................................................................................114
Lime treatment.........................................................................................................116
Clay treatment..........................................................................................................117
CONCLUSIONS ..............................................................................................................117

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Gregory A Maddocks

CHAPTER 6
BIOACCUMULATION OF METALS IN EISENIA FETIDA AFTER EXPOSURE TO
A METAL LOADED BAUXSOL REAGENT. ..............................................................119
ABSTRACT ....................................................................................................................120
INTRODUCTION ............................................................................................................120
METHODOLOGY ...........................................................................................................122
Preparation of the metal loaded Bauxsol reagent. ...............................................122
Assessing acute toxicity of E. fetida after exposure to MLBR................................122
Characterisation of the 0 80 % MLBR treatments................................................123
RESULTS

....................................................................................................................125

Metal concentrations of the MLBR .........................................................................125

Assessing acute toxicity of E. fetida after exposure to MLBR................................125
Characterisation of the 0 80 % MLBR treatments................................................127
Relationships between selective metal fractions and bioavailability in E. fetida....127
DISCUSSION...................................................................................................................131
Assessing acute toxicity of MLBR to E. fetida .......................................................131
Possible mechanisms for shifts in soil metal fractionation after worm digestion ...135
Relationships between selective metal fractions and bioavailability in E. fetida....136
CONCLUSION.................................................................................................................137

CHAPTER 7
CONCLUSIONS ...................................................................................................................138

CHAPTER 8
REFERENCES .....................................................................................................................141

APPENDICES
APPENDIX A
APPENDIX B
APPENDIX C

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Gregory A Maddocks

FIGURES
Figure 1 Site location................................................................................................................19
Figure 2 Field site prior to construction ...................................................................................20
Figure 3 Field site preparations in the BauxsolTM plot .............................................................20
Figure 4 Construction in the Clay plot (left) and the field site prior to planting ......................21
Figure 5 Lysimeter construction used in the field trials ...........................................................21
Figure 6 Field trial tree growth at 12 months ...........................................................................22
Figure 7 Field trial tree growth at 24 months ...........................................................................23
Figure 8 Field site test pit excavation method at 24 months ....................................................24
Figure 9 Root development in the Clay, BauxsolTM and Lime Plots at 24 months ..................25
Figure 10a (pH), 10b (EC) and 10c (% Soil Moisture) in the Control, BauxsolTM (TerraB),
Lime and Clay treatments at 24 Months...........................................................................89
Figure 11 Operationally defined fractionation of metals in the Control (CN), BauxsolTM (TB),
Lime (LM) and Clay (CL) plots at 0-40 cm, 40-80 cm, 80-120 cm and 120-160 cm at 24
months...............................................................................................................................94
Figure 12 Tree mortality (left) and tree growth (right) for the four species used in this study.
........................................................................................................................................109
Figure 13 Leachate data from seven sampling events. All concentrations in mg / L unless
otherwise stated. .............................................................................................................112
Figure 14. Changes in metal fractionation in the 20 % metal loaded BauxsolTM (MLBR)
treatment. ........................................................................................................................128
Figure 15 Total metal concentrations in E. fetida tissue ........................................................134

TABLES
Table 1. Current remediation strategies used in the US to treat metal contaminated sites from
Pierzynski, (1999).............................................................................................................32
Table 2 Summary of the Basecon red mud neutralisation procedure ...................................59
Table 3 TCLP data for neutralised red mud and threshold values for classification as an inert
solid in New South Wales, Australia ................................................................................61
Table 4 Effect of treating water in a 1.6 ML toe dam at Mt Carrington, Australia, using
unblended BauxsolTM and direct addition methods ..........................................................67
Table 5 Effect of treating water in the 1,500 ML tailings dam at Mt Carrington, Australia,
using unblended BauxsolTM and direct addition methods ................................................68
Table 6 Effect of treating a sample of water from Captains Flat, New South Wales, Australia,
using unblended BauxsolTM and direct addition methods ................................................68
Table 7 Effect of treating a sample of water from the Britannia Mine, Canada, by direct
addition methods using a blend of BauxsolTM with 5% MgO ..........................................68
Table 8 Effect of treating a sample of water from Jam Lake, Canada, by direct addition
methods, using a blend of BauxsolTM with 5% MgO and 5% Ca(OH)2 up to pH = 7.0 and
then switching to unblended BauxsolTM to complete the treatment .................................69
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Gregory A Maddocks

Table 9 Some useful BauxsolTM additives and their main purpose ..........................................70
Table 10 Effect of passing water from Captains Flat, New South Wales, Australia, through a
BauxsolTM permeable reactive barrier ..............................................................................72
Table 11 Effect of passing water from Mt Morgan, Queensland, Australia, through a
BauxsolTM permeable reactive barrier ..............................................................................73
Table 12 Sequential extraction scheme used for the determination of the operationally defined
fractionation of metal........................................................................................................83
Table 13 Soil chemistry of the 12 samples of mine waste at 0 months (pH, EC, CRS and
TAA).................................................................................................................................84
Table 14 Initial operationally defined fractionation of metals in the mine waste. ...................85
Table 15 Chemistry of the Bauxsol (pH, EC, acid neutralising capacity (ANC) and the F2
fraction of major ions). .....................................................................................................86
Table 16 Operationally defined fractionation of the Bauxsol...............................................86
Table 17 Major chemical characteristics and operationally defined fractionation of the
biosolids............................................................................................................................87
Table 18 Ammonium acetate extractable soil concentrations. .................................................90
Table 19 Regional average rainfall data and site rainfall data from January 2002 to December
2003. ...............................................................................................................................106
Table 20 Leaf tissue metal concentrations determined using the YFEL method. All
concentrations in mg / kg................................................................................................110
Table 21 Sequential and selective extractant methodology used to determine soil metal
concentrations. ................................................................................................................124
Table 22 Metal concentrations of the Bauxsol reagent after loading with acid mine drainage
........................................................................................................................................126
Table 23 Changes in worm weight from 0 - 28 days and geochemical data of the metal loaded
Bauxsol reagent treatments at 28 days........................................................................127
Table 24 E. fetida and soil metal data....................................................................................129
Table 25 E. fetida and soil metal data.....................................................................................130
Table 26 Estimations of bioavailability (EB) for E. fetida.....................................................131
Table 27. The r2 values for given metals using the Toxicity Characteristic Leaching Procedure
(TCLP) extractant for different treatments. ....................................................................131
Table 28 Comparisons of bioaccumulation factor (BAF) data...............................................133

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Gregory A Maddocks

CHAPTER 1
THESIS OBJECTIVES
Chapter 1

This first chapter defines the objectives of the thesis as they are
presented in each chapter of the thesis.

Chapter 2

The second chapter in this thesis defines the scope of the problems
associated with metal contamination. This chapter then refines the
scope and places it into the context of the problems encountered within
the mining industry and more specifically how these problems are
associated with the extraction and exposure of sulfide minerals to
atmospheric conditions. Exposure of these minerals to atmospheric
conditions coupled with an increase in the surface area of the waste
rock as it blasted and extracted during mining can lead to an
accelerated rate of chemical, physical and biological weathering that
can then contribute to acid and metalliferous drainage (AMD). Acid
and metalliferous drainage is also known as acid mine drainage (AMD)
or acid rock drainage (ARD).

Chapter 3

The third chapter explores how an industrial waste product produced in

the alumina industry (red mud) can be converted into a beneficial coproduct that has applications in the field of environmental remediation.
The applications described in this chapter include the provision of data
that show how BauxsolTM reagents can be used to neutralise acidity and
to immobilise major and minor metals in soil and water.

Chapter 4

The fourth chapter builds upon the knowledge gained in Chapter 3 i.e.,
that BauxsolTM reagents can be used to neutralise acidity and
immobilise soluble metals in water, soils and mine waste rock. The
field trials in this chapter were conducted at the Mt Carrington gold
mine (Figure 1). The Mt Carrington gold mine is located in northern
New South Wales, Australia, at an elevation of 480-570 m Australian
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Gregory A Maddocks

Height Datum (AHD near the town of Drake in the Drake mineral field
which lies within the New England Fold Belt. The Mt Carrington mine
site is currently under care and maintenance. The field trial involved
the following aspects:

The construction of four x 400m2 on a haul road at the Mt

Carrington mine site (Figure 2)

The plots included:

o Bauxsol and biosolids (Figure 3)
o Lime and biosolids (Figure 3)
o A compacted clay and topsoil cover (Figure 4)
o An untreated Control plot (Figure 4)

The objectives of this chapter included the following.

Ascertaining whether BauxsolTM could be mixed with domestic

sewage solids (biosolids) to create a plant growth medium that
could be combined with potentially acid-generating metalcontaminated solid phase media, such as mine waste rock, to
achieve in-situ acid neutralisation and major, minor and trace
metal immobilisation.

Assessing the effectiveness of the in-situ application at a scale

that could be adapted to full-scale implementation at mining or
industrial sites (Figure 2, Figure 3 and Figure 4).

Comparing the results of treating sulfidic mine waste rock using

a mixture of BauxsolTM and biosolids mixed with other methods
of mine waste remediation such as;

Neutralisation of sulfidic mine waste rock with a

mixture of biosolids and lime, applied as Ca(OH)2; and

Encapsulation of sulfidic mine waste rock with clay and

topsoil.

Quantifying the effect that the addition of the BauxsolTM and

biosolids would have on the soil conditions including defining
changes to soil pH, cation exchange capacity and the
operationally defined fractionation of major and minor metals.

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Gregory A Maddocks

Determining how the use of the above reagents would affect the
fractionation or partioning of major and minor metals in the
treatments through the use of selective extractants and
sequential extraction procedures.

Chapter 5

The fifth chapter builds upon the knowledge in Chapters 3 and 4 and
assesses other aspects of the use of BauxsolTM reagents when they are
used, under the field conditions defined in Chapter 4, to neutralise soil
acidity and to immobilise major and minor metals in the remediated
soil profile. The environmental aspects investigated in this chapter were
associated with water chemistry in the vadose zone and ecotoxicology.
The objectives of the field trial in this chapter included the following.

Installing three zero tension lysimeters in each of the test plots

at the beginning of the study (Figure 5) and then collecting
groundwater after rainfall events so that changes in water
chemistry could be assessed and compared between the four
field plots over time.

Planting 100 seedlings in each of the treatment field plots. The

seedlings were from four eucalypt species and were planted as
tube stock at the beginning of the field trial.

Assessing whether the reagents have adverse or beneficial

ecotoxicological effects on the eucalypt tree species used in the
field trials including;

Measuring the differences in tree growth of the four

eucalypt tree species (Figure 6 and Figure 7);

Measuring the differences in tree mortality of the four

eucalypt tree species;

Measuring and comparing the concentrations of major,

and minor metals and major ions in the leaves of the
four eucalypt tree species and determining what effect
this may have on tree growth or mortality; and

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Gregory A Maddocks

Excavating test pits at 24 months (Figure 8) and

comparing root development in the four plots (Figure 9).

Chapter 6

Although it is important to understand how and why the application of

BauxsolTM works when it is applied under field conditions it was also
recognised very early in the study that is also important to understand
how the use of the technology may affect biotic receptor such as
earthworms..
This aspect of ecotoxicology was addressed in Chapters 4 and 5 by
assessing major and minor metal and salt concentrations in the leaves
of the eucalypt species that were used in the field trials. However this
represents only one aspect of ecotoxicology and did not address the
uptake of metals by soil biota that could transfer metals directly into the
food chain of higher order species such as birds.
The sixth chapter addresses additional ecotoxicological questions
related to the use of BauxsolTM reagents. These questions included
determining;

What the possible chronic and acute toxic effects of a metal

loaded Bauxsol reagent (MLBR), could be on the earthworm
species Eisenia fetida: Each kilogram of MLBR contained
approximately 6360 mg of metals that were sorbed from the
AMD. This assessment was undertaken by conducting 30 day
ingestion and bioaccumulation studies that measured acute and
chronic ecotoxicological impacts; and

Whether the bioavailability of the metals in the MLBR could be

defined through the use of selective extractants and sequential
extraction procedures.

Chapter 7

The conclusions of the thesis are summarised in Chapter 7

References

This chapter includes a list of references used throughout the thesis.

Appendices

The appendices in this thesis include;

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Gregory A Maddocks

Appendix A, which contains two publications on the use of

BauxsolTM from preliminary work on the subject of this thesis;

Appendix B, which contains the publication histories and

published papers in Chapters 4 and 5; and

Appendix C, the journal paper, copyright authorisation and

reviewers comments from the publication in Chapter 6.

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Gregory A Maddocks

Figure 1 Site location

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Gregory A Maddocks

Figure 2 Field site prior to site development

Figure 3 Field site preparations in the BauxsolTM plot

These figures show the BauxsolTM and biosolids mixture as it was placed in the plot (top left and top right). These figures
also show how the material was mixed into the waste rock using a 15 tonne excavator fitted with a single ripping tine (bottom
left and bottom right.

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Gregory A Maddocks

Figure 4 Site development in the Clay plot (left) and the field site prior to planting of the seedlings

Figure 5 Lysimeter construction used in the field trials

These figures show the how the lysimeters were constructed and installed.

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Gregory A Maddocks

Figure 6 Field trial tree growth at 12 months

This figure shows the Control, BauxsolTM, Lime and Clay plots (top to bottom) at 12 months.

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Gregory A Maddocks

Figure 7 Field trial tree growth at 24 months

This figure shows the Control, BauxsolTM, Lime and Clay plots in each row (top to bottom). Each row of figures shows the
plot as photographed from each corner of the plot at 24 months.

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Gregory A Maddocks

Figure 8 Field site test pit excavation method at 24 months

Each test pit was excavated to a depth of 2 m next to a tree so that observations could be made on root development. Soil
samples were collected in each test pit. The test pits were backfilled after the samples were removed for analysis..

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Gregory A Maddocks

Figure 9 Root development in the Clay, BauxsolTM and Lime Plots at 24 months
This figure shows the soil profiles in the three tests pits dug in each of the Clay, BauxsolTM and Lime plots (top to bottom) at
24 months. The Control plots were not excavated because root growth in the Control plots was restricted entirely to the tube
stock potting media i.e. there was no root development beyond the tube stock.

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Gregory A Maddocks

CHAPTER 2
INTRODUCTION
During the 1950s and 1960s soil science focused in part on enhancing the
bioavailability of essential trace elements to plants to increase agricultural productivity.
However, in recent decades the emphasis of geochemists and soil scientists has changed from
enhancing the bioavailability of essential trace elements to enhancing the immobilisation of
non-essential or potentially toxic trace elements (Sparks, 1995; Iskander and Kirham, 2001;
Lombi et al., 2002a; Gao et al., 2003). This change in focus arose through the realisation that
by increasing the bioavailability of essential trace elements the potential for the increased
bioavailability of potentially toxic or non-essential trace elements could occur (Iskander and
Kirham, 2001). Recent literature has espoused the need for quantitative information on the
factors that control the bioavailability of elements in the pedosphere so that innovative and
cost-effective methods of soil remediation can be developed (Sparks, 1995; Boisson et al.,
1999; Vangronsveld et al., 2000; Hodson et al., 2001; Iskander and Kirham, 2001; Lombi et
al., 2002b).
In environmental science, the term metal is used to describe a range of elements.
The precise definition of heavy metals is vague throughout scientific literature. (Duffus, 2001)
lists over 40 commonly used definitions for the term metal that are based on specific
gravity, atomic weight or atomic number in addition to terminology referring to biological,
chemical and toxicological sciences. Unless otherwise defined, in this thesis, the terminology
metal will refer to major metals (e.g., Al and Fe), minor metals (e.g., Cd, Cr, Pb and Zn)
and rare earth elements. In most terrestrial and aquatic environments, elements only occur at
trace levels unless they are emanating from localised natural point sources such as
hydrothermal springs or anthropogenic point sources such as mine sites (Vangronsveld et al.,
1996). In this thesis, major ions such as Ca2+, Mg2+, Na+, K+, Cl- and SO42- are often referred
to as salts.

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BIOAVAILABILITY, SPECIATION AND FRACTIONATION

Bioavailability
Bioavailability is another overused and vaguely defined term within environmental
literature and is often used to describe the extractable fraction of metals and major ions can be
removed from soil or water using a selective leaching or sequential extraction method.
Peijnenburg et al (1999) states that bioavailability should comprise two distinct and different
phases: a physicochemically driven desorption process that involves the release of metals
from a given matrix, environmental availability, and a physiologically driven uptake
process, whereby biota assimilate elements environmental bioavailability. Environmental
bioavailability requires the identification of a specific biotic species as an endpoint. The
toxicological bioavailability associated with the redistribution of metals within an
individual and to potential toxic effects, is the third aspect that can be distinguished as a
better-defined sub-category of the (often) vague concept of bioavailability. Toxicological
bioavailability is further complicated by the fact that once taken up, metals may be partitioned
into biologically available, biologically unavailable, or storage fractions. When speaking of
bioavailability and analytical soil extractants the terms speciation and fractionation are
important.

Speciation
Speciation refers to specific metal species such as, organometallic compounds, metals
bonded to different anions (e.g. chlorides, sulfates, sulfides, carbonates, oxides, etc.) or metals
with different redox states that determine elemental toxicity such as Cr3+ (limited toxicity) and
Cr6+ (highly toxic) (Templeton et al., 2000; Quevauviller, 2002).

Fractionation
Fractionation refers to and describes the physical or chemical properties or methods
that are used to remove metals from a soil (Templeton et al., 2000). In this thesis the term
operationally defined fraction (ODF) refers to the metals removed from a soil using a specific
selective extractant. For instance the use of water or 0.01M CaCl2 is often used to describe the
bioavailable soil fraction. In effect these should be described as the water-soluble ODF or
the 0.01M CaCl2 ODF, and can only be referred to as a bioavailable fraction when a

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specific biotic endpoint (e.g. the earthworm species Eisenia. fetida) has total body tissue
metal concentrations that correlate with either of the aforementioned extractants.

SOURCES OF METAL CONTAMINATION

Locally elevated metal concentrations can occur naturally through the weathering of
rocks, the generation of volcanic gases and magmatic water from geothermally active areas
and natural pedogenic processes. There are also increasing numbers of point and diffuse
sources of anthropogenic trace metal contamination from smelters, refineries, sewage
treatment plants, over-application of agricultural fertilisers, cars and other transportation
utilising organic fuels, industrial plants, livestock husbandry and mining.
Mining is an industry where the release of trace metals into the environment occurs at
an accelerated rate due to the exposure, physical weathering and chemical decomposition of
sulfide and non-sulfide minerals, and the leaching of rocks by acid generated as a result of
sulfide mineral oxidation. The focus of this work revolves around mine waste because mines
are a worse case scenario of trace metal soil contamination. Mining can have serious
adverse effects on the environment including the production of acid and metalliferous
drainage (AMD) water, habitat destruction and landscape alteration (Mulligan et al., 1999b).
Acidic metal contaminated drainage is also known as acid mine drainage and acid rock
drainage. AMD, as it is used in this thesis, refers to acidic to neutral saline drainage that may
or may not have elevated concentrations of metals and salts. Environmental degradation
associated with mining and industrial contamination is becoming an increasingly important
environmental, health and socio-economic issue in Australia, the South Pacific region (Hill
and Naidu, 1999), and the rest of the developed world due to the magnitude and widespread
occurrence of the problem (Lombi et al., 1998).
In this thesis waste is used a generic term to describe fresh to weathered mineralised
and non-mineralised waste rock. Waste rock differs from soil in two ways. Firstly, it has a
distinct lack of organic matter because it is essentially non-weathered rock and secondly, it
shows no characteristic signs of soil horizon development unless the dumps or tailings dams
are older than 100- 200 years.

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ACID AND METALIFFEROUS DRAINAGE

Acid and metalliferous drainage (AMD) is one of the highest priorities in the mining
industry in terms of its prediction, prevention, control and treatment (Parker and Robertson,
1999; Chatwin and Verburg, 2008). In areas surrounding mine sites, contamination of the soil
and water by metals and major ions can occur by the transportation of soluble and readily
exchangeable species in surface water, and ground water, by physical redistribution of rock
and mineral materials by gravity and water, or by airborne dispersion (Novotny, 1995) .
The processes of AMD formation are well documented in the literature and will not be
examined in detail in this thesis (Nordstrom and Alpers, 1999; Parker and Robertson, 1999;
Nordstrom et al., 2000; Cherry et al., 2001; DeNicola and Stapleton, 2002). The process of
AMD can be summarised as follows: when pyrite and other sulfide minerals are exposed to
O2 and H2O, hydrogen ions are generated and the pH of mine waters can be reduced to as low
as - 3.6 (Nordstrom et al., 2000); the associated drainage is frequently typically enriched in
metals and other elements (Parker and Robertson, 1999) that become disassociated from
primary and secondary minerals and organic components. The chemical generation of acidity
from the most common sulfide mineral (pyrite) is described below.
In this step, sulfur is oxidised to release hydrogen ions and SO42- (the dissociation products of
sulfuric acid in solution) and soluble Fe2+, which is free to react further.
FeS2 + 7/2O2 + H2O Fe2+ + 2SO42- + 2H+
In the second step, the Fe2+ ions in the presence of oxygen and hydrogen ions react to form
Fe3+ ions and water.
Fe2+ + 1/4O2 + H+ Fe3+ + 1/2H2O
In the presence of water Fe3+ can form oxyhydroxides and generate more acid
Fe3+ + 3H2O Fe(OH)3 + 3H+
Fe3+ ions can also act as an oxidant and increase the rate of pyrite oxidation and acid
generation by up to a million times.
FeS2 + 7 Fe3+ + 4H2O 15Fe2+ + SO42- + 16H+
It was previously assumed that Fe3+ would only oxidise pyrite at pH < 4.5, however,
studies by (Parker and Robertson, 1999) indicated that Fe3+ is still the better oxidant of pyrite
even at near neutral pH and that the role of oxygen is to oxidise Fe2+ thereby perpetuating the

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oxidation of pyrite. Ions such as Fe3+, Fe2+, Mn2+, Al3+, and H+ are the major exchangeable
components of acidity in AMD (Evangelou, 1995), however dissolved species that precipitate
as hydroxides or oxides including Mg2+, H2CO3, or H2S, can also contribute to acidity (Shu et
al., 2001). Under highly acidic conditions, many metals e.g. Al, As, Cd, Cr, Cu, Fe, Hg, Mn,
Mo, Ni, Pb and Zn can be released from waste rock in concentrations that can be toxic to
terrestrial and aquatic plants and animals; the toxicity can also be enhanced by the stress
caused to the organism by the low pH conditions. In aquatic ecosystems acidification is one of
the worst causes of contamination due to its inherent toxicity and the resultant effects on
metal concentrations, fractionation and speciation (Lopes et al., 1999). The direct effect of
acidity on plants is the inactivation of most enzyme systems, the restriction of respiration and
a reduced capacity to assimilate mineral salts and water (Shu et al., 2001).

REMEDIATION OF METAL CONTAMINATED SITES

Global remediation problems
The extent of problems associated with poor mining practices and the resultant soil
contamination is substantial across the globe and in the European Union alone it is estimated
that there are some 150,000 to 400,000 metal contaminated sites containing more than
1,000,000,000 m3 of highly contaminated soil, and waste (Mule and Melis, 1999; Prokop et
al., 2000). Although mining activities have generated AMD for over 2,000 years, much of this
contaminated material is due to activities undertaken between 1800 - 1945 (Lepp, 1999) and
the estimated cost to remediate these sites is in excess of 100 billion US dollars (Lombi et al.,
1998; Prokop et al., 2000).
The costs associated with AMD liability in 1997 were estimated as A$ 0.9 billion in
Australia, C$ 3-5 billion in Canada and US$ 2 to 35 billion in the United States (Chatwin and
Verburg, 2008).
In Australia and New Zealand there are about 60,000 and 50,000 metal contaminated
sites respectively (Hill and Naidu, 1999). In Australia the cost of AMD management at
operating mines was estimated at approximately $60 million / annum (Lee, 1999), and the
construction of cover systems for waste rock dumps in Australia ranges between $10,000 / ha
for simple vegetative covers to about $100,000 / ha for multi layer barrier covers (Wilson et
al., 2003).

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In the U.S. it is estimated that 19,300 km of rivers and streams and more than 180,000
acres of lakes and reservoirs were adversely affected by AMD in 1989 and the cost of
remediating these waterways was in the vicinity of 30 - 75 billion US dollars (Pierzynski et
al., 2000).
In 1997 metal contamination contributed to 65 % of the superfund sites in the United
States (Naidu et al., 1999). In 1998 the estimated number of seriously contaminated sites in
the United States was 35,000 (Lombi et al., 1998) and by 1999 there were 1206 metal
contaminated sites on the United States Superfund National Priority List (Pierzynski, 1999).
It is certain that the real costs associated with managing AMD and metal
contamination are substantially higher than those reported above. For example;

The costs to close an iron ore mine in Australia is reported to be A$ 190 million
(Wilde, 2007);

In New Zealand a coal mine is reported to be committed to spending NZ $1

million per annum for the next 100 years on treating AMD;

In South Africa the cost to rehabilitate abandoned mines is $US 14 billion

(Weiersbye, 2007); and

The Global cost to rehabilitate 300000 to 400000 metal contaminated sites was
estimated at US$1 trillion in 1997 (Weiersbye, 2007).

Remediation definitions
In the past 20 years public opinion has forced major environmental restoration
requirements on the mining industry in the form of environmental legislation (Bates, 1995;
Ashby and Kolar, 1998; Beavis and Lindbeck, 1999). Prior to this mine site remediation was
often not considered or was not successful. The move towards environmental responsibility
has fostered four recognised states of remediation. Remediation refers to the overall
improvement of an environment and includes restoration, reclamation and rehabilitation.
Restoration implies returning an affected area or ecosystem back to its original condition
(Silcock, 1992; Munshower, 1994; Jackson et al., 1995). Reclamation creates a condition that
results in a stable, self-sustaining ecosystem that may or may not include some exotic species
and includes a similar but not identical structure and function to the original land
(Munshower, 1994; Jackson et al., 1995). Rehabilitation refers to making an area of land
useful again after it has been used for some other purpose, as in creating a pasture or forest

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where there used to be a mine (Munshower, 1994; Jackson et al., 1995; Sengupta, 1995). The
type of remediation practices adopted at a site depends very much on the needs of the
proposed end land use along with contractual lease agreements. The final land use must be
compatible with community needs, any legal requirements, climate, soils, the local
topography, and the degree of management available after rehabilitation.

CURRENT PRACTICES: SOIL REMEDIATION

There are two distinct methods of treating soil contaminated with metals that include
in-situ and ex-situ remediation. Some of the in-situ and ex-situ techniques utilised for soil
remediation are shown in Table 1.
Table 1. Current remediation strategies used in the US to treat metal contaminated sites from Pierzynski,
(1999).

Ex-situ
Solidification /
stabilisation

Addition of a cementing agent to produce a hardened, non-porous, non-leachable

material

Vitrification
Washing
Leaching
Particle size segregation
Soil excavation
Soil aeration

Heating to produce a glass like, non-porous, non-leachable material

Chelate or acid extraction
Pile or batch leaching with acids or chelates
Selective removal of fine particles that have the highest metal concentrations
Soil removal and disposal
Tillage or agitation of the soil induces aeration causing volatilisation of elements

Solvent extraction
Thermal desorption

Organic solvents separate organic and inorganic

Wastes are heated so that contaminants and water volatilise, temperatures may
be high 320C 560C (HTTD) or low 90 320C (LTTD).

In-situ

Solidification /
stabilisation

As above

Vitrification
Encapsulation
Attenuation
Electrokinetics
Phytostabilisation
Phytoextraction
Thermally enhanced
recovery

As above
Cover site with impermeable layer
Dilution with uncontaminated material
Electric current induces movement of the ions to the electrodes
Promote vegetative growth to immobilise metals
Removal of metals by plants
Heat increases the rate of volatilisation to facilitate extraction

Immobilisation

The addition of amendments to immobilise contaminants thereby reducing the

bioavailability and mobility of metals

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In-situ

or Ex-situ

Bioremediation

Uses micro-organisms to degrade organic contaminants in soil, sludge or

sediment. Bioremediation can also be used on inorganic contaminants such as
sulfur.

Chemical treatment

Sometimes referred to chemical reduction / oxidation involves redox reactions that

convert hazardous contaminants to non-hazardous or less toxic compounds that
are more stable, less mobile or inert. Reagents can include hydrogen peroxide,
hypochlorite, potassium permanganate etc.

Neutralisation
Soil vapour extraction

Addition of reagents to induce changes to pH

A vacuum is applied to the soil to induce the controlled flow of air to remove
volatile compounds

The most common technique for the remediation of acidic or metal contaminated soil
in Australia is ex-situ offsite management (Khan et al., 2000) whereas encapsulation, topsoil
addition and more recently liming are the common remediation strategies for waste at mine
sites. Ex-situ operations are generally based on civil engineering techniques that are
expensive, environmentally invasive, labour intensive (Vangronsveld et al., 2000; Oste et al.,
2001) and pose ongoing problems with the removal, transportation and the subsequent
redistribution of contaminants into the environment at landfill sites (Pierzynski, 1999). Khan
et al (2000) state there are currently very few viable techniques for the in-situ removal of
metals from soil or waste, however there is increasing work being conducted on the in-situ
immobilisation (also known as inactivation or stabilisation) of metals in contaminated soil
media (Vangronsveld et al., 1995; Vangronsveld et al., 2000; Friesl et al., 2001; Lombi et al.,
2001).
The principle of in-situ immobilisation is to add soil amendments to the root zone of
contaminated soils or, where possible, throughout the entire contaminated profile, to bind the
metals in immobile ODF thereby limiting their environmental availability, while maintaining
the availability of essential elements. The main objective of sound in-situ remediation
techniques is to reduce the long-term environmental availability of contaminants in pedogenic
and aquatic environments. Combined with sustainable revegetation practices in-situ
techniques offer a viable alternative to the invasive and expensive practices that are currently
being used (Vangronsveld et al., 1999). However, one of the major problems with current
remediation techniques is their failure to provide long-term neutralisation of soil acidity and
prevent the release of metals into pedogenic and aquatic environments as bioavailable metals
(Vangronsveld et al., 1999).

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CURRENT PRACTICES: MINE WASTE REMEDIATION

Current remediation practices used at mine sites typically involve re-shaping to reduce
waste pile angles to 15-25 % (Ward, 1993; Bellairs, 1999), capping with clay or topsoil (Bell,
2001), and the addition of soil or waste amendments (attenuation) to stimulate plant growth
and reduce the translocation of contaminants into the environment (Barnhisel et al., 1998;
Brown et al., 2000). Other methods used in the mining industry include saturated covers,
oxygen consuming covers, the generation of hardpans and the addition of bactericides (Parker
and Robertson, 1999). In most cases the use of covers is largely ineffective, particularly in
regions with extreme climatic variables (Parker and Robertson, 1999). A recent paper by
Wilson et al (2003) states that the use of covers (encapsulation) is one of the few remaining
options for the remediation of existing waste rock dumps but that the structural or chemical
integrity of these systems may fail within 10 20 years. It is also acknowledged that
remediating acidic waste with topsoil, clay capping or liming or a combination of these
options works in the short to medium term but does not solve problems associated with longterm acid generation and ecosystem sustainability (Robson, 1989; Derome and Saarsalmi,
1999; Friesl et al., 1999; Pierzynski, 1999; Friesl et al., 2001).
A review by Fourie and Tibbett (2007) has shown that the complexity of covers for
tailings and waste rock storage facilities is increasing within the mining industry and the
analogues of multiple layers covers from the landfill sectors are becoming more widespread.
However, the use of cover designs involving layers of compacted clay has had limited success
because, climatic factors such as rainfall can rapidly render these covers ineffective through
erosion (Parker and Robertson, 1999; Fourie and Tibbett, 2007).
Store and release covers are seen as a preferable option, in environments where
evaporation exceeds rainfall, for storing seasonal rainfall in the cover so that it does not seep
into and then through the underlying waste rock. The stored water is then slowly released
through evapotranspiration. These cover designs are seen as offering substantial advantages
over barrier systems but are relatively new in their design phase (Fourie and Tibbett, 2007).
The basis of these designs is that the store and release cover should be able to retain the
seasonal rainfall and be deep enough to contain the roots of the developing plants species. The
downside of these designs may be that substantial volumes of material could be required and
may not be available at the site. The designs are generally restricted to shallow layers
requiring different machinery and skill sets to the mining phase. Additionally the depth of the

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material may not be sufficient to contain the roots and prevent them from breaking through
into the mine waste (which would lead to preferential pathways for rainfall and vadose water
leaching).
In instances where waste rock dump remediation is to be undertaken on historic,
abandoned or poorly managed sites encapsulation is commonly impossible because there is no
suitable capping media available. In recent years, chemical stabilisation or immobilisation
utilising readily available chemicals or by-products from industrial, municipal and agricultural
enterprises (Tordof et al., 2000) such as lime (Davis et al., 1999), gypsum, organic matter,
biosolids, fly ash, and zeolites (Bengson and Thompson, 1998; Brown et al., 2000; Cox and
Whelan, 2000; Gorman et al., 2000) has been proposed as a means to remediate waste rock
dumps where traditional encapsulation using clay or topsoil is unachievable or where the site
managers are aware of the limitations of encapsulation.

Aims of mine site remediation

Many of the practices used in the past, and still used today, fail to solve problems
associated with contaminant remediation in the long term (Schuiling, 1998) presenting
problems for corporate managers and environmental regulators. The major obstacles to
overcome from the managers point of view are problems associated with cost and functional
ecosystem sustainability (Williams, 1995; Tordof et al., 2000) meaning that they need to be
able to treat the site to a condition that will allow them walk away and avoid ongoing
management and maintenance, whereas environmental regulators may be faced with future
costs if the remediation measures fail over time. There is therefore, a clear need for the
development of sound in-situ techniques for the remediation of metal contaminated soil and
waste (Khan et al., 2000).
The aim of mine site remediation and the degree to which it is implemented varies
within and between countries. In the past Australia has aimed to rehabilitate areas for uses
such as grazing (Williams, 1995) but currently there is an increasing movement towards
reclamation, that aims to create sustainable floral and faunal communities containing native
components. This strategy has been adopted by Pacific Coal Pty. Ltd. (Bellairs, 1999), BHP
(Mulligan et al., 1999b) Alcoa and many other companies.

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Problems associated with waste rock and tailings remediation

Remediation at mine sites involves the treatment of waste rock dumps, exposed open
pits, haul road verges, plant sites and tailings storage facilities. Depending on the mineralogy
of the lithologies at the mine site, waste rock can be acidic or basic. Tailings are often basic
when they reach a containment facility due to the processing of the ore to remove base metals.
However, if the geology of the deposit contains sulfide minerals such as pyrite or chalcopyrite
then these tailings will become acidic if they are oxidised at some point in the future. Other
sulfide minerals in the waste rock or tailings such as galena or sphalerite can also release
some acid but are of more concern in terms of their capacity to release metals into the
environment as they are oxidised.
The view that waste rock and tailings constitute the largest volume of material that
must be stabilised and remediated and are often the hardest to remediate because of their
chemical and physical properties has not changed in the past decade (Kuhn, 1999; Fourie and
Tibbett, 2007). The problems associated with remediating and revegetating acid waste rock
are well documented and include metal toxicity, inherent acidity, high salt concentrations,
poor nutrient content and poor physical structure (Kabata Pendias and Pendias, 1992;
Alloway, 1995b; Dollhopf, 1998; Miekle et al., 1999; Brown et al., 2000). Clay-rich or
hydrothermally altered waste rock can deteriorate rapidly due to accelerated weathering losing
the intact properties of the original material and leading to lower strength, increased
compressibility, a reduction in hydraulic conductivity and increases in consolidation and
settlement (Kuhn, 1999). These geotechnical properties commonly compound the effects of
poor soil chemistry and increase the difficulties faced when remediation of these sites is
required.
While much attention is payed to the remediation of soil media for the establishment
of vegetation there is often a failure to comprehend the importance of the geotechnical
properties of the soil and rock material within waste rock dumps (Kuhn, 1999). Mining
changes earth materials by breaking or loosening them and while engineers may require
compacted stable material for structural purposes, revegetation work requires loose material
and therefore a compromise and understanding is needed between the engineer and the
revegetation scientist.

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Processes of remediation
Initial mine site remediation is concerned with ensuring that the site is able to
withstand the erosive forces of wind and water and is followed by the construction of
encapsulating media or the reconstruction of a suitable soil profile to allow revegetation (Bell,
1999). This is achieved by the construction of a landform that satisfies future land use needs
and invariably includes the incorporation of a suitable growth medium and vegetative cover
(Bell, 1999) that assists in controlling the release of contaminants from the soil and water
bodies to the hydrologic and pedalogic environment. This vegetative cover should be self
sustaining and require little further management (Phillips, 1994; Brown et al., 2000). There is
also a need to treat AMD, waste rock dumps, open pits and tailings dams etc and to establish
new and resilient ecosystems (Bell, 1999).

Landform design
Waste rock dumps are generally designed with minimising costs in mind and little or
no thought is given to the requirements of future remediation (Kuhn, 1999). When
remediation work is undertaken there is a need to consider the redesign of pit walls, waste
piles, tailings impoundments and sludge ponds (Kuhn, 1999). Whereas pit walls often fail
when driving forces from gravity, or water, or both exceed the resistance due to friction and
cohesion along a failure surface such as a geologic discontinuity (Kuhn, 1999), one of the
main problems associated with waste piles is the piling of waste material at the angle of
repose (Kuhn, 1999). This angle will commence at 40-45 degrees but as weathering
proceeds or if the toe of the pile is removed the slope may eventually fail (Kuhn, 1999).
The objectives of landform design are to increase slope stability to reduce physical
erosion, construct a functional drainage basin and provide suitable surfaces for plant
establishment (Munshower, 1994; Bates, 1995; Lindbeck et al., 1998; McRae, 1999).
Attaining erosive equilibrium of the landform means that the climatic forces must be balanced
with the interacting factors of slope geomorphology, the physical properties of the soil
material and the vegetation that is growing on the slope (Munshower, 1994).
Landform design deals with reshaping the landscape for vegetative re-establishment.
Williams (1995) states that the best way of minimising the chances of a disaster in the initial
stages of vegetative establishment is to create a very rough surface so that water ponds until it
can be absorbed rather than running off the surface topography causing erosion. In areas with

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large generally flat surfaces, contour cultivation with chisel ploughs is a common method of
reducing erosion and preparing a surface for sowing but this procedure is limited to slopes
below about 5. Contour ripping, scalloping or moon-scaping of the slope face can be carried
out along the contour lines in steeper areas to catch surface drainage and reduce gully erosion
(Williams, 1995; Lindbeck et al., 1998). The size and depth of these structures varies with
slope angle and the climate of the region (Silcock, 1992).
Reshaping of the landform includes removing and reshaping waste piles and waste
dumps to angles of between 8% and 33% (Silcock, 1992). In Queensland angles of between
10% and 15% are recommended (Bell, 1987) but typical angles of reshaped waste dumps are
around 20(Williams, 1995). Lindbeck et al (1998) support the idea of waste piles with
convex tops (to reduce infiltration) and berms that collect and funnel surface run-off into silt
traps. This reduces AMD and collects sediment that may be laden with metals.
The final landform depends on available expenditure, is dependent on slope length,
density of vegetative cover at ground level and the intended land use (Silcock, 1992) and must
be hydrologically compatible with surrounding land (Ward, 1993; Ward, 1995; Hossner,
1999). Sinusoidal shapes that mirror natural landforms are preferred (Ward, 1993;
Munshower, 1994; Ward, 1995) and ensures that slopes are lowest where the volume and
velocity of overland flow is greatest (Silcock, 1992; Munshower, 1994). One of the main aims
of good landform management is to reduce the rate of erosion of unconsolidated material
(Munshower, 1994; Ward, 1995; Lindbeck et al., 1998), caused by the removal of vegetative
cover. The rate of erosion at mine sites can reach or even exceed 5 - 25 mm / yr and is some 5
- 25 times greater than the acceptable erosion rates in Australian agricultural areas (Williams,
1995). Surface mining removes the vegetation and disturbs the natural soil profile, exposing
the soil to the forces of erosion. Soil erosion occurs when the energy of moving water or air
exceeds the forces binding the soil (Lindbeck et al., 1998). Wind erosion is initiated by coarse
particles driven across the ground by wind. Wind erosion at mine sites is considered to be
insignificant in terms of actual soil loss, but has implications in terms of dust control and
impeding establishing plant life (Lindbeck et al., 1998). Water can cause raindrop splash, rill,
sheet or gully erosion. Raindrops falling on exposed surface soil pulverise and compact the
soil reducing infiltration and increasing the action of the water leading to rill, sheet or gully
erosion. Rill, sheet and gully erosion is related to the flow velocity of the water and the
cohesion and dispersivity of the soil particles. The cohesive ability of the soil is related to soil

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physics and chemistry while the angle and length of the slope, the depth of the water and the
texture of the soil surface affect the velocity of the water (Lindbeck et al., 1998). Although
gully erosion is severe and obvious the effects of rill and sheet erosion, which are spread over
a large area, can be just as severe (Lindbeck et al., 1998).

Pedongenic reformation
Pedogenic reformation of degraded sites involves a multidisciplinary understanding of
plant biology and the physicochemical properties of the media in which the desired vegetation
is to be grown. The major parameters that influence the ability of growth media to support life
include moisture, nutrients, temperature, light, pH, electrical conductivity, sodium content,
organic matter content, cation exchange capacity and the texture, structure, bulk density and
porosity of the soil (Munshower, 1994).
Pedogenesis is a result of the interaction of climate, soil organisms, topography, parent
material and time. Under natural pedogenic formation elements including Ag, As, Cd, Cu,
Hg, Pb, Sb and Zn are often found in the surface layers while Al, Fe, Ga, Mg, Ni, Sc, Ti, V
and Zr are accumulated in the lower profiles with translocated clays and hydrous oxides
(Alloway, 1995b). This natural pattern is broken under cultivated conditions or during mining
operations and allows unwanted or unneeded elements to enter the rhizosphere. Apart from
the effects of AMD, low plant nutrient levels, poor physical soil structure and texture, and
variable oxygen gradients compound the problems of utilising and repairing the soil profile
for sustainable use.
During mining the topsoil and subsoil are removed and are generally stored for later
use or are reapplied to areas undergoing remediation. The process of removal disturbs soil
biota, and the chemical and physical properties of the soil. The productive capacity of the
replaced soil profile will always be limited by the inherent chemical, physical and biological
properties of the soil (Sengupta, 1995) and there are serious problems with soil collection
preservation and application. (Sengupta, 1995) states that even if the exact thickness of topsoil
and subsoil were replaced, two soil properties that likely would not be the same as those in the
pre-mining profile are the size, shape, and volume of pore spaces and the number and kind of
soil micro-organisms.
Waste dump construction generally occurs by end dumping at the angle of repose or
by bottom up construction methods whereby the waste rock is placed in layers (benches) with

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various degrees of compaction that are either intentional or a consequence of the trafficking
during the dumping process. These construction methods often lead to well compacted layers
on top of the waste dumps. During the remediation and revegetation process the compacted
mine waste will need to be fractured to allow mulch and chemical stabilising media to be
mixed into the profile. After this, the use of heavy machinery will contribute to a subsequent
deterioration in physical soil properties including a loss of soil structure, an increase in bulk
density and a reduction in porosity and permeability that will create an impediment to root
growth. Dry soils are far more amenable to soil handling and resist compaction (McRae,
1999) and so spreading and working of the soil should be done when the soil is dry to reduce
compaction.
Establishing an optimum soil profile requires the use of the right machinery at the
right time. Deep ripping with winged tines can be used to open, break and shatter compacted
soils in the initial stages but their operational depth is limited to about 450mm. Ashby (1997)
states that deep ripping to a depth of 1.2m is useful and can increase tree growth by opening
the soil and allowing root penetration. Bacon and Humphries (1988) in McRae (1999)
suggests the single row dump and turn method for reducing compaction of soils whereas
(McRae, 1999) supports the loose tipping method because it avoids compaction completely
and utilises deep ripping methods combined with the application of topsoil with an excavator.
Again the effectiveness and type of remediation operation that can be employed is linked to
time and financial constraints.
Topsoil is always better for plant growth than shattered and less weathered rock from
the lower horizons (Hossner, 1999). Silcock (1992) states that topsoil in mine site remediation
contains the original organic and organo-mineral horizons and can include the underlying A
and B horizons. Although mine soils initially have no pedogenic profile, Hossner (1999)
claims that this problem can be corrected by using site specific chemical, biological and
physical amendments that are combined with existing mine wastes or applicable layers from
deeper in the soil profile. If the topsoil is sterile or unsuitable for sustainable development the
use of mulches and other soil amendments can be used to improve soil pedogenesis. The
success of topsoiling or mulching depends on the depth and type of amendment the existing
phytotoxicity in the soil and available funds (Silcock, 1992). Mulching amendments can be
natural organics like hay or may be artificially enhanced with engineered methods such as
hydroseeding or Jutte matting.

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Gregory A Maddocks

Habitat development and ecosystem sustainability

Some restoration scientists consider that anthropogenically mediated ecological
succession should follow an orderly and readily identifiable pattern (Bradshaw, 2000).
However, most native Australian habitats are however in a non-stable state and are affected
and regulated by disturbance regimes that make them vulnerable or adapted to ongoing
change (Bellairs, 1999). A regulated pattern of ecosystem development is therefore unlikely
to occur under natural succession where the outcomes of the remediation plan can only be
defined in broad terms and where there is immigration of species not included in the expected
vegetation regime. It is therefore more realistic to expect that successional development of
derelict land will follow a natural pattern unless extensive and expensive interaction and
management strategies are used. This means that the perception and expectation from the
public that mine-site remediation should produce instant results, is neither rational nor
ecologically invalid.
Natural mine site revegetation can be very successful. However, it can take 75-100
years to deliver fully functional ecosystems (Bradshaw, 2000): and this may only occur if the
physical and chemical parameters of the soil are acceptable for plant growth (Williams, 1995;
Prach and Pysjek, 2001) and if the surrounding region has seed bearing vegetation (Bradshaw,
2000). Acid mine waste presents on ongoing obstacle to plant growth and natural regeneration
(Bengson and Thompson, 1998) and may do so for many years or decades until oxidation of
the material ceases, acid generation is halted and the material is neutralised. Acid soil
conditions inhibit fungal and bacterial ammonification processes (Silcock, 1992) and plant
growth. Aluminium toxicity is also a major problem affecting plant growth in acid soils
(Kochian and Garvin, 1999; Luster et al., 1999; Nietfeld, 1999) because aluminium interferes
with cell division, increases cell wall rigidity, impedes DNA replication, reduces root
respiration, interferes with enzymes and nutrient assimilation and fixes phosphorous in less
bioavailable forms (Robert, 1995).
In order for rehabilitation to be successful ecosystem reconstruction should aim to
initiate and maintain soil development as a primary goal rather than just establishing
vegetation that may fail in successive years. The importance of a self-sustaining vegetative
cover is highlighted by Partridge (1979 in Silcock, 1992) who states that without permanent
vegetation, the cycling of nutrients and minerals through the system (essential for creating a
stable ecosystem) cannot be achieved and the landscape will remain susceptible to damage.

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Ground stability, initial nutrient content, the presence of nitrogen fixing species, microbial
activity and the ability of the soil to capture and hold nutrients are all critical factors in
developing and maintaining effective nutrient cycling (Bellairs, 1999). The key to long term
habitat sustainability lies in not only in establishing pioneer species on amended soil but also
in developing a self sustaining soil biological community (Frouz et al., 2001) that will achieve
nutrient cycling and successional development of plants (Bell, 1999; Mulligan et al., 1999a;
Wagner and Harrington, 2000).
When the required end land use of remediation at a mine site is a return to native
forest, the starting point is an artificial system composed of native and or exotic pioneer
species, or both (Wagner and Harrington, 2000). The exotic pioneer species can be used to
provide shelter from direct sunlight, reduce surface soil temperature, accelerate soil stability,
promote the development of soil micro-organism populations and enhance soil organic matter
and nitrogen assimilation (Wagner and Harrington, 2000), until the native trees are
established. However, fast growing and persistent exotic species may out-compete native
plants: particularly the understorey species.
Native understorey tree, shrub and herb species are vital in Australian forests and are
dynamic communities that support soil microbial and mesofaunal populations, provide a
quick ground cover (until the secondary successional crop trees are well established), shelter
the soil, improve soil structure, and provide food and shelter for fauna (Mulligan et al., 1999a;
Mulligan et al., 1999b; Wagner and Harrington, 2000). Ground stability, initial nutrient
capital, the presence of nitrogen fixing species, microbial activity and the ability of the soil to
capture and hold nutrients are all critical factors in developing and maintaining successful
nutrient cycling (Bellairs, 1999) in the understorey communities. The development of this
community is, however, a slow process. Mulligan et al (1999a) found that little humus had
developed in rehabilitated topsoil in tree trial areas even after 15 years indicating a deficiency
in the cycling of nutrients.
The standard revegetation method at many Australian mines includes, propagating
grass and pasture species in the initial season and planting shrubs and trees the following year
(Macyk et al., 1998; Mulligan et al., 1999a; Hunt, 2000). The establishment of grass or
pasture species helps protect the soil against the transport of sediment and nutrients off site
(Silcock, 1992; Macyk et al., 1998; Mulligan et al., 1999a) and enhances soil moisture
retention (Miller, 1998). However, where the post-mining land use requires a return to native

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tree habitat these grass and pasture species can inhibit the growth of trees (Silcock, 1992;
Kost et al., 1998; Miller, 1998; Bellairs, 1999), but the weeds species can be partly controlled
by the use of suitable tree compatible ground cover, fire, herbicides (Ashby, 1997) or tree
shelters (Miller, 1998).
In many large-scale remediation programs vegetation is established by broadcasting
seed (Macyk et al., 1998; Bell, 2001) because this technique is cheaper and can give superior
results over tube stock (Miller, 1998). This strategy is being used in many countries (Parrotta
and Knowles, 2001) including Australia (Mulligan et al., 1999a). The species selected
ultimately depends on the final land use intended soil conditions and climate. A quick cover
crop of grass is usually established to minimise erosion but care must be taken in species
selection so that later tree and shrub planting is not impaired by the grasses (Ward, 1995). In
previous rehabilitation programs in the Bowen Basin, where grazing was favoured as the final
land use, rapid growing exotic pasture grasses such as Cenchrus ciliaris (Buffel grass) and
Chloris gayana (Rhodes Grass) have been used effectively as colonising vegetative species
(Mulligan et al., 1999b). Silcock (1992) provides further information on suitable plant species
for use in mine site rehabilitation. Stoloniferous grasses may have greater benefits to
artificially planted grass / tree communities under anthropogenically mediated planting
regimes than tall pasture species. Stoloniferous grasses are advantageous when a native forest
habitat is required because they are low growing, almost incapable of setting viable seed and
are well suited to vegetating dam walls and waste rock piles (Silcock, 1992).
Recently, a new development in Australia relating to remediation and pedogenic
reformation of degraded farmland has been demonstrated by Peter Andrews1. The general
approach is to allow, even facilitate, the establishment and growth of weeds on degraded
farmland in the initial stages of remediation. These weeds are slashed and used as mulch over
successive seasons to create an organic matter rich substrate. Successional development of
native species is then facilitated and encouraged once sufficient organic matter has
accumulated in the soil profile. This Natural Sequence Farming approach has considerable
merit for mine sites where the availability of organic topsoils is often limited.

http://www.nsfarming.com/index.html

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Gregory A Maddocks

THE STUDY SITE

The field work in this thesis was undertaken at the Mt Carrington mine site which lies
within the Drake mineral field and is near the village of Drake (Figure 1). Drake is 52 km east
of Tenterfield and 76 km west of Casino on the Bruxner Highway in NSW, lies at 28 50 00
latitude and 125 20 30 longitude and has an elevation of between 480-570 m Australian
Height Datum (AHD). The climate is cool to subtropical and the region has a distinct wet
season between December and April. The mean annual rainfall and temperature values used
for the site are based on the average records of the four closest Australian Bureau of
Meteorology (ABM) weather stations at Tabulum (elevation 550 m AHD), Urbanville
(elevation 370 m AHD), Girard (670.6 m AHD) and Tenterfield (860 m AHD). The rainfall
records for 2001 were measured from a rain gauge at the project site.

REGIONAL GEOLOGY
The Drake mineral field lies within the New England Fold Belt, and is composed of
Late Palaeozoic and remobilised older Palaeozoic complexes that have been intruded by
Permian and Triassic orogenic granites (Markham and Basden, 1978). The Drake region lies
in the Demon-Emu Creek Block and is characterised by north to northwest trending faults that
separate the Drake volcanics from the older rocks to the west and younger rocks to the east.
Upper Permian to Triassic rock intrudes the older sedimentary base rocks of the region
(Offenburg and Cochrane 1974 in Knight, 1975). The rocks are primarily volcanic in the
south and epiclastic in the north. The area is a complex combination of; andesite - dominated,
calc - alkaline lavas, tuffs and epiclastic rocks together with sub volcanic, comagmatic stocks
and dykes (Solomon and Groves, 1994) epiclastic breccias and laharic deposits (Herbert 1983
in McWatters, 1991). The oldest rocks in the Drake field are Carboniferous sandstones,
siltstones, mudstones and silicified limestone (McWatters, 1991). Rhyolitic flows,
agglomerate and breccia, known as the Mount Carrington Rhyolites overlie the Carboniferous
sediments and these are in turn overlain by the Drake Volcanics. The Drake Volcanics are
some 1000 m in thickness (Solomon and Groves, 1994) incorporate the Drake Andesites and
include andesitic volcanics and sediments (Markham and Basden, 1978).
The ore genesis in the area has been described as epithermal to mesothermal by
various authors although evidence by Perkins (1986 in McWatters, 1991) and

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geothermometry studies by Smith (1989 in McWatters, 1991), who give originating fluid
temperatures of between 222-295C, suggest that the area should be classified as
leptothermal. Although the exact classification of the worked ore bodies at the Mount
Carrington mine site differs between authors, several broad mineralisation types are
represented and include fissure veins, vein stockworks, disseminated sulfide units and breccia
infillings (Markham and Basden, 1978). Solomon and Groves (1994) classified the Mount
Carrington pit as a fissure lode and the White Rock and Lady Hampden pits as a stockwork
system and disseminated system respectively. Offenburg and Cochrane in Knight (1975)
classify Lady Hampden, Adeline, Guy Bell, Mt Carrington and Kylo as fissure loads the
Strauss Pit as a stockwork and Emu Creek and the eastern zone of the Strauss pit as
disseminated. Houston (1993) describes the classification of the Drake mineral field in terms
of stockworks and vein systems.
The area around the Drake mineral field is extremely rich in sulfide minerals but the
precise source of the ore generating fluids within the different mineralised veins is unclear.
Solomon and Groves (1994) state that the New England Fold Belt developed in a part
terrestrial and part marine environment, and find that some of the gold-sulfide deposits are
due to thermal cell development as sea water circulated through the rock mass. Herbert and
Smith in Mc Watters (1991) concluded that the sulfur was derived from volcanogenic and
biogenic sulfur in the country rocks and that the ore forming fluids were due to a combination
of meteoric and magmatic water. In the available literature, there are at least two views on the
mineralisation processes that have taken place. Smith (1989 in Mc Watters, 1991) states that
the mineralisation of the Drake mineral field occurred in four stages and includes quartzhaematite veining and breccia cement, sphalerite +/- pyrite-galena, quartz-chalcopyritetennantite-pyrite +/- bornite-haematite-electrum-gold-aikinite and quartz-chalcopyrite-pyrite
+/- carbonate.
Houston (1993) suggests two stages of mineralisation. The first includes an initial
phase of gold and zinc rich fluids within the Kylo quartz andesite stock. The second stage of
mineralisation occurred slightly later and shows dominant chalcopyrite overprinting of the
earlier phase. This second phase is characterised by copper rich solutions. Within the Strauss
pit two mineralisation systems are evident. Initial intensive intrusions of Zn rich fluids that
are reasonably high in Cd were replaced or overprinted by secondary quartz flooding (or
silicification) bringing jasper, pyrite, chalcopyrite, sphalerite and minor amounts of galena.

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WASTE ROCK AND AMENDMENTS

In order to ameliorate mine site waste and contaminated soil with poor chemical and
physical properties when suitable topsoil and construction materials is limited or absent one
management option is to develop and incorporate an artificial soil media into the waste rock
that will allow plant growth. The soil amendments used must be able to supply the waste with
organic matter and nutrients, neutralise current and future acidity and be able to immobilise
metals to reduce their translocation into the environment. There may also be a requirement to
create soil structure and texture that is conducive either to the requirements of the vegetative
habitat or geotechnical considerations such as reducing erodability or increasing or decreasing
permeability. Mine wastes are highly heterogenous and generally require site-specific
investigation to determine optimal amendments to facilitate their eventual remediation
(Hawkins, 1998).

Waste rock
The waste rock from the mining operations at the study site is stored in four large
waste rock dumps west of the tailings dam (Figure 1). This mine waste is a mixture of fresh
lithic overburden from the oxidised geologic zones and sulfidic and gangue material from
reduced geologic zones. This material is not in chemical equilibrium with the surface
environment and is a primary source of contamination at the site through the oxidation of
sulfide minerals and the subsequent generation of AMD. The mine waste in these dumps is
typical of many waste rock dumps and is characterised by material ranging in size from large
boulders of greater than 2 m to fine clay fractions less than 0.002 mm in diameter.
The sulfide minerals at the site include pyrite, chalcopyrite, sphalerite, galena,
tetrahedrite, bornite and chalcocite and the gangue minerals include quartz, calcite, siderite,
and rhodochrosite; pyrite is by far the most abundant sulfide mineral. Extensive alteration
zones with varying amounts of sericite, quartz, calcite, dolomite, orthoclase, chlorite and clay
minerals are common and are clearly visible within the Strauss and Mt Carrington open pits;
the two major open pits on the site. The main mineral suite around the Mt Carrington area
comprises quartz, illite, kaolinite and smectite, with smaller quantities of volcanic glass,
chlorite, potash feldspars and plagioclase (Offenburg and Cochrane in Knight, 1975).

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Biosolids
From 1998 the dumping of biosolids at sea has been banned in the European Union,
necessitating the need for sustainable reuse of this resource (Gove et al., 1999). Biosolids are
also being viewed as a resource rather than a waste product in Australia (Polglase and Myers,
1996; Simms, 1996) and have long been used as a soil amendment in the US (Brown et al.,
2000) where by 1993, 72 mine sites had been reclaimed using biosolids (Sopper, 1993, in
Rogers et al., 1998). Biosolids used as a soil amendment at mine sites are blended with lime,
log yard waste, sawdust and more recently with coal combustion by-products (Semalulu et al.,
1998; Gorman et al., 2000) to correct soil acidity, provide nutrients and organic matter
(Roberts et al., 1988; Brown et al., 2000) and establish a functional microfaunal and
microfloral community (Bendfeldt et al., 1998; VanderSpiegel and Evans, 1999; Whatmuff,
1999). Single applications of biosolids have been shown to sustain vigorous vegetative cover
for several decades and for conventional soil restoration practices, biosolids appear to be the
most effective and economic method that is currently available to restore soil nutrient
requirements (Brown et al., 2000). It has been found that N added as an organic amendment
rather than inorganic fertiliser provides a more stable source of soil N and also gives greater
crop yield and quality (Schoenholtz et al., 1992, in Kramer et al., 1998).
Possible problems associated with using biosolids include their affinity for
translocating excessive metal, pesticide, nutrient and poly chlorinated biphenyl concentrations
into the environment (Phillips, 1994). These possible problems remain unresolved (Dowdy et
al., 1999) and there is conflicting evidence regarding the chemical forms of metals in
biosolids, their bioavailability and the long term effects on soil biota and plants (Rogers and
McLaughlin, 1999). Rogers and McLaughlin (1999) also state that the metal species and
bioavailability of metals in biosolids are highly variable from one source to the next. The
soluble metal fraction in biosolids is usually only 0.5 7 % of the total amount of sludge
borne metals but it can be a major contributor to the total metal load that is transported
through the soil or taken up by plants following application (Vulkan et al., 1999): this is
dependent on the environment that the biosolids are used. Metals in biosolids can be found as
simple or complexed ions in the soil solution, readily exchangeable ions, organically bound
ions, co-precipitated ions on metal oxides or other secondary minerals and as ions in the
crystal lattice of primary minerals (Kaewrahun et al., 1999).

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There appears to be general agreement that organic matter in biosolids will bind
metals (Zasoski 1981, and others in Kramer et al., 1998) but it has also been found that as the
organic matter content decreases over time (Rule and Martin, 1999) or as soil pH changes
(Planquart et al., 1999; VanderSpiegel and Evans, 1999) the metals in biosolids will become
more bioavailable. Whatmuff (1999) found that under conditions where the soil pH is < 5 Cd
and Zn are bioavailable even when the total concentrations in the biosolids are very low.
These findings are corroborated by Balik et al., (1999) who found a substantial increase in Cd
and Zn concentrations in above ground biomass after biosolids application.
Despite the above findings there is detailed work that offers contrary evidence to that
of the above authors. Brown et al., (1998) found that the possibility of increasing metal
concentrations through biosolids application generally results in no observable increase in
plant metal concentrations. This is corroborated by an eight-year study conducted by
Bourgeois et al., (1999) who state that there is no indication of substantial effects on plants
and soils due to biosolids application. Furthermore, when biosolids are used on mine sites, the
heavy metals that could be available in the biosolids would represent a very small proportion
of the total quantity of available metals.
The use of biosolids to supply nitrogen and phosphorous to nutrient deficient soils is
well known but may have drawbacks because of the leaching of NH4+, NO3- and PO43- from
the soil. A study of native Australian forests irrigated with sewage effluent suggest that 75100 kg total nitrogen /ha can be assimilated by trees before canopy closure is reached but the
uptake rate drops off significantly at that point (Snow et al., 1999). This problem can be
averted by controlled additions but in single applications for mine site remediation some
leaching of nitrogen species (e.g. NO3-) may result. Where concerns over the leaching of
excess NO3- exist, biosolids have been combined with high organic carbon material such as
sawdust or woodchips to reduce the potential for NO3- leaching through the immobilisation of
nitrogen (McLaughlin, 1996; Bhogal et al., 1997; Brown et al., 2000).
Early nitrification studies assumed that nitrification did not occur at soil pH < 5, but
more recent studies confirm that nitrification, mostly by chemolitho - autotrophic bacteria,
does occur in acid soil and will result in increased leaching of NO3- from the soil. The loss of
nitrogen from the soil can be decreased by changing the carbon (C): nitrogen (N) ratio.
Pierzynski et al., (2000) suggest that nitrogen immobilisation and mineralisation are balanced
when the soil has a C:N ratio of 25 : 1 and that a C:N ratio of less than 25:1 can lead to

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excess soluble nitrogen being lost to the environment. Nitrogen mineralisation is mediated by
heterotrophic organisms and immobilisation involves the assimilation of inorganic nitrogen
by soil micro-organisms. Immobilisation is controlled to a large extent by the availability of
carbon that is needed by the soil micro-organisms to produce amino acids and proteins. If
there is an inadequate supply of carbon relative to inorganic nitrogen, microbial growth and
consumption will be reduced leading to a reduction in the conversion of soluble nitrogen to
biomass nitrogen and a loss of soluble nitrogen as NO3- or NH4+. In Eucalypt forests the C:N
ratio can be as high as 70:1 (Bellairs, 1999).
Phosphorous is often the nutrient that limits N fixation during the early stages of soil
development and plant succession in the native Australian landscape (McLaughlin, 1996) and
it can be made available through biosolids application. It can be seen from the above
discussion that the effects of biosolids application are site, plant and media specific and that
their use depends on several parameters and should be evaluated before field application
commences.
Phosphorous concentrations in Australian soils are very low (Handreck, 1997; Atwell
et al., 1999) and therefore phosphorous will most likely be deficient in mine spoil for
introduced plant species, but may not be critical for native plant species such as eucalypts and
acacias (Handreck, 1997). The plant availability of the phosphorous in the spoil will be
affected by the acidity and the Al content of the spoil. From acid to alkaline conditions (pH 49) phosphorous exists mainly as di-hydrogen phosphate (H2PO4-), hydrogen phosphate
(HPO42-) and PO43- (Pierzynski et al., 2000) and the phosphorous in the biosolids would most
likely be released as PO43-. Under acid conditions where there is a supply of Al, Fe or Mn, the
formation of very insoluble metal phosphates could occur, however after the addition of
Bauxsol, increases in soil pH and the subsequent decreases in Al, Fe and Mn would allow
the formation of plant available H2PO4- and HPO42- (Pierzynski et al., 2000). Under acidic
conditions more positively charged binding sites are available on very fine mineral particles in
the soil and these can also bind the negatively charged phosphate species.
If the neutralisation of acid and the removal of soluble Al, Fe and Mn occurs in the
soil profile then soluble and plant available phosphorous could be leached through the upper
profile, however, the leaching of phosphorous would not occur through the acid, metal rich
unamended lower profile and the phosphorous would be bound as low solubility minerals in
this zone.

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BauxsolTM
Red mud is the caustic residue produced during the production of alumina from
bauxite by the Bayer process. In 1999 global red mud production was estimated to be in the
order of 40 million tonnes per year. However, due to dramatic increases in alumina
production, estimates of global red mud production are now closer to 100 million tonnes per
year. Figures on the volumes of red mud in containment facilities world wide are not available
but can be assumed to be the order of 1000s of millions of tonnes range.
When red mud is discharged to containment facilities it contains insoluble solids and
caustic liquor that could not be economically recovered. The supernatant liquor comprises the
caustic-aluminate solution that is used to digest and remove the aluminium. It typically
comprises NaOH, NaCO3, NaHCO3, and NaAlO2 the insoluble bauxite minerals in the red
mud are usually dominated by hematite (Fe2O3) and aluminous goethite ((Fe, Al)OOH) (Hind
et al., 1999) along with the titanium dioxides, anatase (TiO2) and rutile (TiO2) (Hind et al.,
1999). Some boehmite (AlOOH) may also be present if the process is not designed to extract
this form of alumina (Hind et al., 1999). The remaining elements in bauxite are present in the
muds only in minor or trace quantities (Mc Conchie et al., 2000). Clay minerals or quartz
present in the bauxite also react with the digestion liquor to produce a mineral compound
known as Bayer-sodalite, (3(Na2OAl2O32SiO2nH2O)Na2X) where X may be CO3, SO4,
2OH, 2Cl or a mixture of any or all depending upon the impurity composition of the digesting
liquor (Chvedov et al., 2001). Sodalite and cancrinite are desilication products and can
contribute some additional alkalinity (Somes et al., 1998 in Hanahan, 2001). Lime is another
primary component of the Bayer process and reacts to form CaCO3, 3CaOAl2O36H2O and a
form of calcium phosphate, i.e. carbonate or hydroxyapatite (Chvedov et al., 2001). At high
bauxite digestion temperatures (230260C), the lime can also react with the titanium mineral
anatase to form perovskite CaTiO3) and or kassite (CaTi2O4(OH)2) (Chvedov et al., 2001).
These minerals are also potential sources of carbonate alkalinity in the red mud.
Given the large volumes of red mud being produced each year and the costs of
building and maintaining containment facilities, re-use of this industrial by-product can be an
economically and environmentally rational solution. If the red mud can be re-used then the
costs associated with the construction and maintenance of containment facilities can be
reduced. To decrease the environmental liabilities of red mud handling and storage the
causticity of the red mud and supernatant liquor is reduced through various neutralisation

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processes. The red mud produced by ALCOA in Western Australia is neutralised through the
absorption of reducing the pH of the red mud from 11 to 9 . The addition of CO2
combined with Atomer gas sheering technology (developed by CVG Bauxilum) is another
method of reducing red mud pH (12.2 to 7.6) (Galarraga et al., 2002). In the Northern
Territory (Australia) the ALCAN refinery uses separates the SNL from the red mud by a red
mud farming process and then treats the supernatant liquor with seawater to lower the basicity
but elements that form oxyanions (e.g. As, Cr, Mo, Se & V) and some aluminium tend to
remain in solution and the fluid has to be diluted before it can be discharged to the sea. At the
Queensland Alumina refinery (QAL), seawater is used to neutralise the caustic (pH 11-13) red
mud without separating the solids from the residual liquid and there is no loss of the elements
that form oxyanions because they can be bound to the solid particles(McConchie et al., 1996).
At QAL some seawater is added before the red mud is pumped to the red mud dam (this is
done to ensure the slurry can be pumped while conserving fresh water) and the rest of the
required seawater is added at the red mud dam; excess seawater is discharged from the red
mud dam to the sea. In some refineries acid has been used to neutralise the red mud and in
others the red mud has been dumped directly into the sea. Stacking of red mud is also widely
adopted as a method of separating supernatant liquor for solid residues and has been widely
used by ALCAN since the 1970s (Belanger, 2001).
Reuse of red mud is gaining increased acceptance throughout the world. Red mud is
being sold by ALCOA in Western Australia as Alkaloam and is being used for the retention
of phosphorous in sandy soils adjacent to coastal estuarine waters where the loss of
phosphorous to the waterways contributes to eutrophication and algal blooms. MartinentCatalot et al. (2002) report on another commercial product called Bauxaline that is produced
from red mud and is used for dump remediation, as a colouring agent and for arsenic (As)
fixation. Red mud has been used to bind heavy metals, neutralise soil acidity, and retain
phosphorous in soil and in aqueous solutions (Apak et al., 1997; Altundogan et al., 2000;
Gupta et al., 2001; Hanahan, 2001; Kadirvelu et al., 2001; Chunlei et al., 2007; Garau et al.,
2007; Paradis et al., 2007). Other authors have used red mud to adsorb carbon dioxide
released from decomposing sewage sludge, thereby increasing the pH buffering capacity of
compost (Qiao and Ho, 1997) while others have used it as a catalyst in hydrodechlorination
reactions (Ivarez et al., 1999; Ordonez et al., 2001). Red mud is also being used as an additive

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in cements, and is being used in building materials such as bricks, tiles and road construction
material (Mymrin and Vazquez-Vaamonde, 2001).
Virotec International have patented the BaseconTM process that utilises seawater, or Ca
and Mg rich brines, or Ca and Mg chlorides, or some combination of these alternatives to
neutralise red mud by converting soluble alkalinity to solid alkalinity. The Basecon process
produces a red mud derivative known as Bauxsol (Mc Conchie et al., 2003). Bauxsol is
the base reagent in a variety of products being marketed by Virotec International for the
treatment or beneficiation of AMD, acid sulfate soils, acid waste rock dumps, acidic
aquaculture ponds, sewage water and solids, tannery wastes and the treatment of industrial
process waters (McConchie and Clark, 1996; Lin et al., 2002a; Mc Conchie et al., 2002; Lin
et al., 2004b; Maddocks et al., 2004; Maddocks et al., 2005). The quality and chemistry of the
Bauxsol produced by this neutralisation process varies depending on the source of the
bauxite and operational procedures at the refinery (Mc Conchie et al., 2003). In general the
acid neutralising capacity of the Bauxsol ranges between 3.5 and 7.5 mol / kg. The
Bauxsol produced by this process contains some soluble Ca2+, Mg2+, SO42-, Cl-, Na+, and
minor amounts of trace elements: all these metals fall below threshold values set by the NSW
EPA for the US EPAs TCLP test.
The BauxsolTM reagents used in this thesis were obtained from the Queensland
Alumina refinery (Gladstone, Queensland, Australia). Further detail is provided on the
Basecon process and BauxsolTM technology in Chapter 3.

Lime
In recent years some mining companies have responded to the challenges associated
with reducing the risk of waste rock dumps discharging AMD by using in-situ remediation
techniques in the construction of their waste rock dumps. At the Grasberg mine, operated by
PT Freeport Indonesia in Indonesia, the addition of limestone has been trailed and found to be
effective (Miller et al., 2003). Other studies designed to test the concept of in-situ remediation
of mine waste (Taylor et al., 2005) and to assess the effectiveness of these approaches at field
scale level (Rusdinar, 2005) have also been conducted.
Whereas limestone is a common soil additive used to immobilise heavy metals, at sites
where the soil is likely to re-acidify, limestone may have limited use as a single addition
treatment because it may not maintain the desired soil pH over time (Hamon et al., 2002) as

52

Gregory A Maddocks

the particles become armoured by precipitates or leached out by groundwater. Other

limitations on the use of lime are that although it will increase soil pH in the amended soil
zone, it does not contribute to increased soil pH below the amended zone unless it is applied
well in excess of the requirements indicated by acid-base accounting (Cregan et al., 1989, in
Robson, 1989; Derome, 2000). The capacity of limestone to infiltrate into and neutralise
acidity is also constrained by the application approach and the chemical and physical nature
of the limestone (Rusdinar, 2005). Excessive applications of lime, as CaO or as Ca(OH)2 are
also undesirable because soil pH will become alkaline and may adversely affect plant
establishment or growth and can also affect soil chemistry. The failure of lime to remediate
sub-soil pH when the target soils contain sulfide minerals is mainly a result of armouring of
lime particles particularly by precipitated Fe and Al oxyhydroxides (Rose and Elliot, 2000)
and the fact that the neutralisation capacity of the lime is quickly consumed (Ren sheg Li et
al., 1998); gypsum precipitation can also adversely affect soil texture and permeability. Lime
applied as Ca(OH)2 or CaCO3 is also slightly soluble and consequently, it can be leached from
the treated rock units over time. Any under-liming resulting from leaching the lime before all
sulfides have oxidised can compound problems because the resulting bicarbonate ions can
accelerate the decomposition of sulfides and the resulting generation of acid. The
accumulation of heavy metal hydroxides and hydroxycarbonates following lime neutralisation
can create phytotoxic conditions for plant growth (Vangronsveld et al., 1996) and if overliming raises pH conditions much above 9, the higher pH can facilitate the mobilisation of Al
as Al(OH)4- and elements such as As, Cr, Mo, Se, V, etc that form oxyanions under oxidising
conditions.
The addition of lime to acid waste is a common method used to increase soil pH and
immobilise heavy metals like Cd, Zn, Cu and Ni through the formation of sparingly insoluble
hydroxides (Khan et al., 2000). However, if the pH of the soil decreases later, the metal
complexes may be destabilised and the metal ions will be released back into the environment
(Gabler, 1996; Kramer et al., 1998; Schuiling, 1998; Gray et al., 2006).

53

Gregory A Maddocks

CHAPTER 3
THE USE OF BAUXSOLTM TECHNOLOGY IN MINE SITE
MANAGEMENT AND REMEDIATION

Paper removed due to copyright restrictions pp. 55-77

Available via http://www.cim.org/publications/specialvols.cfm

Publication History
Published in the May 2003 Proceedings of the Canadian Institute of Mining: Mining Industry
Conference, Montreal, Canada.
Authors
McConchie1, D., Clark1, M., Maddocks2, G., Pope, S1 and Caldicot, W3.
Affiliation
1
2
3

Virotec Geochemical Research Team, Southern Cross University, Lismore, N.S.W. 2480,
Australia.
School of Environmental Science and Management, Southern Cross University, Lismore
Virotec USA Inc., 54 Grozier Road, Cambridge, MA 02138, USA

54

Gregory A Maddocks

CHAPTER 4
FIELD SCALE REMEDIATION OF MINE WASTES AT AN
ABANDONED GOLD MINE, AUSTRALIA I-EFFECTS ON
SOIL CHARACTERISTICS

Article removed due to copyright restrictions pp. 79- 100.

In press

Publication History
Accepted for publication in Environmental Geology on the 24th July 2008:- In Press
Authors
Maddocks1, G., Lin C1 and McConchie2, D
Affiliation
1 School of Environmental Science and Management, Southern Cross University, Lismore
2 Virotec Geochemical Research Team, Southern Cross University, Lismore, N.S.W. 2480,
Australia.

78

Gregory A Maddocks

CHAPTER 5
FIELD SCALE REMEDIATION OF MINE WASTES AT AN
ABANDONED GOLD MINE, AUSTRALIA II-EFFECTS ON
PLANT GROWTH AND GROUNDWATER

Article removed due to copyright restrictions pp. 102-118.

Maddocks, G, Lin, C & McConchie, d 2009, 'Field scale remediation of mine wastes at an
abandoned gold mine, Australia II: effects on plant growth and groundwater', Environmental
Geology, vol. 57, no. 5, pp. 987-996.
The publisher's version of this article is available at
http://dx.doi.org/10.1007/s00254-008-1383-0

Publication History
Accepted for publication in Environmental Geology on the 14th May 2008:- Vol. 57, No. 3, pp
987-996
Authors
Maddocks1, G., Lin C1 and McConchie2, D
Affiliation
1 School of Environmental Science and Management, Southern Cross University, Lismore
2 Virotec Geochemical Research Team, Southern Cross University, Lismore, N.S.W. 2480,
Australia.
101

Gregory A Maddocks

CHAPTER 6
BIOACCUMULATION OF METALS IN EISENIA FETIDA
AFTER EXPOSURE TO A METAL LOADED BAUXSOL
REAGENT.

Article removed due to copyright restrictions pp. 120- 140.

Maddocks, G, Beichelt-Brushette, A, McConchie, D & Vangronsveld, J 2005,

Bioaccumulation of metals in Eisenia fetida after exposure to a metal-loaded
bauxsolTM reagent', Environmental Toxicology and Chemistry, vol. 24, no. 3, pp. 554-563.
The publisher's version of this article is available at
http://dx.doi.org/10.1897/04-087R.1

Publication History
Received by Environmental Toxicology and Chemistry on the 19th February 2004
Accepted for publication in Environmental Toxicology and Chemistry on the 4th August 2004
Published in Environmental Toxicology and Chemistry Vol. 24, No. 3, pp. 554-563, 2005.
Authors
Maddocks1, G., Amanda Reichelt-Brushett1, David McConchie1, Jaco Vangronsveld2
Affiliation
1 School of Environmental Science and Management, Southern Cross University, Lismore
2 Environmental Biology, Limburgs Universitair Centrum, Diepenbeek, Belgium

119

Gregory A Maddocks

CHAPTER 8
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ICOBTE.

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APPENDICES

160

Gregory A Maddocks

APPENDIX A

Journal articles removed due to copyright restrictions

161

Gregory A Maddocks

APPENDIX B
From:

schwarzbauer@lek.rwth-aachen.de

To:

gmaddocks@golder.com.au

Cc:
Subject:

Environmental Geology - Decision on Manuscript ID EG-08-0280

Body:

05-Aug-2008

Dear Mr. Maddocks:

Manuscript ID EG-08-0280 entitled "Field Scale Remediation of Mine Wastes at an Abandoned Gold
Mine, Australia I-Effects on Soil Characteristics" which you submitted to Environmental Geology, has
been reviewed. The comments of the reviewer(s) are included at the bottom of this letter.
The reviewer(s) have recommended a further review step after some major revisions. Therefore, I
invite you to respond to the reviewer(s)' comments and revise your manuscript.
To revise your manuscript, log into https://mc.manuscriptcentral.com/eg and enter your Author Center,
where you will find your manuscript title listed under "MANUSCRIPTS WITH DECISIONS." Under
"Actions," click on "CREATE A REVISION." Your manuscript number has been appended to denote a
revision.
You will be unable to make your revisions on the originally submitted version of the manuscript.
Instead, revise your manuscript using a word processing program and save it on your computer.
PLEASE ALSO HIGHLIGHT THE CHANGES TO YOUR MANUSCRIPT WITHIN THE DOCUMENT
BY USING THE TRACK CHANGES TOOL IN MS WORD OR BY USING BOLD OR COLORED
TEXT.
Once the revised manuscript is prepared, you can upload it and submit it through your Author Center.
When submitting your revised manuscript, you will be able to respond to the comments made by the
reviewer(s) in the space provided. You can use this space to document any changes you make to the
original manuscript. To expedite the processing of the revised manuscript, please be as specific as
possible in your response to the reviewer(s).
IMPORTANT: Your original files are available to you when you upload your revised manuscript.
Please delete any redundant files before completing the submission.
Because we are trying to facilitate timely publication of manuscripts submitted to Environmental
Geology, your revised manuscript should be uploaded as soon as possible. If it is not possible for you
to submit your revision in a reasonable amount of time, we may have to consider your paper as a new
submission.
Once again, thank you for submitting your manuscript to Environmental Geology and I look forward to
receiving your revision.
Sincerely,
Dr. Jan Schwarzbauer
Associate Editor, Environmental Geology
schwarzbauer@lek.rwth-aachen.de
Reviewer(s)' Comments to Author:

162

Gregory A Maddocks

Reviewer: 1
Comments to the Author
Product trade-names should not be used to identify the soil amendment throughout the paper. The
trade-name may be used once in the paper (along with identified manufacturer) after the product has
been briefly described, i.e. Treatment 2 was a solid amendment complex (henceforth referred to as
"red mud") of Fe-Al oxyhydroxides and alumino-hydroxy-carbonates (TerraB, Virotec International
Limited, Australia), applied along with Biosolids.
Reference to TerraB and Bauxosol should not occur after that and the products should then only be
referred to as "red mud" (or whatever descriptors the authors wish to use to identify them). I would
also strongly suggest that the same change be made to part II (companion manuscript) of this
manuscript if trade-names have been used there as well. If the authors agree to make this suggested
change, I will then review this manuscript in detail.
05-Aug-2008

163

Gregory A Maddocks

From:

pel@dbtech.net

To:

gmaddocks@golder.com.au

Cc:
Subject:

Environmental Geology - Decision on Manuscript ID EG-08-0281

Body: 14-May-2008
Dear Mr. Maddocks:

It is a pleasure to accept your manuscript entitled "Maddocks 2008-Field Scale Remediation of Mine
Wastes at an Abandoned Gold Mine Australia II-Effects on Plant Growth and Groundwater" in its
current form for publication in Environmental Geology. The comments of the reviewer(s) who reviewed
your manuscript are included at the foot of this letter.
Reviewer(s)' Comments to Author:
Submitted paper titled "Field Scale Remediation of Mine Wastes at an Abandoned Gold Mine,
Australia II - Effects of plant Growth and Ground Water" by Maddocks et el., presents a continuation of
already published investigations in this journal. In the manuscript the authors gave a lot of interesting
experimental results with acceptable statistical interpretation. The paper is at the high professional
level with some fundamental input.
Technically, the manuscript has been written at an acceptable level. English language is good, figures
are of high quality as well as the tables. Because of that, with great pleasure, I would recommend the
publishing of this paper in Environmental Geology journal without important changes.
Date Sent:

14-May-2008

164

Gregory A Maddocks

APPENDIX C

165

March 19, 2004

Dr. Greg Maddocks
4 Sovereign Place
Goonellabah NSW
Australia
Dear Dr. Maddocks:
Re: 04-087 Bioaccumulation of Metals in Eisenia fetida after Exposure to Metal Loaded Bauxsol
Reagent"
Your paper has been reviewed for publication in Environmental Toxicology and Chemistry (ET&C) and
has been judged:
Acceptable for publication with minor revisions
Acceptable for publication with major revisions X
One of the reviewers that evaluated your original manuscript still has concerns that you did not
adequate address in your re-submission. Specifically, concern was raised regarding the experimental details.
These comments are significant, thus a major revision is required. I would encourage you to pay particular
attention to these comments.
Please consider carefully the comments of the reviewers and modify the manuscript as appropriate.
Revisions should be completed within a three-month period. Submit the original and a copy of the revised
manuscript with a letter stating (in detail) your disposition of each of the reviewers' suggestions, item by item,
indicating the page and line number of the revised text. Highlight the sections that have been changed on the
copy of the revised manuscript to aid the editor in checking revisions. If you wish to reject all or specific
suggestions, please state your reasons. Include an electronic version of the manuscript on a clearly labeled floppy
disk (manuscript number, name of corresponding author). Place electronic versions of the figures in separate files
on the same disk, if these are available.
If the revisions are acceptable, your paper will be scheduled for early publication in ET&C. If your revised
manuscript is not received in my office within three months, it will be rejected for publication. However, the revised
manuscript may be sent to the Editor-in-Chief as a new submission for peer review.
This manuscript should not be returned until necessary editorial changes, which will be sent from
the office of the Editor-in-Chief, have been incorporated into your final, revised manuscript.
Sincerely,

Todd Anderson
Editor
xc: C.H. Ward

MS No. 04-087

Reviewer No.

Title: Bioaccumulation of Metals in Eisenia fetida after exposure to a metal loaded Bauxsol reagent
by Greg Maddocks, Amanda Reichelt-Brushett, David McConchie, and Jaco Vangronsveld
General
Is the subject matter within the general scope of ET&C?
Is new knowledge presented?
Do the title and abstract describe accurately the contents of the paper?
Should the title be shortened?
Are the hypothesis, methods, results, and discussion presented in a clear
and logical way?
Is the manuscript too long?
Are experimental designs, statistical methods, and data-analysis techniques
adequately described?

Yes
Yes
Yes
No
Yes
No
Yes

Tables and Figures

Are all the tables and figures relevant?
Are all columns in tables labeled properly?
Do inconsistencies between tables and figures exist?

Yes
Yes
No

Language
Does the language or spelling need corrections?
Should the paper be returned to the author with instructions to seek
assistance with the language?
Is the message of the author clearly and concisely conveyed by the
language used?
Determining Acceptability and Criteria for Rejection
Is the quality of the science adequate?
Is the scientific methodology flawed?
Are more experiments needed?
Does the experimental work address the aims stated in the introduction?
Do the results support the conclusion?

No
No
Yes

Yes
No
No
Yes
Yes

Rank of Paper
Please rank (1=highest; 5=lowest) the relative importance of the papers
contribution to the field:
Relevance to the field
Scientific merit (quality of the science)
Relative degree of advancement of the field
Ground-breaking research worthy of advance publicity

2
2
3
No

Manuscript Review Form

MS No. 04-087

Reviewer No.

Title: Bioaccumulation of Metals in Eisenia fetida after exposure to a metal loaded Bauxsol
reagent
General Comments
I found this to be generally well-written paper and easy to understand. Lack of page numbers
made reviewing the manuscript more difficult than it needed to be. The authors are reminded to
include page numbers on future submissions. There are several places where there is a subjectverb tense disagreement; in particular data are plural. The manuscript needs to be carefully
reviewed to ensure tense agreement. My specific comments are listed below:
Specific Comments
Comm.
#

Page

Line

3
(Abst)

18

20

22

20

10

16

12

18

Correction/Suggestion
compared the metal concentrations in Eisenia fetida . . .
While TCLP is defined in the previous sentence, I see no such
definition of SEP. Please provide one.
Australia, were . . .
reagent were added . . . Watch proper tense usage throughout
the manuscript.
The outside of the containers was painted . . .
The worms were allowed to depurate gut contents for 48 hours.
The most recent EPA guidance manual on sediment toxicity
testing includes a discussion of depuration periods for the aquatic
oligochaete, Lumbriculus variegates, indicating that depuration
periods exceeding 6 hours may result in loss of material from
tissues for chemicals with low octanol-water partition coefficients,
such as metals. I think this same argument can be made for
terrestrial oligochaetes. Please discuss how a 48-h depuration
period could affect the concentration of metals in tissues.
data were Data are plural.
Simply throwing out outlier data to achieve better r2 values is not
necessarily a very good way to obtain data correlations. Were
outlier statistical tests to determine if discarded values could truly
be considered outliers? Additional explanation of this data
elimination process is warranted.
Please explain why higher MLBR results in decreasing food
mass.

Manuscript Review Form

MS No.04-87

Reviewer No.

Bioaccumulation of metals in Eisenia fetida after exposrue to a metal loaded Bauxsol reagent
Please reference comments by page and line numbers; do not write comments on the manuscript
unless critical to the review process (e. g., sketched changes to illustrations). Please consult
general guidelines on the reverse side and rank the paper from 1 to 5 according to its relative
importance as a contribution to scientific literature
This work examined the accumulation of metals by the worm after exposure to Bauxsol reagent
that contained high metal load. The speciation of metals in the soil was determined using
traditional Tessier et al. sequential extraction method. Correlation was then conducted to
examine the fraction that may control metal bioavailability. The approach is traditional and the
finding that metals were not bioavailable (or very little bioavailable) is not surprising (given that
these metals were essential in granule forms). However, the methodology in conducting the
experiment may have limitations (see below). The writings also have numerous problems.
Given the confusion on data presentations, some of the findings are in fact not clearly discussed.
The authors are encouraged to re-write this paper,with focus on important findings, and
submitted it to other journals for possible publication.
Specific comments
1. Abstract: needs to be modified. Delete the unnecessary sentences (e.g., line 3-7). Combine
the different paragraphs into one paragraph. Start the however changes occurred.., line 16)
with a new sentence.
2. Introduction. Line 6, have a reaction pH of 9.0 is not clear to me. Line 15, inturn should be
in turn; line 18: SEP should be defined (even though it appears in Abstract).
3. Methodology (P4), last line, After mixing the Bauxsol reagent was allowed.. this is not clear.
4. P5. Line 10-22. The worm (12-15 individuals, each 5-7 cm) in 500 ml beakers. This
crowding effect can be a potential serious problem. The mixture of MLBR with cow manure:
did these earthworms select the food, or they ingested the MLBR? These can considerably
affect the experimental results. For example, the low BAF measured in this study may not be
due to the low bioavailability of metals from MLBR, but was due to the very ingestion of these
materials (e.g., reducing the dose to the animals). Without this information, it is in fact difficult to
interpret the experimental results obtained from this study. A look at Table 6 in fact suggests
that the earthworm weight had decreased as compared to the initial exposure. The authors
mentioned that there was no mortality, but growth should be a critical parameter to assess the
toxicity of these materials to the earthworm (or caused by starvation).
5. P6, line 12, at 0 and 28 days. It seems that only 20% MLBR was measured for the
speciation after exposure (see next page line 3).
6. P6, last paragraph and entire P7, these descriptions of methods need to be integrated and
combined. The relationships between metal fraction and metal accumulation was mentioned in
a few different places (P6, line 22, P7, line 19-22).
7. P7, line 18. Table 2 should be Table 3. However, this should be presented in the Results
section.
8. Results, P8, last paragraph. The growth data may be presented here.

9. P9. Line 3. Estimation of bioavailability (EB): What is this and how is it quantified? I am very
confused by Table 4. The data need to be clearly discussed.
10. P9, line 11. Correlations between. This section can be combined with the previous
section to talk about the correlation analysis.
11. P9, line 18. Again, I am also confused by Table 5. r2 is given for which metal? As it
stands, there were 3 replicates for each treatment. How the correlation was conducted for
different treatments? These data need to be clearly presented and discussed.
12. P9, line 24. Delete These data in at the beginning of this sentence.
13. Discussion. P10, bottom, discuss their ingestion behavior. Approximately how much the
earthworm ingest MLBR?
14. P11, line 5-12. Line 16-21. Very poor English.
15. P11, line 23. The growth data should be mentioned. How about the growth dilution? For
example, an increase or decrease in weight may result in dilution or increase in metal
concentration.
16. P12, line 4, should not and did not occur.. should be revised.
17. P12, last paragraph and P13, first paragraph. I am not very convinced about the discussion.
For example, Fe2+ can be rapidly re-oxidized into Fe3+. Cd does not have a strong affinity (line
19). Other metals have a much stronger affinity. Cr in soil is mostly associated with the
residual (lattice fraction), instead of exchangeable fraction, etc. I suggest the authors remove
these speculations.
P13, line 10, Relationships between selective metals.. This discussion can be important, but I
find that 1) line 12-24 looks like a review 2) the correlation can be more mechanistic (P14). For
example, which fraction is most important, whether it increases or decreases accumulation.
P14, Conclusion. Can be condensed. The last paragraph can be deleted.
P15. table 2 should be table 1.
All the table captions should be changed.
Table 3. Perhaps presenting the data in percentages (instead of concentration) such that it will
be easier to make the comparison.
Table 4 and table 5. Very confusing. How these analyses were conducted?

Society of Environmental Toxicology and Chemistry

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