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March 2008<br />

<strong>TREAT<strong>IN</strong>G</strong> <strong>ACIDITY</strong> <strong>IN</strong> <strong>COAL</strong> <strong>PIT</strong> <strong>LAKES</strong> US<strong>IN</strong>G<br />

<strong>SEWAGE</strong> <strong>AND</strong> GREEN WASTE: MICROCOSM <strong>AND</strong><br />

FIELD SCALE TRIALS AT THE COLL<strong>IN</strong>SVILLE<br />

<strong>COAL</strong> PROJECT (QUEENSL<strong>AND</strong>)<br />

By, Dr. Clint McCullough<br />

Dr. Mark Lund<br />

Mr. Joel May


Prepared for,<br />

March 2008<br />

<strong>TREAT<strong>IN</strong>G</strong> <strong>ACIDITY</strong> <strong>IN</strong> <strong>COAL</strong> <strong>PIT</strong> <strong>LAKES</strong> US<strong>IN</strong>G<br />

<strong>SEWAGE</strong> <strong>AND</strong> GREEN WASTE: MICROCOSM <strong>AND</strong><br />

FIELD SCALE TRIALS AT THE COLL<strong>IN</strong>SVILLE<br />

Centre for Ecosystem Management Report No. 2008-03<br />

Australian Coal Association Research Program (ACARP) Project: C14052<br />

Dr. Clint McCullough BSc, MSc (Hons), PhD (Aquatic Ecotoxicologist),<br />

Dr. Mark Lund BSc (Hons), PhD (Aquatic Ecologist),<br />

Mr. Joel May BE (Environmental Engineer).<br />

<strong>COAL</strong> PROJECT (QUEENSL<strong>AND</strong>)<br />

1<br />

By, Dr. Clint McCullough<br />

Dr. Mark Lund<br />

Mr. Joel May


Treating acidity in pit lakes using sewage and greenwaste<br />

1 Executive Summary<br />

• This research project involved, collaboration and technology transfer from research in<br />

Collie (Western Australia) to Collinsville (Queensland).<br />

• Coal mine lakes represent a potentially valuable resource to both the environment and<br />

the community in inland Australia, if the water can be treated (or remediated) to an<br />

appropriate standard for its proposed end use. Beneficial end uses include:<br />

aquaculture, water for irrigation, recreation, and for nature conservation. Research in<br />

Collie coal mine lakes and internationally has found there is considerable potential for<br />

utilising biological processes to reverse acidity generating processes. This approach<br />

focuses primarily on additions of organic material to support sulfate reducing bacteria<br />

(SRB) which convert sulfate back to sulfides, removing acidity and metals in the<br />

process. The approach also fosters a range of other biological processes which can<br />

increase alkalinity and pH.<br />

• Previous ACARP funded research in Collie had tested the use of SRBs for treating<br />

acidic mine waters with limited success. Limiting the effectiveness of this approach in<br />

Collie are low sulfate concentrations that occur in these pit lakes. Nevertheless, there<br />

are a number of highly acidic mine lakes in the Collinsville Coal Project (CCP) with<br />

high sulfate levels.<br />

• CCP discharged 4 ML of highly acidic mine water (typical of their pit lakes) into a 80<br />

ML sewage evaporation pond. CCP and later the authors (CM & ML) monitored the<br />

effects of this discharge on water quality in the ponds. In approximately 18 months<br />

water quality in the evaporation pond had returned to pre-addition conditions. It<br />

appeared that a combination of processes, including SRB activity were responsible for<br />

the remediation of the mine water. The results of this study suggested that SRB<br />

activity might be useful in the treatment of pit lakes on the CCP site.<br />

• This project aims to establish a full scale demonstration of the application of passive<br />

biological remediation in a pit lake on the CCP lease. This pit lake is located near to<br />

the Bowen Shire’s Collinsville Water Treatment Plant (CWTP) and green waste<br />

transfer station. Organic substrate in the form of primary treated sludge from the plant<br />

were be added to the lake. This wastewater provided a ready source of, BOD<br />

3


Treating acidity in pit lakes using sewage and greenwaste<br />

(Biochemical Oxygen Demand, to reduce oxygen levels to those suitable for SRBs),<br />

available carbon (C), and nutrients (N & P). All of these wastewater components have<br />

been identified as key factors promoting SRB activity. Monitoring of this<br />

experimental lake and control lakes both before and after the addition enabled an<br />

assessment to be made of the success of this innovative remediation method.<br />

• The first two experiments using acrylic tubes (microcosms) containing sediment and<br />

pit lake water were established firstly in Collinsville and then in Perth. These<br />

experiments were used to gain a better understanding of the processes responsible for<br />

mine water remediation and to provide estimates of the quantities of organic matter<br />

that were likely to be required in a full-scale treatment of a pit lake.<br />

• The first microcosm experiment involved testing of greenwaste only, sewage only,<br />

and greenwaste and sewage for their effectiveness in remediation of pit lake water, in<br />

typical Collinsville conditions.<br />

• This first experiment clearly showed remediation of pit lake water pH from 2.2 to 5.5<br />

in 145 days, with commensurate declines in iron, aluminium and toxic metal<br />

concentrations. The presence of greenwaste appeared to be important for the<br />

effectiveness of the treatment. This was mainly believed to be due to the bulk of the<br />

greenwaste which extended the area of SRB activity up through the water column.<br />

• The second experiment repeated the first experiment in design but added different<br />

quantities of organic material and a second sewage type. Another important aim of<br />

this experiment was to demonstrate the repeatability of the initial results given the<br />

heterogeneous nature of the organic materials being used.<br />

• This second experiment demonstrated that results were generally reproducible from<br />

the first experiment. However the performance of greenwaste only was poorer with a<br />

pH of >4 reached after 210 days, while the other treatments produced circum-neutral<br />

pH (~7) after 120 days with the exception being low levels of sewage only which<br />

produced a pH of ~6 after 210 days. Associated with the pH improvements were<br />

reductions in electrical conductivity, sulfate and metal concentrations. Key drivers for<br />

rapid remediation appeared too be the high tropical temperatures, the combination of<br />

greenwaste and sewage, and a ‘fresher’ type of sewage from Bowen rather than<br />

Collinsville. This experiment enabled the team to determine the quantities of organic<br />

materials required for a field trial.<br />

4


Treating acidity in pit lakes using sewage and greenwaste<br />

• Comprehensive risk assessments and stakeholder consultation identified significant<br />

occupational health and safety concern of using sewage and greenwaste at field scale<br />

was of high levels of faecal coliforms in the water creating a risk for operators. The<br />

second experiment revealed that after 180 days there were no faecal coliforms in the<br />

water, although total coliforms were high. These latter coliforms were believed to be<br />

associated with decomposition process and were not believed to pose a contact risk to<br />

operators. Nevertheless, precautions were developed for operators involved in the<br />

project.<br />

• The field scale trial followed 15 months of water quality monitoring on three CCP pit<br />

lakes. These data formed part of the before-after-control impact (BACI) design of the<br />

field experiment.<br />

• A review of the data from the second experiment, indicated that given material<br />

availability that a smaller pit lake was need for treatment. In July 2006, it was decided<br />

to split with an earth wall the Garrick Area East pit lake into a smaller 71 ML<br />

(GAEW) for treatment and the remaining 336 ML (GAEE) to be kept as an untreated<br />

control.<br />

• In August 2006 to January 2007, the smaller lake (GAEW) was filled with dried<br />

sewage sludge (60 t), liquid sewage sludge (3,190 t) and municipal green waste<br />

(980 t). Monitoring of this new treatment lake and the remaining control lake and<br />

other control lakes then continued for another 6 months at monthly intervals.<br />

• Due to groundwater influx and heavy cyclonic rainfall events, it was often unclear<br />

what contribution sulfate reduction process have made to changes seen in water<br />

quality. Nevertheless, physico-chemical changes to control lakes during monitoring<br />

could generally be explained as a result of these two external influences. However,<br />

after four months of filling ceasing, GAEW ORP began to decline from around<br />

600 mV to 200 mV starting from the benthos. Also beginning at the benthos, pH<br />

increased soon afterwards reaching a pH of 3.7 across the lowest 3 m of water column<br />

by July 2007. The lower 3 m mean pH of the GAEE lake was 2.2 at this time.<br />

Similarly, at the end of the experiment electrical conductivity was reduced to<br />

9.0 mS cm -1 compared to 9.4 mS cm -1 in the GAEE lake.<br />

• These field chemistry observations suggest that addition of low-grade organic<br />

materials for remediation of acid mine waters at field scale shows promise. However,<br />

5


Treating acidity in pit lakes using sewage and greenwaste<br />

remediation has only just begun and further monitoring is required to access the<br />

degree of treatment that can be achieved and how long this treatment will continue.<br />

6


Treating acidity in pit lakes using sewage and greenwaste<br />

Frontispiece<br />

Figure 1. Joel May taking a post-organic dosing water sample from treatment lake GAEW.<br />

This document should be referenced as follows.<br />

McCullough, C. D.; Lund, M. A. & May, J. M. (2008). Treating acidity in coal pit lakes<br />

using sewage and green waste: microcosm and field scale trials at the<br />

Collinsville Coal Project (Queensland). ACARP Project Report C14052.<br />

Centre for Ecosystem Management Report p2008-03, Edith Cowan<br />

University, Perth, Australia. 112pp. Unpublished report to Australian Coal<br />

Association Research Programme.<br />

7


2 Contents<br />

9<br />

McCullough, Lund and May (2008)<br />

1 Executive Summary 3<br />

2 Contents 9<br />

3 Introduction 11<br />

3.1 Aims 13<br />

4 The Collinsville Coal Project Area 15<br />

5 Effects of adding mine lake water to a sewage evaporation pond 19<br />

5.1 Overview 19<br />

6 Collinsville microcosms - Experiment 1 21<br />

6.1 Background 21<br />

6.2 Methods 24<br />

6.3 Results 26<br />

6.4 Discussion 34<br />

7 Perth microcosms – Experiment 2 37<br />

7.1 Background 37<br />

7.2 Methods 40<br />

7.2.1 Statistical analyses 43<br />

7.3 Results 44<br />

7.3.1 Changes in water quality by Day 180 of the experiment 47<br />

7.3.2 Sediment 50<br />

7.3.3 Changes in water quality during the experiment 53<br />

7.3.4 Bacterial abundances 55<br />

7.3.5 Gases evolved 56<br />

7.4 Discussion 56<br />

8 Field-scale remediation of a tropical acid mine pit lake with<br />

greenwaste and sewage sludge 61<br />

8.1 Background 61<br />

8.2 Methods 63<br />

8.2.1 Risk Assessment 65<br />

8.2.2 Organic dosing 66


Treating acidity in pit lakes using sewage and greenwaste<br />

8.2.3 Sampling 68<br />

8.2.4 Groundwater interactions 68<br />

8.2.5 Pit lakes 69<br />

8.3 Results 69<br />

8.3.1 Climate 69<br />

8.3.2 Dosing with organic material 70<br />

8.3.3 Physico-chemical parameters 72<br />

8.3.4 Metal/metalloid concentrations 79<br />

8.3.5 Nutrients 87<br />

8.3.6 Groundwater interactions 90<br />

8.4 Discussion 95<br />

9 Conclusions 99<br />

10 Acknowledgements 102<br />

11 References 103<br />

12 Appendix: Publications and Presentations arising from ACARP<br />

Project C14052 113<br />

10


3 Introduction<br />

11<br />

McCullough, Lund and May (2008)<br />

Environmental legacies of open cut mining operations are the large voids created. Too large<br />

to backfill and typically requiring extensive dewatering operations to keep dry, many are<br />

destined to become large, deep lakes. In Australia, these new lakes have few natural<br />

counterparts in size (especially depth) and are a potentially valuable new asset to rural<br />

Australia. Despite considerable improvements in mining practices, acid mine drainage<br />

(AMD) resulting from exposed overburden and void walls can result in these new lakes<br />

becoming highly acidic. Worldwide AMD is potentially the largest negative environmental<br />

impact resulting from coal mining (Robertson, 1987; Ryan & Joyce, 1991; Lowson et al.,<br />

1993; Harries, 1998a, b). In Australia there are many well publicised examples of the<br />

consequences of AMD from coal and other mineral mines including Rum Jungle (Northern<br />

Territory), Captains Flat (New South Wales), Brukunga (South Australia), Mount Lyell<br />

(Tasmania), and Mount Morgan (Queensland) (Zhou, 1994; Lawton, 1996).<br />

Extremely elevated aluminium, iron and sulfate concentrations, combined with extremely low<br />

dissolved carbon and other nutrients, are typical of AMD (Castro et al., 1999; Peiffer et al.,<br />

1999; Fyson, 2000; Woelfl, 2000; Taylor & Waters, 2003). Dissolved metal concentrations<br />

may be so high as to be toxic to most aquatic biota (Spry & Wiener, 1991; Bowell, 2000).<br />

Although literature is sparse for sulfate toxicity (ANZECC/ARMCANZ, 2000a),<br />

concentrations can also reach potentially toxic levels in these lakes. However, acid mine<br />

drainage (AMD) waters also differ greatly between regions and geologies (Robb & Robinson,<br />

1995; Johnson & Hallberg, 2003).<br />

Australian data on remediation techniques specific to our pit lakes is sparse. The expensive<br />

and high-maintenance operations of active remediation strategies (e.g. liming, anoxic<br />

limestone drains) are often not appropriate to the remoteness, high dissolved metal<br />

concentrations and high acidity of many Australian mine lakes (Brown et al., 2003; Taylor &<br />

Waters, 2003). Furthermore, although dealing with low pH issues of AMD waters, active<br />

remediation strategies are often not efficient at removing high dissolved concentrations of<br />

metals such as iron and aluminium, or sulfate.


Treating acidity in pit lakes using sewage and greenwaste<br />

In natural systems and in old mine lakes which have accumulated organic materials in the<br />

sediments, sulfate is removed by SRB reduction in carbon-rich and anaerobic conditions<br />

producing hydrogen sulfide (Frömmichen et al., 2003). Hydrogen sulfide is chemically<br />

highly reactive and binds strongly to heavy metals such as iron, copper, cadmium and zinc<br />

forming insoluble precipitates (Kleeberg, 2000; Brown et al., 2003). Furthermore, elevated<br />

metal ions may also be removed by direct sorption and complexation to organic matter<br />

(Peiffer et al., 1999; Fyson, 2000).<br />

Controlled organic enrichment (saprobisation) of lake sediments in laboratory microcosm<br />

experiments has been found to increase pH and decrease acidity as a result of SRB processes<br />

(Castro et al., 1999; Frömmichen et al., 2003). Sulfate and iron reducing bacteria are a<br />

diverse and ubiquitous group of micro-organisms (Johnson & Hallberg, 2003). However,<br />

their activity is directly limited by the low carbon availability typical of waters in acid pit<br />

lakes (Kafper, 1998). In addition, to sufficient available carbon SRB require an anoxic (no<br />

oxygen) environment to reduce sulfate. In many pit lakes, which stratify over summer, the<br />

hypolimnion (bottom waters) can take a considerable time to become anoxic due to low<br />

biological oxygen demand (BOD) in the sediments (Boland & Padovan, 2002). Addition of<br />

organic matter can provide available carbon and high BOD providing suitable conditions for<br />

SRB activity (Klapper et al., 1998). Most of the research into organic matter additions has<br />

come from the northern hemisphere and has focused on expensive and largely unavailable<br />

sources of carbon for an Australian mine site; such as glucose, ethanol, molasses, whey,<br />

potato processing waste and cattle effluent (Castro et al., 1999; Frömmichen et al., 2003).<br />

Nonetheless, other than establishing that there is a requirement for an easily accessible supply<br />

of carbon, little is understood about differences in the quality of organic substrate for<br />

bacterially-mediated sulfate reduction (Blodau et al., 2000).<br />

In Collie (Western Australia) pit lakes, experiments have trialled a number of organic matter<br />

types in experiments at scales ranging from laboratory, to ponds to mesocosms in pit lakes<br />

(Lund et al., 2000; Phillips et al., 2000; Lund, 2001). Readily available organic materials<br />

such as mulch, hay, manure (cow) and sawdust have been tested (Thompson, 2000).<br />

Although there have been noticeable improvements in biodiversity within the experiments<br />

with organic matter additions, there has been little long term change in pH. This has been<br />

12


13<br />

McCullough, Lund and May (2008)<br />

attributed to low sulfate concentrations (typically


Treating acidity in pit lakes using sewage and greenwaste<br />

The project team undertook the following projects:<br />

• Assessment of the capacity for a sewage evaporation pond to treat acidic pit lake<br />

water.<br />

• Assessments in microcosms of the efficacy of sewage and greenwaste to treat acidic<br />

pit lake waters in Collinsville.<br />

• Field scale trial of the use of sewage and greenwaste to treat a pit lake in Collinsville.<br />

14


4 The Collinsville Coal Project Area<br />

15<br />

McCullough, Lund and May (2008)<br />

Collinsville is a typical small inland Australian mining town located approximately 70 km<br />

from the coast of North Queensland, Australia (Figure 4.1). Together with the mining town of<br />

Scottville, Collinsville is located within a kilometre of the active mining Collinsville Coal<br />

Project coal mining lease (Figure 4.2). Collinsville was underground (bord and pillar) mined<br />

for its coal as early as 1919 at the State Mine working the Bowen Seam, and began open-cast<br />

mining in the mid 1950s. Mining operations are expected to continue until at least 2013. The<br />

combined population of Collinsville and nearby Scottville in 2006 was 2,664 people and is<br />

undergoing growth as mining activity increases.<br />

Figure 4.1 Location of the study site in Collinsville, North Queensland, Australia.


Treating acidity in pit lakes using sewage and greenwaste<br />

Figure 4.2. CCP Project Lease pit lakes and surrounding towns.<br />

Collinsville has a semi-arid tropical climate with a rainfall regime that falls into a transition<br />

between sub-humid and semi-arid. The climate is dominated by a moderately low, highly<br />

episodic and unreliable summer rainfall (708 mm/annum) and a very high evaporation rate<br />

(1,860 mm/annum) (Commonwealth of Australia Bureau of Meteorology, 09/02/2005;<br />

Davies & Willcocks, 1992) (Figure 4.3).<br />

Figure 4.3. Mean temperature and rainfall climate of Collinsville (Commonwealth of Australia Bureau of<br />

Meteorology, 09/02/2005).<br />

16


17<br />

McCullough, Lund and May (2008)<br />

The geology of the region is of highly weathered hard rocks with soils of very low organic<br />

carbon content. Surrounding vegetation is predominantly Eucalyptus and Acacia spp.<br />

dominated open woodland with an annual grass understory. There are some 20 pit lakes in the<br />

CCP lease, all of which are acidic with high concentrations of dissolved solutes. All of these<br />

lakes are of extremely low pH (ca. pH 2) and contain high concentrations of dissolved solutes<br />

(electrical conductivity = 9–19 mS cm -1 ). One of these acid pit lakes, Garrick Area East<br />

(GAE), is the focus of this study due to its proximity to the Collinsville waste water treatment<br />

plant and green waste dump (


Treating acidity in pit lakes using sewage and greenwaste<br />

Figure 4.5. Garrick Area East pit lake at CCP. Note very dark orange colour of water due to high dissolved<br />

iron concentrations (pH = ca.2, dissolved iron concentration = 1,100 mg L -1, electrical<br />

conductivity = ca.9 mS cm -1 ), and efflorescence of elemental sulfur, gypsum and epsomite around<br />

littoral fringe.<br />

18


19<br />

McCullough, Lund and May (2008)<br />

5 Effects of adding mine lake water to a sewage<br />

evaporation pond<br />

The project team has been involved in another project at Collinsville that, while outside this<br />

ACARP project, contributed to its development. Unfortunately as this work has been<br />

published elsewhere it cannot be included here. We have included an overview to illustrate<br />

why we had confidence that the use of sewage and greenwaste was likely to be successful.<br />

5.1 Overview<br />

The addition of acidic mine water to raw sewage and workshop wastewaters in an<br />

evaporation pond provided an opportunity for a field-scale experiment as essentially a<br />

reversal of in-situ treatment of acidic pit lakes by addition of organic carbon. The hyper-<br />

eutrophic evaporation pond initially contained high concentrations of nutrients, a pH >8, high<br />

levels of sulfate (500 mg L -1), and had regular algal blooms. Soon after the addition of the<br />

AMD pit water, the evaporation pond pH fell to 2.4, and electrical conductivity (EC) and<br />

most metal concentrations were elevated by one to two orders of magnitude. Over the<br />

following 18 months, the pH of the pond increased and the EC and metal concentrations<br />

decreased. After only 18 months of addition of AMD, pond water quality had returned to a<br />

level similar to that before AMD addition. These observations suggest that addition of low-<br />

grade organic materials shows promise for remediation of acid mine waters at field scale and<br />

warrants experimental investigation.<br />

McCullough, C. D.; Lund, M. A. & May, J. (in press). Field scale demonstration of the<br />

potential for sewage to remediate acidic mine waters. Mine Water and<br />

Environment 27(1). DOI: 10.1007/s10230-007-0028-y


6 Collinsville microcosms - Experiment 1<br />

A version of this chapter has been published without copyright restrictions as:<br />

21<br />

McCullough, Lund and May (2008)<br />

McCullough, C. D.; Lund, M. A. & May, J. M. (2006). Microcosm testing of municipal<br />

sewage and green waste for full-scale remediation of an acid coal pit lake, in<br />

semi-arid tropical Australia. Proceedings of the 7th International Conference on<br />

Acid Rock Drainage (ICARD). St Louis, Massachusetts, USA. 1177-1197.<br />

6.1 Background<br />

Microbial sulfate reduction is considered to be an efficient and effective remediation for the<br />

treatment of acid mine drainage (AMD), through alkalinity production and precipitation of<br />

metals as sulfides through reaction with sulfide cations (Equation 1) and as carbonates<br />

through increased pH (Equation 2) (Dillon et al., 1997; Küsel & Dorsch, 2000; Benner et al.,<br />

2002; Praharaj & Fortin, 2004). In-lake neutralisation via sulfate reduction is expected to play<br />

a key-role in the remediation of acidic mining pit lakes (Kleeberg, 1998). However, since<br />

Tuttle et al. (1969) first suggested the use of sulfate reducing bacteria (SRB) in the treatment<br />

of AMD, treatment has largely focused on ex-situ treatment in bioreactors. What in-situ<br />

treatment relevant experiments that have occurred have generally been performed at<br />

microcosm (e.g., carboy vessels; (Fyson et al., 1998; Castro et al., 1999; Frömmichen et al.,<br />

2004)) or at best macrocosm (e.g., limnocorrals) scales (Martin et al., 2003). Only recently<br />

has attention switched to in-situ remediation systems at actual field treatment scales (Gibert<br />

et al., 2002).<br />

Equation 1 Metal 2+ + SO4 2- + 2C(organic) → MetalS + 2CO2<br />

Equation 2 Metal 2+ + CO3 2- → MetalCO3<br />

A review by Gibert et al. (2002) found that the nature of the organic matter was a prime<br />

determinant of the efficacy of the passive treatment system. For example, the availability of


Treating acidity in pit lakes using sewage and greenwaste<br />

carbon from plant matter is dependent upon decomposition, which is extremely limited in<br />

acidic and anoxic conditions (Harris & Ragusa, 2001). To this end, Waybrant et al. (1998)<br />

found mixtures containing multiple sources of organic matter demonstrated higher sulfate<br />

reduction rates than those of single sources. Castro and Moore (1997) observed that,<br />

“Therefore, for economic feasibility the added organic matter must be cheap and locally<br />

available.” Hard et al. (2003) echoed this view noting that, “For a microbial process to be<br />

economically feasible, the carbon and energy source should be cheap, widely available and<br />

highly effective.” However, most experiments into the utility of sulfate reduction processes<br />

for ameliorating AMD have instead focused upon highly labile but expensive carbon<br />

substrates such as ethanol (Kolmert & Johnson, 2001; Martin et al., 2003; McNee et al.,<br />

2003), sugar (Pöhler et al., 2002; Wendt-Potthoff et al., 2002; Frömmichen et al., 2003;<br />

Geller et al., 2003; Frömmichen et al., 2004), cow manure (Drury, 1999, 2000), etc. For<br />

many remote mining locations, these materials are unviable for practical and economic<br />

reasons. The only bulk carbon sources likely to be available in these areas will be municipal<br />

sewage, and green waste (including a broad range of plant material collected by local<br />

government from domestic and municipal lawns and gardens).<br />

Using readily-available and economically-viable sources of organic materials, Waybrant et al.<br />

(1998) found all of the eight organic matter types they tested reduced sulfate, with sewage<br />

sludge the fastest to achieve high levels of sulfate reduction. The mixture of sewage sludge<br />

and green waste (leaf mulch, woodchips and sawdust) reduced 4,500 mg L -1 of sulfate to<br />

3 within 30 days of SRB activation and simultaneously decreased<br />

divalent metal concentrations. This mixture proved more effective in ameliorating pH and<br />

metal concentrations than either sewage sludge (little response) or plant material (nil<br />

response). Gusek (2002) even suggested injecting sewage sludge into mine shafts and adits to<br />

remove and prevent production of acidity from these sources.<br />

22


23<br />

McCullough, Lund and May (2008)<br />

More specific data for our particular study area was reported in a 1993 study at the<br />

Collinsville Coal Project Mine in North Queensland, Australia (Fallon, 1994). Although<br />

unquantified, this report details findings that the extremely acid waters of Blake A-cut had<br />

“notably improved” (i.e. reduced acidity, sulfate and metal concentrations) and suggested that<br />

one mechanism may be bacterially-mediated sulfate reduction occurring with the sewage<br />

effluent discharged into this pit being used as a source of carbon. As rates of SRB activity are<br />

enhanced at warmer temperatures, we expect that the warmer tropical conditions of<br />

Collinsville will enhance activity especially compared to that described in the majority of<br />

published literature which is from the cooler temperate regions of Europe and North America.<br />

Consequently, there is a large body of published data to suggest that bacterially-mediated<br />

sulfate reduction processes can ameliorate acid mine drainage waters. Published literature<br />

from laboratory and mesocosm experiments also indicates that sewage is suitable for use as<br />

an organic substrate stimulating sulfate reduction. However, there are few published reports<br />

of field scale attempts of AMD lake remediation. Furthermore, very little bioremediation<br />

work has been carried out on the mining pit lakes of Australia using these methods, especially<br />

in semi-arid tropical Australia where a significant number of acid pit lakes historically occur<br />

and are still being developed of increasing sizes (Harries, 1997). As an arid continent with<br />

increasing pressure on water resources, there is growing demand for new sources of water to<br />

meet a variety of end uses (Doupé & Lymbery, 2005).<br />

The end use of many of these pit lakes may also often be only for slightly remediated water<br />

quality of lower salinity for mining operation dust suppression or similar industrial use.<br />

Consequently, financially viable treatment to this lower standard may still be very achievable<br />

in even remote mining areas. Consequently, this first experiment was intended to test the<br />

potential of using sewage and greenwaste in concert or individually to remediate GAE pit<br />

lake water.


Treating acidity in pit lakes using sewage and greenwaste<br />

6.2 Methods<br />

Microcosm experiments were designed to mimic the hypolimnetic water column and<br />

sediment regions of a typical strongly stratified Collinsville pit lake. Twelve clean 100 mm<br />

diameter and 600 mm long (4.5 L) acrylic tubes were set up in an uninsulated laboratory on<br />

the mine site as microcosms containing 140 mm of sediment and 440 mm of GAE pit lake<br />

water. Cores were pushed into the littoral sediment of GAE to a depth of 200 mm and sealed<br />

with rubber bungs at the top and bottom. The height of sediment in the bottom of the core<br />

was then adjusted by sliding it downwards out the bottom of the core to a final depth of<br />

140 mm across all cores. Three replicate cores were then allocated to each of the following;<br />

control (untreated), green waste only (G), sewage (S), or green waste and sewage (GS) at<br />

dosing rates realistic of that able to be achieved in a typical CCP pit lake using regional<br />

sources for several month’s filling.<br />

Green waste was sourced from the Collinsville shire green waste dump nearby the<br />

Collinsville Coal Project lease. Greenwaste consisted of a wide range of garden clippings<br />

from both woody and herbaceous species that had been exposed to Dry season drying<br />

climatic conditions for some weeks. Primary-treated sewage sludge was sourced from the<br />

Collinsville Municipal Wastewater Treatment Plant. Due to the over-capacity of the plant for<br />

the declining town size, the sewage sludge had been exposed to the sun in drying beds for<br />

around 12 weeks.<br />

The cores were then filled with GAE water to within 100 mm of their brim, green waste was<br />

then added where appropriate, and then sewage in the following scheme (Table 6.1).<br />

Microcosm core water levels were topped-up to with 20 mm of the core’s brim and a loose-<br />

fitting rubber bung was applied to the top (not airtight) to reduce air infiltration into the core<br />

water as would a strongly stratified epilimnion (Figure 6.1). The entire suite of microcosm<br />

cores were then placed in a 500 mm high opaque black plastic planter tub which was filled<br />

with water to evenly distribute ambient temperatures between cores and to reduce the<br />

incidence of leakage. The lower water-filled tub was then capped with an identical inverted<br />

planter tub to occlude light, as PAR levels are extremely low in the hypolimnion of these<br />

lakes (author’s unpublished data).<br />

24


25<br />

McCullough, Lund and May (2008)<br />

The cores were then sampled for the physico-chemical variables; temperature, pH specific<br />

conductance, oxidation-reduction potential and dissolved oxygen (% saturation and mg/L)<br />

with a Hydrolab Quanta multiparameter meter.<br />

Table 6.1. Experimental design for organic dosing of pit lake cores.<br />

Treatment level Organic dosing mass Water:green Number of<br />

(g)<br />

waste:sewage ratio replicates<br />

Control 0 1:0:0 3<br />

Green waste 200 16:1:0 3<br />

Green waste and sewage 100 and 200 32:1:2 3<br />

Sewage 200 16:0:1 3<br />

Figure 6.1. Microcosm cores on day 0. Treatment allocations from left to right are control, green waste,<br />

sewage and green waste and sewage.<br />

Physico-chemical measurements were taken at one day after filling, two days after, and then<br />

at approximately weekly intervals thereafter for 145 days.<br />

A 100 mL water sample was taken after 82 days and analysed for concentrations of solutes.<br />

Cations (aluminium, arsenic, bromine, calcium, cadmium, chromium, cobalt, copper, iron,<br />

lead, magnesium, mercury, sulfate, selenium, silica, tin, zinc) were analysed via ICP-AES.


Treating acidity in pit lakes using sewage and greenwaste<br />

Ammonia and NOx (nitrate and nitrite) anions were analysed on an auto-analyser using the<br />

Berthelot and persulfate digestion methods respectively, with subtraction (APHA, 1998).<br />

Primary treated municipal sewage was collected from drying beds of the Collinsville Water<br />

Treatment Plant. Due to a very low output from the plant, this material had been dried for<br />

around 12 weeks and was thus of an extremely low water content (specific<br />

density = 1.35 kg/L). A sample from this sewage was taken for analysis.<br />

Green waste (specific density = 1.2 kg/L) was collected from the Collinsville green waste tip.<br />

This material was largely representative of Australian garden waste and included lawn<br />

clippings, palm fronds and other leafy and woody material. Green waste was chopped into<br />

approximately 50 mm sections to fit into the cores. A representative sample of green waste<br />

was prepared in Perth (where the chemical analysis was conducted) from similar local plants<br />

and was dried at 25 o C for one week to simulate ambient conditions at Collinsville municipal<br />

green waste dump. The sewage and green waste samples were then analysed for total<br />

nitrogen, total phosphorus and total organic carbon content as well as for dissolved heavy<br />

metals<br />

6.3 Results<br />

Garrick East pit lake had a very low pH and high total iron concentrations indicative of an<br />

iron buffered system (Table 6.2), with heavy metals at environmentally toxic concentrations<br />

(ANZECC/ARMCANZ, 2000b). Nutrient levels were also very low in this pit lake;<br />

especially for phosphorus as is typical of AMD waters (Lessmann et al., 2000; Borg & Holm,<br />

2001).<br />

Collinsville sewage sludge was high in sulfur (10 g kg -1 ) and also contained notable levels of<br />

aluminium (17 g kg -1 ), iron, calcium and magnesium. However, concentrations of some<br />

heavy metals including zinc (1,500 mg kg -1 ) and nickel (39 mg kg -1 ) were also surprisingly<br />

high. S was moderately high in nitrogen (31 mg kg -1 ) and phosphorus (12 mg kg -1 ), had<br />

26


27<br />

McCullough, Lund and May (2008)<br />

relatively high organic carbon content (29%) and contributed significant alkalinity to the<br />

dosed AMD water as indicated by the alkaline pH paste test (Table 6.2).<br />

Although G contributed less alkalinity to the AMD water, it contained the highest percentage<br />

of organic carbon (39%) (Table 6.2). G also contained moderate amounts of sulfur (1,700 mg<br />

kg -1), nitrogen (20 mg kg -1) and phosphorus (2.3 mg kg -1). Although calcium and magnesium<br />

levels were higher in G compared to S, heavy metal concentrations were very low.<br />

Table 6.2. Chemistry of GAE pit lake water and organic materials used in core experiments.<br />

Parameter GAE water<br />

(mg L -1 )<br />

Sewage<br />

(mg kg -1 )<br />

Total sulfur No data 10,000 1,700<br />

Green waste*<br />

(mg kg -1 )<br />

Sulfate 2,610 No data No data<br />

Total nitrogen 0.51 П 31 П 20<br />

Total phosphorus


Treating acidity in pit lakes using sewage and greenwaste<br />

Although the control treatment looked largely unchanged over the course of the experiment,<br />

G had darkened considerably; probably through leaching of labile organic material and with a<br />

sweet odour indicative of fermentation processes. The presence of this process was further<br />

reinforced by the development of a blue-green coloured mould on the surface of both G and<br />

on GS throughout the experiment (Figure 6.2). S became more orange in colour, although<br />

when inspected from above this was found to be due to a precipitate (probably iron) settling<br />

on the inside of the acrylic tube. The water in S appeared to have lost the orange tinge which<br />

the control cores still retained. The space between the GS and the sediment surface began to<br />

blacken in GS after only a few weeks of the experiment beginning. After Castro et al. (1999),<br />

this black material was assumed to be ferrous sulfides from the activities of sulfate reducing<br />

bacteria, as the space above the mesocosm sediments of this treatment which were likely to<br />

be anaerobic. A strong sulfide smell, (confirmed as hydrogen sulfide using an ITX- Industrial<br />

Scientific Multigas Meter), also evolved as the black precipitate extended upwards through<br />

the mesocosm above GS solids. This smell and the presence of black precipitate indicated<br />

that sulfate reduction was occurring in these GS treatments.<br />

Two days after addition of organic substrates to AMD cores there was a statistically<br />

significant mean increase in pH above the control for the treatments of GS, and S<br />

(F 3,8 = 23.060, p0.05). All treatments also showed a significant decrease in redox<br />

compared to the control (F 3,8 = 16.673, p = 0.001).<br />

Figure 6.2. Mould growing on the surface of green waste-only cores at day 72.<br />

28


29<br />

McCullough, Lund and May (2008)<br />

Figure 6.3. Microcosm core mean pH and redox potential on day 2 after addition of organic substrates. Error<br />

bars indicate single standard errors of the mean. Bars with same letter are not significantly<br />

different, bars with different letter are significantly different (p


Treating acidity in pit lakes using sewage and greenwaste<br />

(i.e., day 37). Although treatments containing sewage were very variable between replicates,<br />

both treatments containing sewage appeared to decline in solute concentrations greater than<br />

did green waste alone.<br />

Figure 6.4. Change in a). pH, and b). specific conductance, of core microcosm treatment levels over time.<br />

Error bars indicate single standard errors of the mean.<br />

30<br />

a).<br />

b).


31<br />

McCullough, Lund and May (2008)<br />

Aside from iron and magnesium which increased in the G treatment; and cadmium, calcium,<br />

copper, lead and zinc which increased in the S treatment, other solutes had decreased in all<br />

treatments by day 86 (Figure 6.5). However the only statistically significant difference<br />

(P


Treating acidity in pit lakes using sewage and greenwaste<br />

Figure 6.5. Day 86 concentrations of a). major, and b). minor, analytes for each treatment level. Error bars<br />

indicate single standard errors of the mean.<br />

32<br />

a).<br />

b).


33<br />

McCullough, Lund and May (2008)<br />

A Principal Components Analysis (PCA) indicated that addition of organic matter appeared<br />

to increase the variability of water chemistry parameters over that of the control (Figure 6.6).<br />

There also appeared to be synergistic effects on variability with the combined GS treatment<br />

producing the most varied response between replicates. Addition of green waste moved the<br />

water chemistry primarily along the first principal component axis, addition of sewage<br />

separated along the second principal component axis. After 86 days, addition of sewage was<br />

correlated with increases in dissolved concentrations of the heavy metals cadmium, copper,<br />

lead and zinc; and ammonia. Addition of sewage was correlated with decreases in iron,<br />

chromium, sulfate and electrical conductivity. Addition of green waste was correlated with<br />

increases in pH and with decreases in dissolved oxygen, redox, aluminium, nickel, sulfate<br />

and selenium. Nevertheless, although more variable, water chemistry correlations with green<br />

waste and sewage were very similar to green waste.<br />

Figure 6.6. PCA of day 86 microcosm core solute concentrations and physico-chemistry. Vectors indicate<br />

variables contributing │>0.25│ to an eigenvector. Ellipses represent range of variation within<br />

treatment levels.


Treating acidity in pit lakes using sewage and greenwaste<br />

6.4 Discussion<br />

The decrease in sulfate concentrations in all of the treatment microcosms provides further<br />

support for biological sulfate reduction occurring at varying rates and removing cations as<br />

precipitates in the dosed mesocosms. However, the success of sulfate reduction in low pH<br />

waters appears to be contrary to Postgate’s (1984) assertion that sulfate reducing bacteria<br />

(SRB) activities only occur at pH >5. Nevertheless, published studies some time ago have<br />

reported SRB activity at pH values below this threshold. For example, SRB activity in an<br />

acid lake has been found by Herhily and Mills (1985) at pH 2.5, and at pH 2.7 by Gyure et al.<br />

(1987). In these studies and our own, it appears that slightly-acid microclimates, facilitated in<br />

part by alkalinity produced through some sulfate reduction, enabled sulfate reducing bacteria<br />

to survive and to chemically reduce sulfate, producing alkalinity as part of this biological<br />

process (Küsel & Dorsch, 2000; Küsel et al., 2001).<br />

Depending on its source, sewage sludge can contain high concentrations of heavy metals<br />

(Berrow & Webber, 1971). This is especially so of cadmium, which is often concentrated in<br />

sewage sludge from vegetables which have been fertilised with inorganic phosphates; a<br />

common application in depauperate Australian soils (Nursita et al., in press). Unexpectedly<br />

for a non-industrial content sewage source, the Collinsville sewage also displayed high<br />

concentrations for nickel, lead, and zinc. However, these high heavy metal concentrations are<br />

still unlikely to present a problem over a longer remediation time. Along with iron, these<br />

toxic heavy metals are expected to precipitate out of solution by reaction with hydrogen<br />

sulfide, such that their toxic effect is removed from the water column to levels lower than<br />

observed at day 86. Further reduction in biological availability is likely to occur through<br />

formation of complexes with organic chelators present as components of the refractory green<br />

waste, such as organic acids (Tipping & Hurley, 1992). Nevertheless, the contribution that<br />

organic materials may make to the overall heavy metal burden of a pit lake needs to be<br />

considered in any remediation project. This concentration of heavy metals presents an<br />

opportunity for minerals reprocessing, one which other mining companies (including Xstrata<br />

PLC. LTD. involved in this project) are investigating (Zinck, 2006). This study found a<br />

straight green waste treatment performed similarly to that of green waste and sewage, with<br />

fewer heavy metals contributed to the water column. In this respect, remediation strategies<br />

34


35<br />

McCullough, Lund and May (2008)<br />

may be best placed by choosing green waste as the bulk contribution to electron donors over<br />

that of sewage. As discussed, green waste also has an additional advantage of providing<br />

organic substances such as humic and fulvic acids, with which heavy metals may directly<br />

complex to. Ligand formation between heavy metals and refractory organics will further<br />

remove these toxic components from biological availability, albeit at a likely reduced<br />

capacity to that of sulfate reduction processes (Brown Jr., 2001).<br />

The initiation of alkalinity production in green waste and green waste and sewage in only<br />

37 days is likely to be due to a combination of two important factors unique to this study.<br />

Firstly, most other research published to date has occurred in cool temperate areas of Europe<br />

and North America e.g., (Küsel & Dorsch, 2000; Küsel et al., 2001; Benner et al., 2002;<br />

Tostche et al., 2003; Frömmichen et al., 2004). The higher temperatures experienced in<br />

Collinsville, even during the middle of the Dry season (19.5–28.2 o C) are likely to have<br />

exponentially increased biochemical rates of carbon diagenesis and metabolism. Seasonal<br />

change in ambient temperatures has also been identified as limiting rates of sulfate reduction<br />

in some experiments with reduced rates of sulfate reduction occurring over cooler seasonal<br />

periods (Gammons et al., 2000; Benner et al., 2002).<br />

Secondly, the use of largely fresh green waste as opposed to refractory organic substrates<br />

such as straw (Frömmichen et al., 2003; Frömmichen et al., 2004), rye grass (Harris &<br />

Ragusa, 2000, 2001), etc., distinguishes this research from many others in the published<br />

literature. The greater labile fraction of organic material available in this fresher material may<br />

have contributed directly to electron donors for sulfate reduction. For example, chlorophyll<br />

was seen to be leached from the green waste and it is likely that highly labile sap sugars<br />

would have leached also. Consequently, the use of fresh green waste to acid pit lakes, with or<br />

without complementary additions of sewage, may prove to be a novel practicable remediation<br />

strategy for AMD issues in remote mining locations.


7 Perth microcosms – Experiment 2<br />

7.1 Background<br />

37<br />

McCullough, Lund and May (2008)<br />

Open-cut mining can create pits that are below the natural watertable. Once dewatering<br />

operations stop, these pits will form pit lakes as surface and groundwaters equilibrate (Castro<br />

& Moore, 1997). Mining can lead to the exposure of rock strata to weathering which can<br />

result in acidification and metal contamination of contacting waters as in Acid Mine Drainage<br />

(AMD) (Banks et al., 1997). Receiving environments for AMD typically have reduced<br />

environmental and social values, and the resultant water is less valuable as a resource to the<br />

mining company (McCullough & Lund, 2006). Acid Mine Drainage is arguably the greatest<br />

environmental problem facing water management in the international mining industry today<br />

(Gray, 1997; Harries, 1998a). The large quantities of water in pit lakes potentially represents<br />

a potentially valuable resource to mining companies, the environment and community; if<br />

appropriate water quality can be achieved (Doupé & Lymbery, 2005; McCullough & Lund,<br />

2006).<br />

Sulfate reducing bacteria (SRB) can reverse the acidification process by converting sulfates<br />

to sulfides in low redox environments when supplied with labile carbon sources (see King et<br />

al, 1974). Dissolved metals can bind with sulfides or ultimately carbonates to form insoluble<br />

precipitates increasing pH.(Dillon et al., 1997; Hard et al., 1999; Küsel & Dorsch, 2000;<br />

Benner et al., 2002; Praharaj & Fortin, 2004). Tuttle et al. (1969) first suggested the use of<br />

SRB in the treatment of AMD. However, most large scale applications of the approach have<br />

focused on ex-situ treatment in bioreactors or interceptions of contaminated flows such as<br />

anoxic limestone drains and successive alkalinity producing systems. King et al. (1974)<br />

describes the recovery of acid strip mine lakes through the natural accumulation of organic<br />

matter. On this basis they advocated the acceleration of the natural process through additions<br />

of bulk organic matter such as sawdust, wheat straw, newspaper, manure, and wastewater<br />

sludge. In-lake neutralization via sulfate reduction is expected to play a key-role in the<br />

remediation of acidic mining pit lakes (Kleeberg, 1998).


Treating acidity in pit lakes using sewage and greenwaste<br />

A review by Gibert et al. (2002) found that organic matter type was the prime determinate of<br />

the efficacy of SRB treatment systems, providing both a suitable redox environment and<br />

carbon source (Harris & Ragusa, 2000, 2001; Gibert et al., 2002; McCullough et al., 2006).<br />

The availability of carbon from plant matter is dependent upon the rate of decomposition,<br />

which can be extremely limited in acidic and anoxic conditions (Harris & Ragusa, 2001).<br />

Castro and Moore (1997) and Hard et al. (2003) observed that in many sites, the viability of<br />

this approach required an organic matter source that was effective, economical and locally<br />

available. This issue is particularly acute in remote mine sites, which prompted Lund et al.<br />

(2006) to trial Local Council mulch for remediation of a regional Australian pit lake. In many<br />

remote mining locations, the only bulk carbon sources likely to be available in large<br />

quantities are sewage from the site or support town, and green waste (a broad range of plant<br />

material collected through clearing of areas on the mine or in the towns from domestic and<br />

municipal lawns and gardens and also plant material from clearing of native vegetation as<br />

part of open cut mining process) (McCullough et al., 2006). Testing similar bulk materials in<br />

permeable reactive barriers, Waybrant et al. (1998) found they successfully reduced sulfate,<br />

with sewage sludge the fastest to achieve high levels of sulfate reduction. Testing in<br />

bioreactors, Harris and Ragusa (2000) also found a mixture of sewage sludge and plant<br />

material (fresh rye grass) was effective in laboratory experiments at increasing pH (2.3 to<br />

>3), reducing acidity and divalent metal concentrations of AMD waters through sulfate<br />

reduction within 30 days. The combined mixture proved more effective in ameliorating pH<br />

and metal concentrations than either sewage sludge (little response) or fresh plant material<br />

(nil response) on their own.<br />

Potential problems with in situ treatment of AMD affected pit lakes include Postgate’s (1984)<br />

assertion that SRB activities only occur at a pH>5. However, Herhily and Mills (1985) found<br />

SRB activity in a lake at pH 2.5, and Gyure et al. (1987) in a lake at pH 2.7. McCullough et<br />

al. (2008) recorded remediation of pH 2.4 pit lake waters by SRB activity in a sewage<br />

evaporation pond. It appears that less acidic microenvironments in the system can allow SRB<br />

activity to occur and this activity sustains and increases the size of the microenvironment<br />

(Küsel & Dorsch, 2000; Küsel et al., 2001). Peine et al. (2000) found that in German pit lakes<br />

that acidification of the lakes was maintained by the establishment of an acidity driven iron<br />

cycle. This cycle is dependant on the formation of the mineral Schwertmannite, constant<br />

38


39<br />

McCullough, Lund and May (2008)<br />

input of Fe 2+ and no SRB activity below pH of 5.5. In this model, the benefits of addition of<br />

organic matter to the sediment would eventually be overcome as the cycle became<br />

established. Other issues that might reduce the effectiveness of this approach to treatment are<br />

large inputs of acidity from the catchment.<br />

Very little bioremediation work has been carried out on mining pit lakes in Australia<br />

(Harries, 1997). As an arid continent, the effects of drought and climate change pose<br />

particular challenges for mining companies as heavy water users such that in some areas<br />

water is becoming as valuable as the ore (P. Lilly, AUSIMM, pers. comm.). Therefore there<br />

is a growing demand for new sources of water to meet a variety of end uses (Doupé &<br />

Lymbery, 2005; McCullough & Lund, 2006).<br />

At CCP, water availability for the operation is a priority concern due to competing demands<br />

for the main water source (Bowen River). Treatment of pit lake water even to only marginal<br />

quality would reduce pressure on other sources of water (including the Bowen River) for uses<br />

such as dust suppression (McCullough and Lund, 2006).<br />

In Chapter 6, we demonstrated in a pilot study in Collinsville that sewage and greenwaste in<br />

combination had the potential to successfully treat GAE mine lake water. The aim of<br />

Experiment 2 in Chapter 7, which was conducted in Perth (under more controlled conditions)<br />

was to demonstrate that the positive effects were reproducible, determine whether reduced<br />

quantities of organic material would be equally effective and investigate the mechanisms<br />

responsible for the improvements more closely. Furthermore in Experiment 1 the sewage<br />

sludge used was from Collinsville Waste Water Treatment Plant. Due to the low production<br />

from the Collinsville Plant, the sludge had been baked in the sun for several months. In<br />

Experiment 2 we wanted to test a combination of sewage from Bowen and Collinsville, as<br />

Bowen sewage is wetter and larger quantities are available.


Treating acidity in pit lakes using sewage and greenwaste<br />

7.2 Methods<br />

Experiment 2 consisted of 21 microcosms, with 3 replicates for each of 7 treatments. The<br />

treatments included an untreated control, and additions (100 g or 200 g) of greenwaste,<br />

sewage or greenwaste and sewage combined (Table 7.1). However, one replicate of treatment<br />

S200 failed soon after establishment leaving only two replicates for this treatment. Sewage<br />

consisted of 1 part of Bowen waste to 2 from Collinsville.<br />

Table 7.1. Experimental design for organic dosing of pit lake cores.<br />

Treatment Code Individual<br />

organic mass<br />

(g)<br />

40<br />

Water:greenwaste:sewage<br />

ratio<br />

Control Control 0 1:0:0<br />

Greenwaste (G100) 100 32:1:0<br />

(G200) 200 16:1:0<br />

Greenwaste and Sewage (GS100) 100 32:1:1<br />

(GS200) 200 16:1:1<br />

Sewage (S100) 100 32:0:1<br />

(S200) 200 16:0:1<br />

Experiment 2 microcosms were made from clean 100 mm diameter and 600 mm long (4.5 L)<br />

acrylic tubes, sealed at the base with a rubber bung, and at the top with a loose-fitting PVC<br />

cap which allowed for limited gas exchange between the water and surrounding air. Although<br />

GAE is thermally stratified for several months each year during which the hypolimnion<br />

becomes anoxic, for the remainder of the year it is well mixed and oxic (author’s unpublished<br />

data). The loose covers attempt to simulate reduced mixing and resultant hypoxia caused by a<br />

thick layer (0.5 to 1 m) of greenwaste added to GAE. Littoral sediment from GAE was added<br />

to a depth of 140 mm in the microcosm, this sediment had a similar pH in the interstitial<br />

water to that of the overlying water when collected. A 10 mm diameter fibreglass mesh<br />

(flywire) tube was placed in each microcosm to permit sampling of bottom waters once<br />

organic matter was added (Figure 7.1). The microcosms were then filled to within 20 mm of<br />

the top with GAE water.


41<br />

McCullough, Lund and May (2008)<br />

The lower 300 mm of the microcosms were placed in an opaque black plastic tub which was<br />

filled with tap water to evenly distribute ambient temperatures between cores and to reduce<br />

the possibility of leakage. The tubs were then wrapped to the top of the microcosms in black<br />

PVC sheeting to occlude light, as PAR levels are extremely low in the hypolimnion of these<br />

lakes (Author’s unpublished data).<br />

Liquid sludge was collected from Bowen and primary-treated sewage sludge was collected<br />

from drying beds of the Collinsville and Bowen Municipal Wastewater Treatment Plants and<br />

analysed (as per Chapter 6). Homogenised samples of sewage and greenwaste were pH paste-<br />

tested (water:solid ratio of 10:1). Samples were also analysed for total nitrogen, total<br />

phosphorus and total organic carbon content and a range of solutes.<br />

On 10 occasions at increasing intervals, a Hydrolab Datasonde 4a multiparameter meter was<br />

used to measure temperature, pH, specific conductance (EC), oxidation-reduction potential<br />

(ORP, platinum reference electrode), and dissolved oxygen (DO, % saturation and mg L -1<br />

) in<br />

the water of the microcosm.


Treating acidity in pit lakes using sewage and greenwaste<br />

Figure 7.1. Microcosm design showing placing of sediment, organic matter and mesh tube for an S200<br />

treatment.<br />

A 60 mL water sample was taken 180 days after dosing, filtered through 0.5 µm glassfibre<br />

filterpaper (Pall Metrigard) and kept at 4 o C prior to analysis for a range of solutes, total<br />

filtered nitrogen (TFN) and total filtered phosphorus (TFP).<br />

Microcosm sediment geochemistry was sampled on day 230 by removing unsolidified<br />

surface material and then homogenizing the remaining upper 20 mm of sediment of each<br />

microcosm core. Samples were analysed for a range of solutes.<br />

Sulfate reducing bacteria abundances for each treatment were semi-quantitatively assessed at<br />

180 days by pooling within a treatment 5 mL aliquots of surface water from each microcosm<br />

in a “SRB-BART” which measured SRB activity (Droycon Bioconcepts Inc.). SRB-BART<br />

vials were incubated at 25 o C for 9 days with assessments of their activity made daily.<br />

42


43<br />

McCullough, Lund and May (2008)<br />

Sewage, greenwaste, and sediment samples were digested using aqua-regia as per (USEPA,<br />

1995). The digestate and water samples were analysed by Inductively Coupled Plasma<br />

Atomic Emission Spectrophotometry (ICP-AES) for Al, As, B, Ca, Cd, Cr, Co, Cu, Fe, Pb,<br />

Mg, Hg, S, Se, Si, Sn, Zn. Total Kjeldahl N and Total P were measured in sewage and<br />

greenwaste samples as per APHA (1998). Total Organic C was measured in sewage and<br />

greenwaste samples on a TOC Analyser 700 (OI Corporation). Water samples were subject to<br />

a persulfate digestion and analysed for TFN and TFP as per APHA (1998). All analyses were<br />

undertaken at NATA accredited commercial laboratories.<br />

The potential for human health risks associated with a field trial of the approach were<br />

assessed by measuring faecal coliforms and gas production. Faecal Coliforms were measured<br />

in the water of the microcosms on day 180 by the standard total coliform membrane filter<br />

procedure for total members of the coliform group (APHA, 1998). Sample blanks and 10 mL<br />

samples of microcosm surface water were taken with sterile 10 mL syringes, filtered with<br />

20 mL sterile buffered water onto sterile gridded filters and then placed upon sterile<br />

rehydrated agar pads staining for total coliforms (Sartorius AG 14053 N, ‘endo media’).<br />

Coliform colonies were counted following 24 h dark incubation at 35 oC. The concentrations<br />

of emitted gases (ammonia and hydrogen sulfide) were measured in the capped headspace on<br />

days 8, 74 and 125. A single sample (400 mL) was collected from each replicate for controls<br />

(only 3 sampled) and 200g treatments and combined for a total of 1.2 L which was pumped<br />

through Draeger tubes for both gas types (levels of detection to 0.8 ppm).<br />

7.2.1 Statistical analyses<br />

Differences between treatments’ chemistry was determined by ANOVA with pair-wise<br />

differences determined by Tukey’s Honestly Significant Difference (HSD) post hoc test<br />

(Tukey, 1953). Multivariate physico-chemical data from day 180 was analysed by ANalysis-<br />

Of-SIMilarity (ANOSIM) (Clarke, 1993) and Principal Components Analysis (PCA) in the<br />

PRIMER 6 software package (PRIMER-E Ltd, 2001).


Treating acidity in pit lakes using sewage and greenwaste<br />

7.3 Results<br />

On 10/11/2004 Garrick East pit lake had a very low pH (2.41 - 2.33), high EC (9.04 -<br />

9.26 mS cm -1 ), high ORP (594-623 mV), and thermally stratified (temperature changes over 6<br />

m from 27.1 to 21.2 o C) and anoxic in the hypolimnion (DO surface - 7.37 mg L -1 , bottom -<br />

0.03 mg L -1 and high total iron concentrations (Table 7.2) indicative of a strongly iron<br />

buffered system (Totsche et al., 2003), with heavy metals at environmentally toxic<br />

concentrations (ANZECC/ARMCANZ, 2000b). Nutrient levels were also very low in this pit<br />

lake; especially phosphorus, as is typical of many AMD waters (Lessmann et al., 2000; Borg<br />

& Holm, 2001). This water was used to create the microcosms and is a reference condition<br />

for the controls (Table 7.2). By Day 180, the effects of the microcosm on water quality in the<br />

absence of treatment can be assessed through comparison of the original GAE water and the<br />

control. Sulfate levels increased substantially and nitrogen appeared to decline substantially<br />

(although the change from TN to TFN could account for the change). All other parameters<br />

changed little in concentration (Tables 7.2). pH ranged between 2.15 and 2.45 (mean±s.e.;<br />

2.34±0.009), EC ranged from 7.24 to 10.42 mS cm -1 (9.48±0.06 mS cm -1 ), DO ranged<br />

between 3.0 mg L -1 (37% saturation) and 7.4 mg L -1 (93%) (5.5±0.1 mg L -1 ) and ORP ranged<br />

between 534 and 657 mV (601±3 mV). The water temperature for all the microcosms ranged<br />

between 20.9 and 27.5 o C (25.0±0.1 o C).<br />

44


45<br />

McCullough, Lund and May (2008)<br />

Table 7.2. Chemistry of GAE pit lake water (April 2006) at collection and control microcosms at Day 180.<br />

Parameter GAE water<br />

(mg L-1)<br />

Day 180<br />

Controls<br />

(mg L-1)<br />

Sulfate 2,610 9707±942<br />

Total N 0.51 0.5±0.2 (TFN)<br />

Total P


Treating acidity in pit lakes using sewage and greenwaste<br />

Table 7.3. Chemistry of the sewage and greenwaste used in the experiment.<br />

Parameter Collinsville<br />

sewage<br />

(mg Kg -1 )<br />

46<br />

Bowen<br />

sewage<br />

(mg Kg -1 )<br />

Greenwaste<br />

(mg Kg -1 )<br />

Total sulfur 10,000 14,000 1,700<br />

Total N 31 П 60 П 20<br />

Total P 12 19 2.3<br />

Total organic C 29% 34% 39%<br />

pH 6.1 6.5 5.6<br />

Aluminium 17,000 7,600 1,000<br />

Arsenic 7 7 1<br />

Cadmium 3.2 2.1


47<br />

McCullough, Lund and May (2008)<br />

Table 7.4. Maximum increase in GAE water solute concentrations from each treatment in the microcosms<br />

with reference to initial GAE water quality (– = No data; *Total nitrogen as Kjeldahl nitrogen).<br />

Maximum potential addition to GAE water concentration (mg L -1 )<br />

GAE Greenwaste Sewage Greenwaste & Sewage<br />

(mg L -1 ) 100g 200g 100g 200g 100g 200g<br />

Total sulfur – 24 47 266 531 145 289<br />

Sulfate 2,610 – – – – – –<br />

Total N 510 280 560 1,060 2,120 670 1,340<br />

Total P


Treating acidity in pit lakes using sewage and greenwaste<br />

improvements in pH, with greenwaste and sewage combined treatments providing the<br />

greatest improvement, followed by sewage and then greenwaste alone. Adding more organic<br />

material, with the exception of greenwaste only, improved the pH reached at day 180. For<br />

example, GS100 produced a similar pH and water quality to S200. Improvements in pH were<br />

associated with reductions in S, sulfate, ORP, DO, Al, Cd, Co, Cr, Ni, Zn, Cu, Pb, and Fe<br />

concentrations, which are consistent with sulfate reduction processes. The heterogeneous<br />

nature of the greenwaste appears reflected in the variability between replicates which was<br />

larger than for other treatments especially at the 200g level. ; Interestingly, S100 was<br />

associated with higher Se, TFN, TFP, Mg and Ca concentrations compared to all other<br />

treatments. The addition of more organic matter (200g) to the treatments, resulted in lower<br />

EC, despite potentially adding more solutes (see Table 7.4).<br />

Figure 7.2. PCA of day 180 microcosms physico-chemical data. The amount of variability explained by each<br />

axis is shown as a percentage. Lines indicate eigenvectors, the direction of the line indicates the<br />

relationship to a PC axis and the length of the line indicates its relative importance (longer lines are<br />

more important).<br />

48


49<br />

McCullough, Lund and May (2008)<br />

Day 180, total nutrients increased from below detection (


Treating acidity in pit lakes using sewage and greenwaste<br />

Table 7.6. Mean (± standard error) of selected major cations in water from microcosms collected on Day 180<br />

(no standard error is shown for S200 treatment as there were only two replicates available)<br />

Microcosms Al Ca Fe K Mg Mn Na Zn<br />

mg L -1 mg L -1 mg L -1 mg L -1 mg L -1 mg L -1 mg L -1 mg L -1<br />

Control 142.5±8.5 398±20 468±156 0.8±0.5 550±19 47.3±1.5 408±13 13±0.7<br />

G100 56.5±34.1 470±0 560±50 147±30 577±17 46.3±0.9 533±15 4±3.5<br />

G200 65.8±32.3 463±20 284±234 179±59 563±18 42.7±2.0 470±21 6.5±3.4<br />

G100 0.02±0.01 400±11 24±23 47±0.7 583±26 30.7±3.3 577±32 0.08±0.04<br />

G200 0.02 395 0.2 82 565 3.2 710 0.05<br />

GS100 0.2±0.1 367±35 112±109 167±12 526±26 5.5±0.5 600±6 0.07±0.006<br />

GS200 0.01±0.01 52±4 0.5±0.1 333±20 443±23 0.7±0.1 773±71 0.18±0.06<br />

Table 7.7. Mean (± standard error) of selected minor cations in water from microcosms collected on Day 180<br />

(no standard error is shown for 200 g Sewage treatment as there were only two replicates<br />

available. *contains replicates that had concentrations below detection levels – As & Pb


51<br />

McCullough, Lund and May (2008)<br />

3.0 mg kg -1 in control to 2.1 mg kg -1 in GS200. Conversely, B concentrations were raised in<br />

greenwaste and sewage-dosed treatment sediments; from 5.9 mg kg -1 in control to a mean<br />

maximum of 8.5 mg kg -1 in GS200. Mean Ca concentrations were raised from 1.7 g kg -1 in<br />

control in all treatments other than GS100 where it was reduced to 1.3 g kg -1 . Mean Co<br />

concentration was greatly increased in G treatments from 2.5 mg kg -1 in control to a mean of<br />

12 mg kg -1 in G100. Mean Cr also increased in all treatments from 2.0 mg kg -1 to means of<br />

2.7 and 2.8 mg kg -1 in GS100 and S100 respectively. Mean Cu concentrations increased in<br />

proportion to the amount of sewage in the microcosm to a mean of 21 mg kg -1 in S200. Mean<br />

Fe sediment concentrations decreased in all dosed treatments from 9.1 g kg -1 in control to a<br />

mean minimum of 6.9 g kg -1 in GS200; greatest reductions occurred in treatments containing<br />

sewage. Mean K, Na , Pb and S concentrations changed little across treatments. Mean Mg<br />

sediment concentrations increased in all treatments from 602 mg kg -1 in the control to a<br />

maximum of 1.1 g kg -1 in S100, except for GS200 where it decreased to a minimum of<br />

563 mg kg -1 . Mean manganese concentrations increased from 65 mg kg -1 in the control to<br />

100 mg kg -1 in both G100 and S100, but reduced to only around 42 mg kg -1 in GS treatments.<br />

Sediment Ni concentrations decreased from 4.6 mg kg -1 in all sewage containing treatments<br />

except for S100, but increased in both G treatments. Ni concentrations were lowest in MS200<br />

at 2.9 mg kg -1 , and highest in G100 at 20.3 mg kg -1 . Sediment concentrations of Zn also<br />

increased in all treatment, from a mean control concentration of 37 mg kg -1 to a maximum of<br />

79 mg kg -1 in S100.


Treating acidity in pit lakes using sewage and greenwaste<br />

Figure 7.3. Day 230 concentrations of a). major, and b). minor, sediment analytes for each organic matter type<br />

and dosing rate. Error bars indicate single standard errors of the mean.<br />

52


7.3.3 Changes in water quality during the experiment<br />

53<br />

McCullough, Lund and May (2008)<br />

Temperature was very similar within treatments, ranging from 23.9–27.4 o C and averaging<br />

25.0 o C (Figure 7.4). The coefficient of variation for temperature over time and between all<br />

treatment replicates was only 5%. The pH of the control treatment level changed little (0.05<br />

pH units) over the course of the experiment. pH was not seen to increase as much in either G<br />

treatments, with a maximum of pH 4.5 reached by final day 228. However, sewage, and<br />

green waste and sewage treatments both showed a rapid increase in pH to circum-neutral pH<br />

by day 282, except for S100 which began to plateau at pH 6. There also appeared to be<br />

greater variation in the pH response within the G treatments than for either S or GS<br />

treatments.<br />

Specific conductance appeared to increase in all treatments following addition of organic<br />

material with the greatest increase in the green waste treatment (Figure 7.4). Although there<br />

was a slight increase in control specific conductance over the experiment from 9.4–<br />

9.9 mS cm -1<br />

, specific conductance appeared to only decline in both greenwaste treatments and<br />

S100 at around the same as alkalinity increased (i.e., around day 37). Although treatments<br />

containing sewage were very variable between replicates, both treatments containing sewage<br />

appeared to decline in solute concentrations greater than did green waste alone.


Treating acidity in pit lakes using sewage and greenwaste<br />

54


55<br />

McCullough, Lund and May (2008)<br />

Figure 7.4. Change in a). pH, b). EC, and c). ORP of microcosm treatment levels over time for different<br />

organic dosing treatments. Error bars indicate single standard errors of the mean.<br />

Although there was generally little different between upper and lower pH of microcosms,<br />

S200 had higher pH near the sediment than near the water surface in the first 30 days<br />

following dosing. Conversely GS100 had higher pH near the water surface than near the<br />

sediment in the first 90 days following dosing. However, after 60–90 days, the difference in<br />

pH between upper and lower of all treatment microcosms was less than 1 pH unit (Figure<br />

7.5).<br />

Figure 7.5. Treatment pH difference (top pH - bottom pH) of microcosms over time for different organic dosing<br />

treatments. Error bars indicate single standard errors of the mean.<br />

7.3.4 Bacterial abundances<br />

Faecal coliforms were not observed in any treatments. However, total coliform counts were<br />

too abundant to be enumerated in all treatments amended with greenwaste. Sulfate reducing<br />

bacteria activity was only found in the organic-supplemented treatments containing sewage<br />

(GS100, GS200, S100 and S200). A black precipitate also formed immediately upon mixing<br />

in all of these treatments, except S100, indicating excess dissolved H 2S.


Treating acidity in pit lakes using sewage and greenwaste<br />

7.3.5 Gases evolved<br />

Hydrogen sulfide was also evolved as the black precipitate extended upwards through the<br />

microcosm waters above the green waste and sewage solids. The sulfide smell and the<br />

concomitant presence of a black precipitate indicated that sulfate reduction was likely<br />

occurring in all treatments containing greenwaste. There were no detectable traces of<br />

ammonia or hydrogen sulfide on day 8. However, by day 180 there were 74 ppm NH 3 and<br />

12 ppm H 2 S in GS200, and 17 ppm H 2 S in S200. By day 125 there remained 12 ppm NH 3 in<br />

GS200, and 7 ppm of NH 3 and H 2 S in S200. As the microcosms cores were loosely sealed at<br />

the top, these concentrations are indicative only of the nature and relative rates of<br />

biochemical processes taking place in the cores.<br />

7.4 Discussion<br />

The decrease in sulfate concentrations in all treatment microcosms provides support for<br />

biological sulfate reduction producing alkalinity and removing sulfate and cations as<br />

monosulfides. The success of sulfate reduction in these low pH waters appears to be contrary<br />

to Postgate’s (1984) (amongst other authors) assertion that sulfate reducing bacteria (SRB)<br />

activities only occur at pH >5. Nevertheless, other published studies have reported SRB<br />

activity at pH values below this threshold. For example, SRB activity in an acid lake has been<br />

found by Herhily and Mills (1985) at pH 2.5, and at pH 2.7 by Gyure et al. (1987). It appears<br />

that mechanisms of adaptation and/or less-acid microenvironments, enabled sulfate reducing<br />

bacteria to begin reducing sulfate, promoting alkalinity as part of this biological process<br />

(Küsel & Dorsch, 2000; Küsel et al., 2001).<br />

Variability within control sediment metal concentrations was likely to be due to natural<br />

sediment heterogeneity. However, contrary to that expected by sulfate reduction, sediment<br />

total sulfur concentrations were not necessarily increased where water column concentrations<br />

of sulfate were greatly reduced. However, unlike oxic lakes, pyrite has also been found to<br />

form in the anoxic water column of natural water bodies (i.e., syngenetic pyrite) due to<br />

56


57<br />

McCullough, Lund and May (2008)<br />

limited availability of reactive iron in benthic sediments, (Suits & Wilkin, 1998).<br />

Consequently, although the intention of removing organic sludge from the sediment surface<br />

was to prevent confounding by remaining organic matter, it is likely that amorphous metal<br />

monosulfides were also removed by this activity, confounding sediment results.<br />

All treatment faecal coliform abundances were below detection level of 10 MPN 100mL -1<br />

,<br />

which met ANZECC/ARMCANZ (2000a) contact limits of 150 faecal coliforms 100 mL -1<br />

.<br />

However, the extremely high total coliform count (greater than could be enumerated) may<br />

mean that further organic decomposition than 180 days is required before contact may be<br />

possible in pit lakes remediated with greenwaste. Nevertheless, the presence of equally high<br />

abundances of total coliforms in greenwaste-only samples indicates that they are likely to be<br />

simply non-pathenogenic decomposers that occur in benthic sediments of many natural water<br />

bodies.<br />

Depending on its source, sewage sludge can contain high concentrations of heavy metals<br />

(Berrow & Webber, 1971). Both the Collinsville and Bowen sewage displayed high<br />

concentrations for many heavy metals. However, these heavy metals are also likely to be<br />

trapped in the sediments as metal sulfides due to SRB activities. Careful management of the<br />

remediated pit lake would then be required to prevent oxidation of these sediments and<br />

subsequent remobilised (Simpson et al., 1998).<br />

Further reduction in biological availability of metals and metalloids is also likely to occur<br />

through formation of complexes with organic chelators present as components of the<br />

refractory green waste, such as organic acids (Tipping & Hurley, 1992). Nevertheless, the<br />

contribution that organic materials may make to the heavy metal burden of a pit lake needs to<br />

be considered in the choice of organic materials for remediation. This study found sewage<br />

treatment performed similarly to that of greenwaste and sewage, whilst others have found<br />

vegetation has performed equally (Waybrant et al., 1998; McCullough et al., 2006). In this<br />

respect, remediation strategies may be best placed by choosing greenwaste as the bulk<br />

contribution to electron donors over that of sewage. As discussed, greenwaste also has an<br />

additional advantage of providing organic substances such as humic and fulvic acids, with<br />

which heavy metals may directly complex to. Ligand formation between heavy metals and


Treating acidity in pit lakes using sewage and greenwaste<br />

refractory organics will further remove these toxic components from biological availability,<br />

albeit at a likely reduced capacity to that of sulfate reduction processes (Brown Jr., 2001).<br />

Nevertheless, a clear concern of the use of sewage is the introduction of human pathogens.<br />

The coastal town of Townsville, only 170 km to the north-north-west of Collinsville, receives<br />

a very high mean annual ultraviolet (UV) exposure of 4 300 J m -2 , and a maximum of around<br />

60 J m -2 in December (personal communication John Javorniczky, Australian Radiation<br />

Protection and Nuclear Safety Agency), indicative of the high UV levels experienced in<br />

Collinsville pit lake surface waters. Consequently, deactivation of coliforms in the warm<br />

saline waters of the pit lakes under this high level of UV exposure is likely to be very rapid<br />

(Smith et al., 1994; Sinton et al., 1999), occurring within days. Furthermore, even if bacteria<br />

remain unexposed in sediments and deeper waters, our mesocosm results (conducted under<br />

nil UV exposure) indicate that faecal bacteria are not able to survive for extended periods<br />

away from host organisms and in acidic waters.<br />

Although lake release of ammonia gas is unlikely to be significant, release of toxic hydrogen<br />

sulfide from the water body may occur when dissolved concentrations of iron are<br />

significantly decreased. Nevertheless, “run away” sulfate reduction may be feasibly<br />

controlled by introducing more low pH iron-laden AMD water to react with excess hydrogen<br />

sulfide and lower water pH to that sub-optimal for sulfate reduction bacteria. These findings<br />

were incorporated into a formal risk assessment for the field-scale experiment (Chapter<br />

8.2.1).<br />

Consequently, this study has demonstrated remediation of AMD water pH and high metal<br />

concentrations within months of dosing with green waste and sewage. This work builds on<br />

other work demonstrating that readily available and cheap organic matter may be used to<br />

develop alkalinity though microbially-mediated in situ sulfate reduction. For example,<br />

Waybrant et al. (1998) tested eight bulk organic matter types, with sewage sludge fastest to<br />

achieve high levels of sulfate reduction. Again using locally available bulk materials, Harris<br />

and Ragusa (2000) also found a mixture of sewage sludge and plant material (fresh rye grass)<br />

effective in remediating acidity and high metal concentrations of acid mine waters through<br />

58


59<br />

McCullough, Lund and May (2008)<br />

sulfate reduction. Different to this current study, their combined mixture proved more<br />

effective in ameliorating pH and metal concentrations than either sewage sludge (little<br />

response) or plant material (nil response). Conversely, an observation at the Collinsville Coal<br />

Project Mine in North Queensland, Australia (Fallon, 1994) suggested that reduced acidity,<br />

sulfate and metal concentrations in a pit lake was due to bacterially-mediated sulfate<br />

reduction with the sewage effluent discharged into this pit functioning as a carbon source.<br />

In conclusion, mine water research and management is a very new and rapidly developing<br />

field (Wolkersdorfer, 2004) and corrective measures for acidic mining lakes also greatly<br />

differ from those in use for eutrophication control (Klapper, 2003). Best practice AMD pit<br />

lake treatment is likely to be required to be made on a case-by-case basis where potential pit<br />

lake end uses and availability of organic substrates have been identified and a remediation<br />

strategy has consequently only then been constructed. Consequently researchers, consultants<br />

and regulatory agencies need to maintain an open-mind to treatment solution options for<br />

these unique environmental issues. Part of the challenge for both mining companies and<br />

regulatory waterbody managers with this assessment will be the ability to think laterally as to<br />

what the current values of the pit lake are, what treatments may be feasible, and what type of<br />

pit lake (water quality and quantity) is desirable for either social, environmental or other<br />

enduses (Doupé & Lymbery, 2005; McCullough & Lund, 2006).


61<br />

McCullough, Lund and May (2008)<br />

8 Field-scale remediation of a tropical acid mine pit<br />

lake with greenwaste and sewage sludge<br />

8.1 Background<br />

The last half century has seen development of technologies resulting in large-scale open-cut<br />

mining in areas which would previously have been worked underground, if mined at all. This<br />

activity has left a legacy of many thousands of mine pit lakes worldwide (Klapper & Geller,<br />

2002). As these technologies continue to develop, the result is likely to be ever larger and<br />

deeper mining pits. Most mine pits are abandoned as ‘open voids’, with the burden and<br />

tailings left outside of the pit as this is the cheapest and most practicable option for mining<br />

companies (Castro & Moore, 1997). This type of mine closure allows easier access to re-mine<br />

tailings and lower grade ores if technology or economic change renders this feasible.<br />

However, open voids may also be the only practical option for very large pits which are not<br />

directly linked to significant regional water resources and are too large to even partially<br />

backfill; either at completion or during active working.<br />

Pit lakes form in these voids when dewatering ceases in a mine pit that extends below the<br />

watertable. As groundwater, rainfall and surface runoff slowly fills the pit, this water may<br />

react with oxidised seams and pit walls resulting in dissolution and oxidation of exposed<br />

minerals (Castro & Moore, 1997). Pit lakes may be terminal groundwater sinks when the<br />

climate is net-evaporative, with the pit lake creating a localised depression in the surrounding<br />

water table. Under these net-evaporative conditions, soluble ions may increase in<br />

concentrations by evapo-concentration (Commander et al., 1994). Alternatively, under a net-<br />

precipitation regime, pit lakes may contribute as sources to local hydrology with either<br />

surface or ground water outflow or may function as flow-through “groundwater windows”<br />

(Johnson & Wright, 2003).<br />

In these two latter cases of net precipitation, the open void strategy may have long-term<br />

benefits or liabilities to associated communities and the natural environment (McCullough et<br />

al., in review). Whilst mining companies and communities have often failed to appreciate the


Treating acidity in pit lakes using sewage and greenwaste<br />

benefits and opportunities of such a large waterbody in post-mining landscapes, various<br />

opportunities frequently exist for pit lakes and their water (McCullough & Lund, 2006).<br />

These include water for commercial operations such as tourism, aquaculture, tree farming and<br />

horticulture; as well as recreational opportunities such as swimming, fishing, water skiing,<br />

and wildlife observation. Nevertheless, pit lakes of low water quality may threaten the health<br />

and well-being of both local communities and the natural environment (Doupé & Lymbery,<br />

2005).<br />

Acid Mine Drainage is the most common problem affecting pit lake water quality globally<br />

(Charles, 1998; Klapper et al., 1998). Receiving environments for AMD typically have<br />

reduced environmental and social values, and the resultant water is less valuable as a resource<br />

to the mining company (McCullough & Lund, 2006). Acid Mine Drainage is arguably the<br />

greatest environmental problem facing water management in the international mining<br />

industry today (Gray, 1997; Harries, 1998a). The large quantities of water in pit lakes<br />

potentially represents a potentially valuable resource to mining companies, the environment<br />

and community; if appropriate water quality can be achieved (Doupé & Lymbery, 2005;<br />

McCullough & Lund, 2006). For example, the Bowen region in North Queensland of<br />

Australia is currently facing a long-term drought and the large volumes of water, even of low<br />

quality, are of great benefit (Côte et al., 2006). Mining lease pit lakes therefore represent<br />

significant short-term resources to adjacent operations, and furthermore reduce pressure on<br />

regional natural water resources over a longer period (McCullough & Lund, 2006).<br />

Microbial sulfate reduction can be an efficient and effective remediation for the treatment of<br />

AMD contaminated waters. Sulfate reducing bacteria (SRB) can reverse the acidification<br />

process by converting sulfates to sulfides in low redox environments when supplied with<br />

labile carbon sources (see King et al, 1974). Tuttle et al. (1969) first suggested the use of<br />

SRB in the treatment of AMD. Such in-situ neutralisation by sulfate reduction is expected to<br />

play a key-role in the remediation of acidic mining pit lakes (Kleeberg, 1998). However,<br />

primarily due to carbon and P limitation, acid mine lake tropic status is ultra-oligotrophic to<br />

oligotrophic (extremely low in nutrients) (Lessmann et al., 2000; Nixdorf et al., 2005) and<br />

acid autogenic carbon accumulation in is typically very low (Kleeberg & Grüneberg, 2005).<br />

62


63<br />

McCullough, Lund and May (2008)<br />

In Experiments 1 and 2, we tested sewage and greenwaste in microcosms for the treatment of<br />

AMD waters from a Collinsville Coal Project pit lake (GAE). Results were extremely<br />

positive with rapid remediation from pH 2.2 to >5.5 over 145 days. However, the application<br />

of this science now required on-site experiments at lake-scale to demonstrate this new<br />

technology of remediation with bulk low-grade organic sources. This chapter reports on a<br />

field-scale experiment that aimed to test the suitability of greenwaste and sewage sludge as an<br />

organic matter source for in situ AMD pit lake remediation.<br />

8.2 Methods<br />

The proposed experiment underwent an extensive and comprehensive risk assessment and<br />

occupational health and safety assessment prior to being approved. These assessments were<br />

led by the author (JM) and is detailed in Chapter 8.2.1.<br />

Previous microcosm experimentation with an AMD:sewage:greenwaste ratio of 16:1:1 had<br />

been successful in remediating GAE water to pH 5.5 in under 5 months (see Chapter 7). Due<br />

to the large size of the GAE pit lake, it was divided by earthworks in July 2006 into a smaller<br />

eastern lake (GAEE), to be treated, and a larger western (GAEW) control (untreated) lake.<br />

This was to ensure that the organic loading required could be achieved over six-months<br />

(Figure 8.1). In addition to GAEE, three representative pit lakes on the lease were used as<br />

further controls (Ramp 8, Ramp 5 and Ramp 5a). Operational reasons prevented continued<br />

monitoring of control Ramp 5 after 3 months of data collection . The small dataset that had<br />

been accrued during this time was therefore not used in further analysis. Ramp 8 also became<br />

inaccessible before project completion, however 20 months of data had been collected and<br />

was this was used in analysis. Although Ramp 5a is shallower, Ramp 8 was comparable to<br />

GAEE (Table 8.1).


Treating acidity in pit lakes using sewage and greenwaste<br />

Figure 8.1. GAE after being divided into two new lakes; GAEE and GAEW.<br />

Table 8.1 Morphology of project control and treatment lakes.<br />

Pit lake Maximum depth (m) Surface area (ha) Volume (ML)<br />

Ramp 5 4 4.6 404<br />

Ramp 5a 5 3.4 117<br />

Ramp 8 12 1.2 95<br />

GAE 13.8 5.9 470<br />

GAEE 13 4.4 336<br />

GAEW 12 1.1 71<br />

64


8.2.1 Risk Assessment<br />

65<br />

McCullough, Lund and May (2008)<br />

The location and nature of the field-scale trial necessitated extensive consultation and<br />

assessment from a number of stakeholders prior to the commencement of the trial. A list of<br />

the key stakeholders and their input into the project is shown below:<br />

Bowen Shire Council: supported the project in providing the organic materials<br />

(sewage sludge and green waste) for the project;<br />

Queensland Environmental Protection Agency: provided state government<br />

environmental approval for the research project;<br />

Mine workforce: a presentation was made to representatives of the local CFMEU<br />

lodge, and a cross-section of workforce was engaged in the formal risk assessment<br />

process;<br />

Local community groups: a presentation was made to the Retired Miners’<br />

Association, and newsletters mailed to the local communities of Collinsville and<br />

Scottville which provided a description of the proposed project and subsequent<br />

updates seeking feedback from the community; and,<br />

Industry organisations: presentations were made to local, regional and international<br />

industry organisations and feedback received on aspects of the project.<br />

The outcome of these consultation sessions involved the development of a specific project<br />

work procedure which detailed the requirements at various stages of the project including<br />

communication, occupational health and safety requirements. These requirements are<br />

summarised below:<br />

Communication requirements:<br />

o external communication involved project updates to key stakeholders, and also<br />

specific communication at particular stages of the project (i.e., Bowen Shire<br />

Council and the waste transport contractors were regularly contacted during<br />

the addition of waste stage);


Treating acidity in pit lakes using sewage and greenwaste<br />

o internal communication involved coordination of project activities within<br />

general mining operations (i.e., communication with Open Cut Examiner<br />

when work was being conducted in Garrick East pit area, restricting the<br />

project site to project personnel as part of general mine safety procedures).<br />

Occupational health and safety:<br />

o Due to the nature of the material (especially the sewage sludge) that was<br />

involved in the project, all personnel involved in the transport of sludge waste<br />

and contact of waters which contained this material as part of the monitoring<br />

program, underwent appropriate immunisation (i.e., hepatitis injections) and<br />

were required to follow a hygiene protocol;<br />

o As the laboratory core experiments had detected some gas emanating from the<br />

8.2.2 Organic dosing<br />

cores, gas monitoring was conducted by both mine and project specific<br />

personnel at regular intervals. This monitoring was supported by a trigger<br />

action-response plan (TARP) as part of the work procedure. Similarly, project<br />

specific and other general mine emergency procedures were linked to provide<br />

an effective framework for dealing with an emergency.<br />

Over six months from August 2006 to February 2007, primary-treated sewage sludge and<br />

liquid was collected from the Bowen Municipal Wastewater Treatment Plant and green waste<br />

was collected from the Collinsville Municipal Landfill. The quantity of organic added was<br />

obtained from estimates of volumes, and number and volume of cartage trips for all organic<br />

matter types and from sewage and greenwaste density data from Experiment 2 and for Bowen<br />

liquid sewage from a calculated specific density of 1.02 kg L -1 . From July–December 2006<br />

approximately ca.440 t of liquid sewage was added to GAEW per month. Sludge drying rates<br />

were reduced during the wet season, therefore this dosing rate was reduced from January–<br />

February 2007 to ca.290 t per month. Dried Collinsville sewage sludge was added as 20 t in<br />

November 2006 and 40 t in January 2007. Greenwaste was added as ca.730 t and ca.250 t in<br />

66


67<br />

McCullough, Lund and May (2008)<br />

August and October 2006 respectively. This 13:1:1 ratio of sewage:greenwaste:water<br />

represented around 80% of the most effective laboratory-derived dose of 16:1:1 (see Chapter<br />

7), with greenwaste the limiting available organic material. Greenwaste was largely<br />

representative of Australian garden waste and consisted of lawn clippings, tree branches and<br />

palm fronds, and other leafy and woody material. Sewage was deposited from 4 points<br />

around GAEW with green waste further spread by a long-arm excavator as it was deposited<br />

(Figure 8.2).<br />

Figure 8.2. Green waste being spread across the surface of treatment lake GAEW. Control lake GAEE is in<br />

the background (Photo: Joel May, Xstrata Pty Ltd).<br />

A sample of the sewage sludge was digested after APHA (1998) and analysed for total<br />

nitrogen, total phosphorus and total organic carbon content, as well as the cations Al, Ba, Be,<br />

Ca, Cd, Cr, Co, Cu, Fe, Mn, Na, Ni, Sb, Sn and V by Inductively Coupled Plasma Atomic<br />

Emission Spectrophotometry (ICP-AES). Representative chemical data for green waste was<br />

taken from McCullough et al. (2006).


Treating acidity in pit lakes using sewage and greenwaste<br />

8.2.3 Sampling<br />

8.2.4 Groundwater interactions<br />

Ground water monitoring bores were located immediately to the west (GAR01, 14.5 m deep),<br />

east (GAR02, 15 m deep) and south (GAR03, 23 m deep) of GAE pit lake (Figure 8.3).<br />

sampled using a bailer. Monitoring bore water levels was sampled from December 2003 to<br />

October 2007. GAE and GAEE/GAEW water levels were sampled from July 2004 to October<br />

2007. From July 2004 till October 2007 monitoring bores were sampled in situ monthly for<br />

water level, pH, EC and temperature with a Hydrolab Minisonde meter. From November<br />

2005 to July 2007 groundwater solute samples were taken at quarterly intervals using<br />

standard sampling protocols and monthly intervals in the second-half of 2006. A water<br />

sample was kept chilled prior to analysis in a commercial NATA registered analytical<br />

laboratory for dissolved metals by ICP-MS (Al, As, Be, Bi, Cd, Cr, Co, Cu, Pb, Li, Mn, Mo,<br />

Ni, Sb, Se, Ag, U, V, Zn) and hydrocarbon and total nutrients.<br />

Figure 8.3. Location of GAE pit lake monitoring bores.<br />

68


8.2.5 Pit lakes<br />

69<br />

McCullough, Lund and May (2008)<br />

A vertical profile of the water column was taken in the centre of each lake at the end of every<br />

month between April 2005 and July 2007. Temperature, pH, specific conductance (EC),<br />

oxidation-reduction potential (ORP, platinum reference electrode), turbidity (NTU), and<br />

dissolved oxygen (DO, % saturation and mg L -1<br />

) were measured at 1 m intervals using a<br />

Hydrolab Quanta multi-parameter meter. Chlorophyll a was measured with a Turner Designs<br />

Cyclops fluorometer attached to a volt meter calibrated against known chlorophyll<br />

concentrations in pit lake water. Known chlorophyll concentrations were determined by<br />

filtering five different concentrations of GAEW pit lake surface waters (0.5 µm Pal<br />

Metrigard). The filter paper was frozen, and following extraction with Dimethylformamide<br />

(DMF) (Speziale et al., 1984) chlorophyll a was measured with a Schimadzu UV-1201<br />

spectrophotometer as per APHA (1998) to derive a calibration curve (r 2 = 0.997).<br />

A water sample was collected for analysis of nutrients and metals from the lake surface as<br />

well as another from ca.0.30 m above the benthos using a Kemmerer bottle. Upon collection,<br />

each water sample was split into one 250 mL aliquot of unfiltered and one aliquot filtered<br />

through glassfibre filterpaper (0.5 µm Pal Metrigard). Aliquots were stored in acid washed<br />

high-density polyethylene bottles and stored at 4 o C prior to analysis. Part of the filtered<br />

aliquot was analysed for SO4 2- by ion chromatograph (Dionex ICS-1000). Another portion of<br />

the filtered sample was analysed for dissolved organic carbon as gilvin 440 by absorbance on a<br />

spectrophotometer at 440 nm. The remaining filtered sample was then acidified with reagent<br />

grade HCl and selected metals/metalloids analysed by Inductively Coupled Plasma Atomic<br />

Emission Spectrophotometry (ICP-AES; Al, Ba, Be, Ca, Cd, Cr, Co, Cu, Fe, Mn, Na, Ni, Sb,<br />

Sn and V). Unfiltered samples were digested using a persulfate digestion and then analysed<br />

by discrete analyser for total P and total N.<br />

8.3 Results<br />

8.3.1 Climate<br />

Australian Bureau of Meteorology data (Australian Bureau of Statistics, 2007) indicate that<br />

over the sampling period, rainfall was characteristically unpredictable with low rainfall in


Treating acidity in pit lakes using sewage and greenwaste<br />

2005 until the Wet season rains in January 2006. Late Wet season rains then followed in<br />

April, followed by low rainfall again until very heavy rainfall episodes in January and<br />

February 2007. June 2007 was uncharacteristically wet, with no rainfall in July (Figure 8.4).<br />

Warmer over the late Dry and Wet season months of October through to April, mean monthly<br />

temperatures were more predictable, albeit slightly warmer on average in 2005–2006<br />

(27.8 o C) than in 2006–2007 (26.1 o C). Nevertheless, rainy days in June 2007 led to<br />

particularly cold days, and clear skies in July to particularly cold nights.<br />

8.3.2 Dosing with organic material<br />

Figure 8.4. Collinsville climate for April 2005 to July 2007.<br />

Organic material was dosed in treatment lake GAEW from July 2006 to February 2007. Total<br />

chemical loadings were calculated from tonnage of loading and concentrations of chemicals<br />

in organic materials samples (Table 8.2). Unsurprisingly, the bulk of organic loading was<br />

70


71<br />

McCullough, Lund and May (2008)<br />

with organic carbon (402 t). Total Kjeldahl nitrogen and calcium were the next greatest loads<br />

at 29 and 28 t respectively.<br />

Table 8.2. Chemistry and total loading of organic materials dosed. *Data from Experiment 2. – = no data<br />

available.<br />

Parameter Bowen sewage liquid Bowen sewage sludge* Green waste* Total loading<br />

Loading (t) 3,193 61 979 4,233<br />

Analyte concentrations (mg/Kg) Total analyte load (kg)<br />

TN 1,800 60,000 20,000 29,000<br />

TP 440 19,000 2,300 4,800<br />

TOC 340,000 390,000 402,000<br />

Al 83 7,600 1,000 1,700<br />

As


Treating acidity in pit lakes using sewage and greenwaste<br />

8.3.3 Physico-chemical parameters<br />

Ramp 5a temperature was around 20 oC and well-mixed during Dry seasons from June to<br />

September (Figure 8.5a). Warming began at the end of the Dry season from October with<br />

slight thermal stratification occurring in both sample years around December and lasting to<br />

June. However, curiously, water temperatures were warmest in the centre of the water<br />

column, from then until June, when mixing was complete again. The water temperature of<br />

Ramp 8 (Figure 8.5b) became strongly stratified at around 3 m in September, at least three<br />

months earlier than Ramp 5a. Stratification was also much stronger, with a sharp temperature<br />

transition in the first 0.5 m, with the hypolimnion proper beginning at around 6 m. Although<br />

this lake only barely stratified prior to splitting in mid 2006, GAEE mixed completely from<br />

May to October each year (Figure 8.5c). Nonetheless, following splitting a strong<br />

thermocline developed with the epilimnion in the upper 2 m from January to May 2007. The<br />

western side of GAE (GAEW) mixed and warmed at the same time as the eastern side,<br />

however a strong thermocline at 2 m developed in this side from September to March 2006<br />

(Figure 8.5d). Following splitting, this thermocline deepened to 4 m and was maintained until<br />

June 2007.<br />

Oxidation-Reduction Potential was very high (ca.600 mV) in all control lakes (Figure 8.6).<br />

Ramp 8 showed a regular bi-annual decrease in ORP of hypolimnion waters, decreasing in<br />

both mid-Dry season and mid-Wet season (Figure 8.6b). Sometimes these low ORP waters<br />

extended right through to the epilimnion. However, following the heavy cyclonic rains of<br />

December–January 2006, Ramp 5a and GAEE showed large well-mixed decreases to<br />

450 mV in ORP (Figure 8.6). GAEW also showed a moderate decrease in epilimnion ORP,<br />

however this pit lake was not well mixed. As early as October 2006, ORP in GAEW was<br />

much lower in hypolimnion waters, with ORP increasing in value as it neared the lake surface<br />

and with water column ORP decreasing after dosing to a minimum of 65 mV near the lake<br />

benthos.<br />

pH was stable around 2.2 in control lakes except for Ramp 8 where it increased to pH 2.7<br />

during 2005 and 2006 Dry seasons (Figure 8.7). GAEE pH was as low as control lakes prior<br />

72


73<br />

McCullough, Lund and May (2008)<br />

to dosing, however, following dosing in August, GAEW hypolimnion pH began to increase<br />

from December 2006 to a maximum of 4.1 in July 2007. Unlike the second mesocosm<br />

experiment (Chapter 7) pH was not lower at the water’s surface.<br />

Although specific conductance (EC) was consistently high across all lakes at around<br />

15 mS cm -1, specific conductance painted a complex picture over time (Figure 8.8). There<br />

appeared to be a general trend of increasing EC over time, however this was interrupted,<br />

across all lakes, by a sudden decrease in EC in February 2006. This interruption coincided<br />

with heavy January 2006 rainfalls after a prolonged Dry period to at least April 2005 (Figure<br />

8.8). Further heavy rains occurred in January 2007. The epilimnion of Ramp 5a then formed a<br />

lower EC halocline at around 9 mS cm -1 through to July 2007. Although EC dropped to<br />

around 10 mS cm -1 in Ramp 8 it did not form a halocline. Both GAEE and GAEW also<br />

formed haloclines of around 8 mS cm -1. These two haloclines appeared to mix through and<br />

disappear by May 2007, although a lower EC epilimnion was still maintained in GAEW.<br />

Although generally below detection limits, pit lake chlorophyll a also showed high variability<br />

over time (Figure 8.9). Except for Ramp 8, all lakes showed a 2–3 months period of high<br />

chlorophyll concentrations up to at the start of monitoring in May 2005. Ramp 8 also<br />

demonstrated two chlorophyll blooms of 6–8 months each over the Wet seasons of 2005–<br />

2006 and 2006–2007. Unlike its counterpart GAEE, GAEW showed a whole-water column<br />

increase in chlorophyll a beginning September 2006, two months after dosing. These<br />

chlorophyll concentrations gradually reduced in the downwards extent to the monitoring<br />

completion in July 2007.


Treating acidity in pit lakes using sewage and greenwaste<br />

(a).<br />

(b).<br />

(c).<br />

(d).<br />

Depth (m)<br />

Depth (m)<br />

Depth (m)<br />

Depth (m)<br />

0<br />

1<br />

2<br />

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7<br />

8<br />

9<br />

10<br />

11<br />

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7<br />

8<br />

9<br />

10<br />

11<br />

18<br />

20<br />

22<br />

24<br />

26<br />

28<br />

30<br />

32<br />

34<br />

12<br />

32<br />

34<br />

5/2005 7/2005 9/2005 11/2005 1/2006 3/2006 5/2006 7/2006 9/2006 11/2006 1/2007 3/2007 5/2007 7/2007<br />

Figure 8.5. Temperature profiles of pit lakes (a) Ramp 5a, (b) Ramp 8, (c) GAEE, (d) GAEW from May 2005 to<br />

August 2007.<br />

74<br />

Date<br />

18<br />

20<br />

22<br />

24<br />

26<br />

28<br />

30<br />

18<br />

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24<br />

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30<br />

32<br />

34


(a).<br />

(b).<br />

(c).<br />

(d).<br />

Depth (m)<br />

Depth (m)<br />

Depth (m)<br />

0<br />

1<br />

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200<br />

300<br />

400<br />

500<br />

600<br />

700<br />

100<br />

200<br />

300<br />

400<br />

500<br />

600<br />

700<br />

75<br />

McCullough, Lund and May (2008)<br />

Figure 8.6. ORP profiles of pit lakes (a) Ramp 5a, (b) Ramp 8, (c) GAEE, (d) GAEW from May 2005 to August<br />

2007.<br />

100<br />

200<br />

300<br />

400<br />

500<br />

600<br />

700


Treating acidity in pit lakes using sewage and greenwaste<br />

(a).<br />

(b).<br />

(c).<br />

(d).<br />

Depth (m)<br />

Depth (m)<br />

Depth (m)<br />

Depth (m)<br />

0<br />

1<br />

2<br />

3<br />

4<br />

0<br />

1<br />

2<br />

3<br />

4<br />

5<br />

6<br />

7<br />

8<br />

9<br />

10<br />

11<br />

0<br />

1<br />

2<br />

3<br />

4<br />

5<br />

6<br />

7<br />

8<br />

9<br />

10<br />

0<br />

1<br />

2<br />

3<br />

4<br />

5<br />

6<br />

7<br />

8<br />

9<br />

10<br />

11<br />

2.0<br />

2.5<br />

3.0<br />

3.5<br />

4.0<br />

2.0<br />

2.5<br />

3.0<br />

3.5<br />

4.0<br />

12<br />

5/2005 7/2005 9/2005 11/2005 1/2006 3/2006 5/2006 7/2006 9/2006 11/2006 1/2007 3/2007 5/2007 7/2007<br />

Figure 8.7. pH profiles of pit lakes (a) Ramp 5a, (b) Ramp 8, (c) GAEE, (d) GAEW from May 2005 to August<br />

2007.<br />

76<br />

Date<br />

2.0<br />

2.5<br />

3.0<br />

3.5<br />

4.0<br />

2.0<br />

2.5<br />

3.0<br />

3.5<br />

4.0


(a).<br />

(b).<br />

(c).<br />

(d).<br />

Depth (m)<br />

Depth (m)<br />

Depth (m)<br />

Depth (m)<br />

0<br />

1<br />

2<br />

3<br />

4<br />

0<br />

1<br />

2<br />

3<br />

4<br />

5<br />

6<br />

7<br />

8<br />

9<br />

10<br />

11<br />

0<br />

1<br />

2<br />

3<br />

4<br />

5<br />

6<br />

7<br />

8<br />

9<br />

10<br />

0<br />

1<br />

2<br />

3<br />

4<br />

5<br />

6<br />

7<br />

8<br />

9<br />

10<br />

11<br />

6<br />

8<br />

10<br />

12<br />

14<br />

16<br />

18<br />

20<br />

22<br />

6<br />

8<br />

10<br />

12<br />

14<br />

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18<br />

20<br />

22<br />

6<br />

8<br />

10<br />

12<br />

14<br />

16<br />

18<br />

20<br />

22<br />

12<br />

5/2005 7/2005 9/2005 11/2005 1/2006 3/2006 5/2006 7/2006 9/2006 11/2006 1/2007 3/2007 5/2007 7/2007<br />

77<br />

Date<br />

McCullough, Lund and May (2008)<br />

Figure 8.8. EC profiles of pit lakes (a) Ramp 5a, (b) Ramp 8, (c) GAEE, (d) GAEW from May 2005 to August<br />

2007.<br />

6<br />

8<br />

10<br />

12<br />

14<br />

16<br />

18<br />

20<br />

22


Treating acidity in pit lakes using sewage and greenwaste<br />

(a).<br />

(b).<br />

(c).<br />

(d).<br />

Depth (m)<br />

0<br />

1<br />

2<br />

3<br />

4<br />

5<br />

6<br />

7<br />

8<br />

9<br />

10<br />

11<br />

Figure 8.9. Chlorophyll a profiles of pit lakes (a) Ramp 5a, (b) Ramp 8, (c) GAEE, (d) GAEW from May 2005 to<br />

August 2007.<br />

78<br />

0<br />

5<br />

10<br />

15<br />

20<br />

25<br />

30<br />

35<br />

40<br />

45<br />

50<br />

55<br />

60<br />

65


8.3.4 Metal/metalloid concentrations<br />

79<br />

McCullough, Lund and May (2008)<br />

There was greater variability in metal/metalloid concentrations than expected (Figure 8.10).<br />

Aluminium concentrations were generally stable over time, with highest concentrations of<br />

around ca.900 mg L -1 in Ramp 5a and lowest to ca.40 mg L -1 in Ramp 8 with GAEE/GAEW<br />

intermediate at 190 mg L -1. Ramp 5a surface waters Al concentration dropped drastically to<br />

ca.190 mg L -1 following heavy Wet season rains in January 2007, before slowly increasing<br />

again. GAEE and GAEW surface Al concentrations also decreased to 170 mg L -1 and<br />

120 mg L -1 respectively at this time, before also beginning to return to previous<br />

concentrations, albeit interrupted by further rains in June 2007. Although pit lake bottom<br />

waters remained largely unchanged over the monitoring period in Control lakes, GAEW<br />

bottom waters also decreased following 2006–2007 Wet season rains to 120 mg L -1 at the end<br />

of monitoring in July 2007.<br />

Conversely, B (boron) concentrations were very inconsistent over time at ranging from below<br />

detection limit 0.05 mg L -1 to


Treating acidity in pit lakes using sewage and greenwaste<br />

Ramp 5a and GAEW surface waters, which dropped following heavy rains in early 2007, Cd<br />

concentrations of other lakes stayed relatively stable to the end of monitoring.<br />

Cobalt concentrations were also high in all pit lakes. They were highest in Ramp 5a at around<br />

5 mg L -1 , lowest at 0.9 mg L -1 in Ramp 8 and 2.5 mg L -1 in GAEE/GAEW. Cobalt<br />

concentrations held at very constant concentrations for all lakes, except for Ramp 5a and<br />

GAEW surface waters which both showed decreases to around 0.9 mg L -1 following heavy<br />

Wet season rains in early 2007 before beginning to increase again in the following Dry<br />

season.<br />

Starting at high concentrations of around 0.4 and 0.15 mg L -1 for Ramp 5a bottom and<br />

surface waters respectively, and GAEE/GAEW at around 0.06 mg L -1, these three pit lakes<br />

also held relatively constant Chromium (Cr) concentrations until early 2007. Wet season<br />

rains occurred whereupon Ramp 5a surface water concentrations dropped sharply to around<br />

0.04 mg L -1. GAEE/GAEW surface waters also saw weaker declines to similar<br />

concentrations. Although GAEE/GAEW bottoms waters did not show significant Cr<br />

concentration changes during this time, the second-half of 2007 saw declines in GAEW<br />

bottom waters to around of 0.03 mg L -1 . Ramp 8 monitoring Cr concentrations began below a<br />

detection limit of 0.01 mg L -1 , rose to 0.02 mg L -1 in bottoms waters and 0.03 mg L -1 in<br />

surface waters over the second half of 2005 and first half of 2006, to again largely falling<br />

below the detection limit after the end of the 2006 Dry season.<br />

Copper concentrations followed a very similar trend to Cr, starting at high concentrations of<br />

around 2.2 and 1.0 mg L -1 for Ramp 5a bottom and surface waters respectively, and<br />

GAEE/GAEW at around 0.03 mg L -1. Nevertheless, although Ramp 5a and GAEE/GAEW<br />

surface waters showed a similar decline following early 2007 Wet season rains, aside from an<br />

outlier peak, GAEW bottoms water showed a decline to below a detection limit of 0.05 mg L -<br />

1 for this analyte in the first-half of 2007.<br />

Albeit with concentrations around 2,000 and 1,000 mg L -1 for Ramp 5a bottom and surface<br />

waters respectively, and GAEE/GAEW around 1,000 mg L -1 , Fe also showed a similar trend<br />

as Cr. Relatively stable Fe concentrations existed early 2007 Wet season rains, then there<br />

80


81<br />

McCullough, Lund and May (2008)<br />

were sudden decreases to 17 and 420 mg L -1 for Ramp 5a and GAEW surface waters. These<br />

decreases were then followed by increases to concentrations at July 2007 below those of<br />

initial monitoring concentrations for Ramp 5a waters and at the initial monitoring<br />

concentrations for other lakes. As with other solutes, Ramp 8 Fe concentrations were lower<br />

for Fe than other lakes, with bottom waters around 400 mg L -1 and surface waters around<br />

1,100 mg L -1 .<br />

Starting at concentrations of around 1,000–1,800 mg L -1 , Mg showed a different trend to the<br />

other alkali metal Ca, but similar to that of the heavy metals. Following early 2007 rains, Mg<br />

concentrations declined to 270 and 590 mg L -1 in Ramp 5a and GAEW surface waters<br />

respectively. All lakes and depths then increased back to initial monitoring concentrations<br />

over the 2007 Dry season, albeit with Ramp 5a surface waters the slowest to return.<br />

Manganese also showed a similar trend to other heavy metals, with initial monitoring Mn<br />

concentrations of around 100 mg L -1 for Ramp 5a bottom waters, 40 mg L -1 for both Ramp 8<br />

depths and 60 mg L -1 for other lakes and depths. Following early 2007 rains, Mn<br />

concentrations declined to 15 and 30 mg L -1 in Ramp 5a and GAEW surface waters<br />

respectively before then beginning to increase back again.<br />

Initial monitoring Na concentrations of all lakes were around 650 mg L -1 , except for Ramp 5a<br />

with bottom waters around 450 mg L -1 an surface waters around 1,000 mg L -1 . Following<br />

early 2007 rains, Na also showed declines to 160 and 270 mg L -1 in Ramp 5a and GAEW<br />

surface waters respectively. All lakes and depths then increased back to initial monitoring Na<br />

concentrations over the 2007 Dry season, albeit with Ramp 5a surface waters the slowest to<br />

return. Ramp 5a bottom waters had reached around 1,000 mg L -1 by the end of monitoring in<br />

July 2007.<br />

Nickel concentrations also followed the general heavy metal trend of high initial monitoring<br />

concentrations of around 8 and 12 mg L -1 for Ramp 5a surface and bottom waters<br />

respectively, 2 mg L -1 for both Ramp 8 depths and 5 mg L -1 for GAEE/GAEW lakes and<br />

depths. Following early 2007 rains, Ni concentrations declined to 1.7 mg L -1 in both Ramp 5a


Treating acidity in pit lakes using sewage and greenwaste<br />

and GAEW surface waters before then beginning to increase back to around 5 mg L -1 in<br />

Ramp 5a surface waters. Both GAEW water depths remain below initial monitoring<br />

concentrations at around 3 mg L -1.<br />

High Pb (lead) concentrations in all lakes of around 3 mg L -1 decreased to below a detection<br />

limit of 0.1 mg L -1 from late Dry season 2005 to late Dry season 2006. Following early 2007<br />

rains, Pb concentrations declined to 1 and 0.25 mg L -1 in Ramp 5a and GAEW surface waters<br />

respectively before then beginning to increase back to around previous concentration levels<br />

by July 2007.<br />

Sulfur concentrations were at extremely high concentrations of 6,000 mg L -1 for Ramp 5a<br />

bottom waters and 3,500 mg L -1 for all other lakes and depths until the beginning of 2007<br />

Wet season rains. Sulfur concentrations then increased by 2–3 times for a few months, until<br />

then decreasing back to initial concentrations. At the end of July 2007 monitoring, Ramp 5a<br />

and GAEW surface waters continued to decrease past previous concentrations to around<br />

2,000 mg L -1 .<br />

Zinc concentrations were high around 30 and 40 mg L -1 for Ramp 5a surface and bottom<br />

waters respectively, 6 mg L -1 for both Ramp 8 depths and 15 mg L -1 for GAEE/GAEW lakes<br />

and depths. Following early 2007 rains, Zn concentrations declined to 7 mg L -1 and 5 mg L -1<br />

in Ramp 5a and GAEW surface waters respectively before then beginning to increase back to<br />

initial monitoring concentrations. However, following early 2007 rains, GAEW bottom water<br />

Zn concentrations declined erratically to a July 2007 concentration of around 1 mg L -1.<br />

82


83<br />

McCullough, Lund and May (2008)


Treating acidity in pit lakes using sewage and greenwaste<br />

84


85<br />

McCullough, Lund and May (2008)


Treating acidity in pit lakes using sewage and greenwaste<br />

Figure 8.10. Changes in metal concentrations of Collinsville pit lakes and layers from April 2005 to August 2007. Note log(10) y-axis scale.<br />

86


87<br />

McCullough, Lund and May (2008)<br />

At the project completion in July 2007, aside from Ca, most mean water column metal<br />

concentrations in GAEW were different to that of GAEE (Table 8.3). Some mean GAEW<br />

metals’ concentrations such as Cd, Cr, Cu Fe and Pb were up to 10–20% higher than in the<br />

control lake. Potassium was 5,600% higher concentration. Nevertheless, Al, Ca, Co, Mg, Mn,<br />

Na, Ni and S and Zn all showed decreases in concentration of around 1–30%.<br />

Table 8.3. Mean GAEW metal concentrations relative to mean GAEE concentrations at July 2007 (mg L -1 ).<br />

Maximum concentrations indicate concentrations if all dosed mass were in solution.<br />

Solute Al Ca Cd Co Cr Cu Fe K Mg Mn Na Ni Pb S Zn<br />

GAEE 200 240 0.07 2.5 0.06 0.34 1,070 0.5 850 63 610 4.7 2.6 3,400 15<br />

GAEW 140 230 0.08 1.8 0.07 0.42 1,220 28 790 57 550 3.1 2.8 3,200<br />

Maximum<br />

concentrations<br />

%Change 69 97 106 72 120 120 110 5,600 92 89 90 67 110 94 43<br />

8.3.5 Nutrients<br />

Total nitrogen levels of all control lakes were generally less than 10 mg L -1 although<br />

hypolimnion waters of Ramp 5A were generally highest and displayed the highest<br />

concentration of 22 mg L -1 in August 2006 (Figure 8.11). Total nitrogen levels increased in<br />

the hypolimnion of GAEE only, both during and after dosing, to around five times (TN,<br />

46 mg L -1 ) background levels of total nitrogen. Rapid increases in both TN concentration to<br />

around 46 mg L -1 and TP to around 10 mg L -1 occurred after filling had ceased in January<br />

2007. Peculiarly, in July 2007 TN displayed a sudden decrease from around 45 mg L -1 to<br />

7 mg L -1 and TP concentrations dropped from 10 mg L -1 to around 5.8 mg L -1 . Concentrations<br />

of TN nevertheless rose over the next quarter to around 42 mg L -1 .<br />

Total phosphorus of control lakes was generally under 1 mg L -1 (Figure 8.11). However,<br />

hypolimnion waters of Ramp 5A were often elevated in TP, cycling every 4–5 months from<br />

1 mg L -1 to a high of 6 mg L -1 in September 2006. Epilimnion waters of Ramp 5A were<br />

generally under 1 mg L -1 although they suddenly spiked to 4 mg L -1 in April 2007. Total


Treating acidity in pit lakes using sewage and greenwaste<br />

phosphorus levels rapidly increased soon after filling began in August 2006, first in the<br />

epilimnion of GAEE to 9 mg L -1 before increasing in the hypolimnion to 10 mg L -1 around a<br />

month later. Total phosphorus epilimnion concentrations then declined in February 2007 and<br />

fluctuated around 4 mg L -1 afterward. GAEE hypolimnion waters also declined to 6 mg L -1<br />

around 3 months later, before spiking back to 10 mg L -1 the next month and then declining<br />

again.<br />

Gilvin of all control lakes displayed very high levels likely to be caused by confounding by<br />

the high dissolved iron concentrations of the AMD matrix (Figure 8.11). Nevertheless,<br />

GAEW epilimnion gilvin did appear to increase after organic additions in August 2006,<br />

peaking at 187 m -1 in June 2007, before declining to 110 m -1 in July 2007.<br />

The large additions of nutrient-rich organic material to GAEW resulted in greatly elevated<br />

concentrations of macro-nutrients (Table 8.4). However, there was a large difference between<br />

mean GAEW measured concentrations and maximum potential nutrients concentrations<br />

(assumed with a model of nutrients completely mixed but behaving conservatively).<br />

88


89<br />

McCullough, Lund and May (2008)<br />

Figure 8.11. Changes in (a) total nitrogen (TN), (b) total phosphorus (TP) and (c) dissolved organic carbon (as<br />

gilvin440) concentrations of Collinsville pit lakes and depths from April 2005 to August 2007.


Treating acidity in pit lakes using sewage and greenwaste<br />

Table 8.4. Mean depth GAEW nutrient concentrations compared to mean GAEE concentrations at July 2007<br />

(mg L -1) .<br />

8.3.6 Groundwater interactions<br />

TN TP<br />

GAEE 0.50 0.47<br />

GAEW 21 4.5<br />

GAEW maximum concentrations<br />

Factor of change 43 9.6<br />

Three water level data outliers were removed from the dataset; the first point for bore GAR01<br />

as it was assumed the bore was still stabilising after establishment, and a data point from<br />

GAR01 and GAEE/GAEW as for a single month they deviated grossly from surrounding data<br />

dates and monitoring points.<br />

Throughout the 46 month sampling period, groundwater levels were consistently above<br />

GAEE/GAEW water surface levels (Figure 8.12). Groundwater height also greatly increased<br />

generally following heavy rainfall events in early 2007. Groundwater height was greatest in<br />

GAR01 to the west of GAEE/GAEW, and lowest to the south in GAR03 with GAR02 depth<br />

slightly greater than GAR03.<br />

pH was circum-neutral across all monitoring bores at all times. Although groundwater pH<br />

fluctuated from 0.5–1.0 units between sampling months, there may have been a trend of<br />

decreasing pH in the three years of monitoring (Figure 8.13a). Groundwater specific<br />

conductance was highest in GAR01 at ca.13 mS cm -1 and lowest in GAR03 at ca.2 mS cm -1<br />

with GAR02 intermediate ca.10 mS cm -1. Groundwater specific conductance fluctuated very<br />

little in the southern monitoring bore GAR03. Groundwater at GAR03 did not respond in the<br />

same way as the more northern bores where there were troughs in specific conductance in<br />

April 2005 and October 2006 and a large spike in around July 2007 (Figure 8.13c).<br />

Groundwater solute concentration in all monitoring bores were dominated by SO 4 , Cl, Ca and<br />

Na (Figure 8.14). The proportion of major solutes were similar in the northern-most bores<br />

GAR01 and GAR02, however calcium represented only 7% of these total solute<br />

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91<br />

McCullough, Lund and May (2008)<br />

concentrations in the southern-most bore GAR03. Reflecting relative specific conductance<br />

values, major solute concentrations appeared to be fairly stable over time. Groundwater major<br />

solute concentrations were highest in eastern-most GAR02 and lowest in southern-most<br />

GAR03.<br />

Lower concentrations of Al, As, B, Co, Cr, Cu, Li, Mn, Mo, Ni, Se, U and Zn, were also<br />

detected in groundwaters, although Be, Bi, Sb and V were all below detection limits. Iron<br />

was the highest concentration solute for all groundwaters, and then Mn although southern-<br />

most GAR03 had higher concentrations of F than Mn (Figure 8.15). Although more variable<br />

than major solutes, relative and absolute concentrations of minor solutes still appeared to be<br />

fairly stable over time. Groundwater minor solute concentrations also reflected relative<br />

specific conductance values, being highest in eastern-most GAR02 and lowest in southern-<br />

most GAR03.<br />

Figure 8.12. Relative GAEE/GAEW groundwater and water surface levels between July 2004 to October 2007.


Treating acidity in pit lakes using sewage and greenwaste<br />

Figure 8.13. GAEE/GAEW groundwater monitoring bore water a) pH, b) acidity and, c) specific conductance<br />

between August 2004 to October 2007.<br />

92<br />

b)


Concentration (mg L -1)<br />

93<br />

McCullough, Lund and May (2008)<br />

Figure 8.14. Changes in major solute concentrations in monitoring bores a) GAR01, b) GAR02, and c) GAR03<br />

between November 2005 and July 2007.


Treating acidity in pit lakes using sewage and greenwaste<br />

Concentration (mg L -1)<br />

Figure 8.15. Changes in minor solute concentrations with mean values


8.4 Discussion<br />

95<br />

McCullough, Lund and May (2008)<br />

Remediation treatment of GAEW after only 6 months still appears to be in the early stages of<br />

development, however some trends have already become evident. Depth and duration of<br />

stratification is an important decider in the efficacy and viability of sulfate reduction as a<br />

remediation measure in any pit lake (Martin et al., 2003; McNee et al., 2003). Generally,<br />

CCP pit lakes appear to thermally stratify in the late Dry season although this stratification is<br />

broken when Wet season wind and rains arrive. Consequently, water column stratification is<br />

expected to occur in the treatment pit lake for at least 6 months of the year. Although heavy<br />

cyclonic rainfall events, as seen in early 2007 may destabilise thermal stratification earlier<br />

than usual, the halocline that forms as a result of this low conductivity water overlaying the<br />

denser high conductivity pit lake water may be more stable and effective at preventing<br />

mixing and consequently reduced metal oxidation than thermal stratification during warmer<br />

months (Wen et al., 2006). As shown by 2006 data, the unpredictable climate of this site<br />

makes prediction of remediation performance difficult as heavy rains and mixing events can<br />

still occur at any time of the year.<br />

Pit lakes do not appear to be thermally stratified over the cooler Dry season. Inversion of the<br />

thermocline during cooler months of the mid-Dry season are not likely to be due to<br />

exothermic re-oxidation of reduced sulfides in the hypolimnion as has been observed with<br />

cool-temperate AMD pit lakes (Gammons & Duaine, 2006) as the hypolimnion ORP did not<br />

markedly change at this time under the continuing influence of the halocline. Rather, it this<br />

inverted thermocline is more likely due to exothermic biological activity of anaerobic<br />

bacteria breaking down the rich the organic material.<br />

Low ORP groundwater appears to influence hypolimnions of Ramp 5a, and Ramp 8 in<br />

particular, it does not appear to be significantly intruding into GAEE or GAEW. The low-<br />

ORP cycles of Ramp 8 in mid-Dry season and mid-Wet season may be due to low pit lake<br />

levels due to evaporation, and high groundwater levels due to precipitation in the Dry and<br />

Wet seasons respectively. The water level differences would lead to hydraulic head in the<br />

favour of groundwater intrusion during these times. Similarly, although low ORP rainwater<br />

improved water quality for some time across Ramp 5a, the size of GAEE and GAEW appears


Treating acidity in pit lakes using sewage and greenwaste<br />

to have reduced the impact of the rainfall on ORP in these lakes. Nevertheless, catchment<br />

area the decreasing ORP in GAEW hypolimnion waters appears to be due to sulfate reductive<br />

processes in the lake’s sediment. These reductive process may also have been facilitated by<br />

halocline formation early in the 2006–2007 Wet season.<br />

Other control pit lakes have seen a slight decrease in epilimnion pH due to cyclonic rain<br />

waters, and Ramp 8 has seen a significant increase in hypolimnion waters due to groundwater<br />

ingress. However, unlike the very similar GAEE, GAEW demonstrated an increasing pH<br />

developing in the hypolimnion since late 2006, only a few months after organic dosing began.<br />

This pH increase is indicative of alkalinity-producing sulfate reduction in these low ORP<br />

waters.<br />

Not surprisingly, phytoplankton biomass is generally very low in the low nutrient<br />

environment of CCP pit lakes. Nevertheless, the addition of large amounts of macronutrients<br />

(carbon and phosphorus in particular) appears to have stimulated phytoplankton growth in<br />

GAEW a few months after organic dosing began. It is conceivable that benthic microbial<br />

communities may be supporting phytoplankton communities through reducing iron and<br />

aluminium bound P, effectively remobilising it, making it again available for absorption by<br />

phytoplankton (Kleeberg & Grüneberg, 2005). In turn, phytoplankton may be supporting<br />

sulfate reduction by fixing carbon in photosynthesis with dead algal cells then falling to the<br />

benthos where this carbon is made available to bacterial sulfate-reducers (Nixdorf et al.,<br />

2005).<br />

The sudden mid-2007 increase in surface water concentrations of metals to previous<br />

concentrations, including conservative ions such as Na may be due to evapo-concentration of<br />

epilimnions previously diluted by the heavy early 2007 Wet season rains. Although halocline<br />

epilimnion waters are lower EC, the slightly lower EC of GAEW bottom waters is probably<br />

primarily due to precipitation of iron and sulfate as monosulfides as indicated by decreases in<br />

S concentrations. Other, lower solubility metals such as Zn may also have precipitated as<br />

(oxy)hydroxides in this higher pH environment. The low EC that has been maintained in<br />

surface waters of well-mixed GAEW in July 2007 may similarly be due to increased algal<br />

96


97<br />

McCullough, Lund and May (2008)<br />

activity adsorbing some solutes (in particular nitrogen compounds) and again forming a<br />

higher pH local environment precipitating some metals by producing alkalinity during nitrate<br />

assimilation.<br />

Consequently, changes in metal/metalloid concentrations in the epilimnion can partially be<br />

explained through dilution during heavy rainfall events, and in the hypolimnion by<br />

immobilisation as sulfide and hydroxides as a result of sulfate reduction processes.<br />

Notwithstanding the effects of these processes, there was greater variability in hypolimnion<br />

metal/metalloid concentrations than expected. This may be due to subtle but significant<br />

differences in sampling height above the benthos at different sampling times. As the benthos<br />

is neared, a steep ORP gradient becomes apparent, and this is likely to correspond to a steep<br />

solute gradient for non-conservative species.<br />

Fe(III) reduction has been observed as the initial step of microbial sulfate reduction (Wendt-<br />

Potthoff et al., 2002). Although there have not yet been significant reductions in total<br />

dissolved Fe or S concentrations indicative of sulfate reduction, this may be due to Fe(III)<br />

reduction and consequent mobilisation showing an increase in total dissolved Fe<br />

concentration, prior to iron sulfide formation.<br />

The initial high concentration of chlorophyll in GAE at the beginning of monitoring in mid-<br />

2005 is difficult to explain as water quality throughout monitoring was extremely poor for<br />

algal growth. Nevertheless, as found with other studies eutrophying acid pit lakes (Lessmann<br />

et al., 2000; Fyson et al., 2006), chlorophyll concentrations, an indicator of phytoplankton<br />

biomass, have been shown to increase quickly following additions of limiting carbon and<br />

phosphorus nutrients. Consequently, the algal blooms of GAEW months after dosing are not<br />

unexpected.<br />

Although a northern monitoring bore is absent due to coal outcropping there, local<br />

groundwater movement appears to be from north to south toward nearby Corduroy Creek.<br />

Nevertheless, the consistently greater height of groundwater around the pit lake indicating<br />

that the pit lake is a local groundwater sink, with contamination of downstream groundwater


Treating acidity in pit lakes using sewage and greenwaste<br />

by leachate from this pit unlikely. Specific conductance appears to increase from west to east<br />

across GAE, however not across the expected flow direction of north to south implying a<br />

localised source of groundwater contamination immediately north of GAE. The elevated iron<br />

in the presence of marine salts implies that AMD evolution may be occurring in the presence<br />

of buffered saline groundwaters in this region, possibly originating from prehistoric saline<br />

intrusions. These waters, although circum-neutral, are likely introducing acidity and salinity<br />

to the GAE pit lakes.<br />

98


9 Conclusions<br />

99<br />

McCullough, Lund and May (2008)<br />

For long-term remediation purposes, organic matter additions are expected to be required at<br />

an ongoing, albeit lower, dosing rate. The use of refractory organic forms such as woody<br />

green waste, may also be advantageous to long-term remediation efforts, in that they will<br />

continue to degrade into more labile fractions available for sulfate reducers over long periods<br />

of time. Nevertheless, whilst denitrification is another alkalinity-generating process (Abril &<br />

Frankignoulle, 2001) that will remove excess TN over time, over-dosing of organic matter or<br />

changes in availability of P may lead to eutrophication (Yokum et al., 1997). Depending on<br />

final desired water quality and the location, eutrophication might be of concern (McCullough<br />

et al. (2008). It is unlikely, given the high iron levels that eutrophication of GAEW is likely<br />

in the short term to medium term, however as the rate of remediation is likely to increase as<br />

we move from extreme to more circum-neutral pH caution is recommended with regards to<br />

the quantities and nature of further organic matter additions. Nevertheless, eutrophied water<br />

bodies have an extensive research history and ‘toolbox’ for management, and will likely<br />

present more benefit to the environment and communities than the otherwise acidic pit lakes<br />

do.<br />

Depth and duration of stratification will remain an important decider in the efficacy and<br />

viability of sulfate reduction as a remediation measure in any pit lake (Martin et al., 2003;<br />

McNee et al., 2003). Water column stratification is expected to remain strong in this<br />

remediated pit lake over late Dry seasons due to the ambient hot tropical climate. In much the<br />

same way as straw has been postulated to change mixing in other studies (Koschorreck et al.,<br />

2002) greenwaste is likely to act as a mixing barrier for the water body directly above the<br />

sediment surface. Coupled with a high biochemical oxygen demand from continuing organic<br />

decomposition and carbon diagenesis, the hypolimnion should remain sufficiently anaerobic.<br />

Depending on its source, sewage sludge can contain high concentrations of heavy metals<br />

(Berrow & Webber, 1971). Both the Collinsville sewage displayed high concentrations for<br />

many heavy metals. However, these high heavy metals are unlikely to be biologically<br />

available, as if mobilised are likely to be precipitated as metal sulfides.


Treating acidity in pit lakes using sewage and greenwaste<br />

Further reduction in biological availability of metals and metalloids is also likely to occur<br />

through formation of complexes with organic chelators present as components of the<br />

refractory green waste, such as organic acids (Tipping & Hurley, 1992). In this respect, green<br />

waste may have an advantage of providing recalcitrant organic substances such as humic and<br />

fulvic acids, with which heavy metals may directly complex to. Ligand formation between<br />

heavy metals and refractory organics would further remove these toxic components from<br />

biological availability, albeit at a likely reduced capacity to that of sulfate reduction processes<br />

(Brown Jr., 2001).<br />

The early initiation of alkalinity production in green waste and green waste and sewage in<br />

only 37 days is likely to be due to a combination of two important factors unique to this<br />

study. Firstly, most other research published to date have occurred in cool temperate areas of<br />

Europe and North America e.g., (Gammons et al., 2000; Küsel & Dorsch, 2000; Küsel et al.,<br />

2001; Benner et al., 2002; Tostche et al., 2003; Frömmichen et al., 2004). The higher<br />

temperatures experienced in Collinsville, even during the middle of the Dry season (20–<br />

28 o C), and mimicked in the constant-temperature laboratory are likely to have exponentially<br />

increased biochemical rates of carbon diagenesis and metabolism.<br />

Secondly, the use of largely fresh green waste as opposed to refractory organic substrates<br />

such as straw (Frömmichen et al., 2003; Frömmichen et al., 2004), rye grass (Harris &<br />

Ragusa, 2000, 2001), etc., distinguishes this research from many others in the published<br />

literature. The greater labile fraction of organic material available in this fresher material may<br />

have contributed directly to electron donors for sulfate reduction. For example, chlorophyll<br />

was seen to be leached from the green waste and it is likely that highly labile sap sugars<br />

would have leached also. For long-term remediation purposes, organic matter additions are<br />

expected to be required at an ongoing, albeit lower, dosing rate. In this way, the use of<br />

refractory organic forms such as woody green waste, may be advantageous to long-term<br />

remediation efforts, in that they will continue to degrade into more labile fractions available<br />

for sulfate reducers over long periods of time (Place et al., 2006). Consequently, the use of<br />

fresh sewage to acid pit lakes, with or without complementary additions of green waste, may<br />

prove to be a novel practicable remediation strategy for AMD issues in remote mining<br />

locations. Indeed, Gusek (2002) even suggested injecting sewage sludge into mine shafts and<br />

100


101<br />

McCullough, Lund and May (2008)<br />

adits to remove and prevent production of acidity from these sources. For long-term<br />

remediation purposes, organic matter additions are expected to be required at an ongoing,<br />

albeit lower, dosing rate. The use of refractory organic forms such as woody green waste,<br />

may also be advantageous to long-term remediation efforts, in that they will continue to<br />

degrade into more labile fractions available for sulfate reducers over long periods of time.<br />

The ongoing monitoring of the field study component of this project is expected to reveal<br />

these sustainability considerations over these long treatment durations.<br />

This study has demonstrated promise for remediation of AMD water pH and high metal<br />

concentrations via sulfate reduction with green waste and sewage as organic substrates. This<br />

study also illustrates that corrective measures for acidic mining lakes also greatly differ from<br />

those in use for eutrophication control (Klapper, 2003). For example, average species<br />

number, bird numbers and biomass have been found to positively correlated with lake trophic<br />

status (Hall et al., 2006), demonstrating greater potential wildlife value for a eutrophic than<br />

an ultra-oligotrophic mining lake.<br />

Best practice AMD pit lake treatment is likely to be required to be made on a case-by-case<br />

basis where potential pit lake end uses and availability of organic substrates have been<br />

identified and a remediation strategy has consequently been constructed. Consequently<br />

researchers, consultants and regulatory agencies need to maintain an open-mind to treatment<br />

solution options for these unique environmental issues. Part of the challenge for both mining<br />

companies and regulatory waterbody managers with this assessment will be the ability to<br />

think laterally as to what the current values of the pit lake are, what treatments may be<br />

feasible, and what type of pit lake (water quality and quantity) is desirable for either social,<br />

environmental or other enduses (Doupé & Lymbery, 2005; McCullough & Lund, 2006).


Treating acidity in pit lakes using sewage and greenwaste<br />

10 Acknowledgements<br />

Thanks to Collinsville Coal Project (Xstrata Coal Queensland Pty Ltd) for logistical support<br />

and lease access. Thanks to Bowen Shire for in-kind support with materials and transport.<br />

Thanks to Queensland Environmental Protection Authority for consideration of the field<br />

project component. Thanks also to Joseph Steenbergen and Carlieke te Beest of Hogeschool<br />

Zeeland for laboratory assistance, to Gary Ogden for some of the chemical analyses, and to<br />

Tim Walker and Carl Wallis for field assistance. This project was made possible by<br />

Australian Coal Association Research Council grant C14052.<br />

102


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Charles, D. (1998). Wasteworld. New Scientist 157: 32.<br />

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Commander, D. P.; Mills, C. H. & Waterhouse, J. D. (1994). Salinisation of mined out pits in<br />

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International Association of Hydrogeologists. Adelaide, South Australia November,<br />

527-532pp.<br />

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Davies, N. & Willcocks, J. (1992). Climate variability in the Fitzroy Catchment. Proceedings<br />

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Treating acidity in pit lakes using sewage and greenwaste<br />

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112


113<br />

McCullough, Lund and May (2008)<br />

12 Appendix: Publications and Presentations<br />

arising from ACARP Project C14052<br />

Lund, M. A. & McCullough, C. D. (2004). Mine Lakes - More than just acidic, toxic scars on<br />

the landscape. In, Australian Society for Limnology 43rd Annual Congress. Adelaide,<br />

Australia 29th November - 3rd December, 2004.<br />

May, J.M., McCullough, C. D. & Lund, M. A. (2007), “Using Bioremediation to Tackle Acid<br />

Mine Drainage Water at Collinsville Coal Mine, QLD", Presentation made at XCN<br />

Environment & Community Forum, Kirkton Park, NSW, 7th May 2007.<br />

May, J.M. (2006). "Using bioremediation to tackle acid mine drainage water", Presentation<br />

made to Retired Miners’ Association, Collinsville, QLD,18th July 2006.<br />

May, J.M.(2006). "Using bioremediation to tackle acid mine drainage water", Presentation<br />

made to CFMEU Collinsville Lodge Representatives, Collinsville, QLD, 20th July<br />

2006.<br />

May, J.M. (2005), "A case study aimed at assisting CCP to meet its XCQ Sustainable<br />

Development, Biodiversity, Water, Community & Rehab Targets: Remediation of acid<br />

coal mine voids using biological processes and organic material", Presentation made at<br />

XCQ Environment & Community Meeting, Abbot Point, QLD, 17th August 2005.<br />

May, J.M., McCullough, C. D. & Lund, M. A. (2005). "ACARP Project C14052:<br />

Remediation of acid coal mine voids using biological processes and organic material",<br />

Presentation made at Central Queensland Mining Rehabilitation Group Meeting, Oaky<br />

Creek, QLD, 25th October 2005.<br />

McCullough, C. D. (2007). Approaches to remediation of acid mine drainage water in pit<br />

lakes. International Journal of Mining, Reclamation and Environment. 21 DOI:<br />

10.1080/17480930701350127.<br />

McCullough, C. D.; Hunt, D. & Evans, L. H. (in press). Social, Economic, and Ecological<br />

End Uses – Incentives, regulatory requirements and planning required to develop<br />

successful beneficial end uses. In Workbook of Technologies for the Management of<br />

Metal Mine and Metallurgical Process Drainage, Castendyk, D.; Eary, T. & Park, B.<br />

(eds.) Society for Mining Engineering (SME), Kentucky, USA,<br />

McCullough, C. D. & Lund, M. A. (2006). Pit lakes: benefit or bane to companies,<br />

communities and the environment? Proceedings of the Goldfields Environmental<br />

Management Group Workshop on Environmental Management 2006. Kalgoorlie,<br />

Australia 24th - 26th May. 12p.<br />

McCullough, C. D.; Lund, M. A. & May, J. M. (2005). The addition of green waste and<br />

municipal sewage to a tropical acid pit lake, a novel approach to remediation; or, 'Why<br />

we filled a pit lake with dead plants and poo'. Proceedings of Australian Society for<br />

Limnology 44th Annual Congress. Hobart, Australia 28th November - 2nd December,<br />

2004.<br />

McCullough, C. D.; Lund, M. A. & May, J. M. (2006). Microcosm testing of municipal<br />

sewage and green waste for full-scale remediation of an acid coal pit lake, in semi-arid<br />

tropical Australia. Proceedings of the 7th International Conference on Acid Rock<br />

Drainage (ICARD). St Louis, Massachusetts, USA. 1,177-1,197.


Treating acidity in pit lakes using sewage and greenwaste<br />

McCullough, C. D. & Lund, M. A. (2006). Pit lake sustainability; what is it, and how do I get<br />

it? Proceedings of the 2006 Water in Mining conference. Brisbane, Australia 24th -<br />

26th November, Australasian Institute of Mining & Metallurgy. 323-330.<br />

McCullough, C. D. & Lund, M. A. (2006). Opportunities for sustainable mining pit lakes in<br />

Australia. Mine Water and the Environment. 25(4): 220-226.<br />

McCullough, C. D.; Lund, M. A. & May, J. (2008). Field scale demonstration of the potential<br />

for sewage to remediate acidic mine waters. Mine Water and the Environment. 27(1)<br />

DOI 10.1007/s10230-007-0028-y.<br />

114

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