International Journal of Coal Geology 78 (2009) 161168

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International Journal of Coal Geology

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / i j c o a l g e o

Greenhouse gas emissions from low-temperature oxidation and spontaneous combustion at open-cut coal mines in Australia
John N. Carras, Stuart J. Day , Abou Sagha, David J. Williams
CSIRO Energy Technology, PO Box 330, Newcastle NSW 2300, Australia

a r t i c l e

i n f o

a b s t r a c t
Spontaneous combustion and low-temperature oxidation of waste coal in open-cut coal mines represents a potentially large source of greenhouse gas emissions. In this paper, emission uxes of CO2 and CH4 from spoil piles and waste coal dumps measured at 11 mines in the Hunter Valley and Bowen Basin in Australia are presented. The data displayed considerable scatter, which is consistent with the inhomogeneous nature of spoil pile material and permeability of surfaces. Despite the scatter, emissions were able to be classied into three broad categories according to the intensity of the spontaneous combustion present in the material. Average emissions ranged from about 12 kg CO2-e yr 1 m 2 to 8200 kg CO2-e yr 1 m 2, depending on the intensity of the spontaneous combustion. There was also, within the scatter of the data, an approximately linear trend of increasing emission ux with increasing surface temperature. A key nding of the research is that the emission rates of greenhouse gases from spoil piles where there is no spontaneous combustion, but only low-temperature oxidation of coal and coal waste, are similar to the emission rates due to biological activity from vegetated surfaces. However, further research is required to quantify the degree to which spoil piles that have no spontaneous combustion contribute to the anthropogenic atmospheric CO2 burden. 2008 Published by Elsevier B.V.

Article history: Received 9 September 2008 Received in revised form 27 November 2008 Accepted 2 December 2008 Available online 24 December 2008 Keywords: Coal mining Greenhouse Carbon dioxide Methane Spontaneous combustion Open-cut

1. Introduction Open-cut coal mining produces large amounts of waste material that is dumped into spoil piles behind the active mining area. Often these spoil piles contain appreciable amounts of coal from seams that are not economic to recover and other carbonaceous waste material. In addition, large quantities of carbonaceous reject material from coal preparation plants may be dumped around mine sites either as coarse rejects or tailings. These waste materials are usually exposed to the atmosphere for extended periods thus providing the opportunity for low-temperature oxidation to proceed, leading in some cases to outbreaks of spontaneous combustion (e.g. Stracher and Taylor, 2004; Pone et al., 2007; Kuenzer et al., 2007). Low-temperature oxidation occurs whenever carbon-containing material is exposed to oxygen in the air. Along with a certain amount of heat, oxidation produces CO2 and smaller quantities of other gases, chiey carbon monoxide. The rate of oxidation for a particular material depends on, inter alia, temperature, particle size, oxygen partial pressure, water content and extent of previous oxidation (see e.g. Carras and Young, 1994; Wang et al., 2003). The rate of reaction increases exponentially with temperature. If the heat generated by this process is not dissipated, as is often the case in large structures like coal stockpiles or spoil piles, the temperature will increase and the
Corresponding author. Tel.: +61 2 4960 6052; fax: +61 2 4960 6054. E-mail address: stuart.day@csiro.au (S.J. Day). 0166-5162/$ see front matter 2008 Published by Elsevier B.V. doi:10.1016/j.coal.2008.12.001

material will begin to self-heat (Carras and Young, 1994). Spontaneous combustion is the end result of this process where the temperature increases sufciently to cause the carbonaceous material to ignite. Both low-temperature oxidation and spontaneous combustion generate greenhouse gases. While low-temperature oxidation and spontaneous combustion arise from the same basic processes and represent different extremes of the same phenomenon, the greenhouse gas emissions from each are different. At ambient temperatures the major greenhouse gas emission from oxidation is CO2. However, at the elevated temperatures present in material affected by spontaneous combustion, parts of the coal can be starved of oxygen with the result that the chemical reactions change and appreciable quantities of CH4 can be produced. Note that this methane is produced as a result of the heating and is therefore separate to seam gas trapped in the coal. The extent to which the carbonaceous material is exposed to oxygen depends on the mining method and the rehabilitation cycle. Modern mining operations have active rehabilitation programs where spoil is covered with topsoil and revegetated. This restricts the ingress of oxygen into spoil piles thus reducing the rate of generation of greenhouse gases. However, there is often a long period before rehabilitation is completed during which time the material is exposed to the atmosphere. In some older mines, where past practices have not been as effective, spoil may be exposed for many years. Consequently, low-temperature oxidation and spontaneous combustion represent a potentially large source of greenhouse emissions from open-cut coal mining.

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Fig. 1. Schematic diagram of a dragline spoil pile showing spontaneous combustion and greenhouse gas emissions.

Fig. 1 illustrates some of the features of a coal mine waste dump, in this case dragline spoil, which will inuence the rate of greenhouse gas emissions. The rate of emission will depend on the location of spontaneous combustion and the nature of the spoil pile surface i.e.: The location of fuels (coal and carbonaceous waste). The voidage and particle size distribution in the dump, which will determine the diffusion and permeability characteristics of the dump. The extent of oxygen transport into the dump, which is important in determining the ratio of CO2 to CH4 produced. The presence of cracks in the dump, which act as conduits to the surface for the gases produced from spontaneous combustion and low-temperature oxidation. The concentration of oxygen within a spoil pile will depend on the dominant oxygen transport mode and the rate at which oxygen is being consumed. For instance, diffusion will restrict appreciable oxygen concentration to within about 10 m of the surface, whereas forced and natural convection can transport oxygen into the centre of a spoil pile, particularly if there are large cracks (Bainbridge et al., 1994). The ratio of CH4 to CO2 in the gases will depend on these physical factors, the temperature of the material as well as the chemical processes taking place (Walker, 1999). Different waste piles give rise to different surface structures. For instance, bare spoil or spoil that is over-dumped by inert material can form large cracks which act as conduits for the emission of combustion products including greenhouse gases. Other waste materials, such as coarse reject or block tipped spoil, tend to exhibit less cracking as the material is generally more homogeneous than spoil. Large cracks emitting hot gases will tend to dominate the local emissions. Smaller cracks or higher permeability regions will assist to distribute the overall emissions more widely. Consequently, emission uxes are likely to vary widely across spoil piles from individual mines. In Australia, the occurrence of spontaneous combustion in opencut coal mines is very variable. Some mines have extensive outbreaks with visible smoke and steam over large areas of spoil while many others have no history of spontaneous combustion at all. Lowtemperature oxidation, on the other hand, is likely to be present at all mines since all mines produce some level of carbonaceous waste. The extent of emissions from low-temperature oxidation will, of course, depend on the amount of carbon exposed to the atmosphere. Despite the potential magnitude, there are virtually no data available on the emissions of greenhouse gases from low-temperature

oxidation and spontaneous combustion. The reason for this is that direct measurement of these emissions is difcult due to the diffuse nature of the emissions and the large scale of mine sites. Measurements of fugitive methane emissions from open-cut coal mines have been made previously using a plume tracking method (Williams et al., 1993) and, in principle, this methodology could also be applied to estimating emissions from low-temperature oxidation and spontaneous combustion. In this technique, a vehicle tted with gas analysers is driven during appropriate meteorological conditions downwind of the mine site and the concentration of the resultant gas plume is measured across its width. A plume dispersion model is then used to calculate the ux of methane from the mine. Although this method has been used successfully to estimate fugitive methane emissions, there are a number of practical problems which limit its general applicability. Firstly, it is dependent upon prevailing weather conditions and, where mines are closely spaced, it may not be possible to separate emissions from individual mines. A second problem is that the concentrations of the gases measured may be only slightly above ambient levels, especially in the case of methane. Hence, there may be large relative errors associated with the measurements. Importantly, emissions of CO2 and methane from spontaneous combustion are not easily separated from the fugitive seam gas emissions. Greenhouse gas emissions from spontaneous combustion in opencut coal mines are recognised by the Intergovernmental Panel on Climate Change (IPCC) but due to the lack of measurement methodology they note in the most recent Guidelines for National Greenhouse Gas Inventories (IPCC, 2007): Uncontrolled combustion in waste piles is a feature for some surface mines. However, these emissions, where they occur, are extremely difcult to quantify and it is infeasible to include a methodology. Consequently, emissions from low-temperature oxidation and spontaneous combustion are not currently included in national greenhouse gas inventories but this could change in the future. The primary aim of this study, therefore, was to investigate a potential method of estimating emissions of CO2 and CH4, based on direct measurements, from low-temperature oxidation and spontaneous combustion at operating open-cut coal mines. 2. Experimental methods Emissions of the direct greenhouse gases, CO2 and CH4, from spontaneous combustion and low-temperature oxidation in spoil piles

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were measured at 11 open-cut coal mines. The indirect greenhouse gases, carbon monoxide and non-methane volatile organic compounds, which may be associated with spontaneous combustion, were not considered. The mines were located in two of the main coal producing regions in Australia; the Hunter Valley in NSW and the Bowen Basin in Queensland. All mines produce bituminous coal with total carbon contents between about 80 and 90% C (daf). Mines were selected to include those with little or no spontaneous combustion ranging through to mines with severe occurrences covering large areas of the mine site. Fluxes of greenhouse gases from sections of coal mine waste were determined directly by placing a purpose-built chamber on the ground surface and measuring the concentration of CO2 and CH4 emitted into the chamber. Two different chambers were used for these measurements, depending on the emission rate of greenhouse gases. For low emission rates, measurements were made using a cylindrical chamber 37.5 cm in diameter and 40 cm high with a total volume of about 45 L and an area of coverage of 0.11 m2. In these measurements the rate of gas emission was low enough so that the accumulation of the gas could be measured over a period of several minutes without exceeding the dynamic range of the instruments. For these runs, the chamber was placed on the ground and sealed by placing sand around its base. A small solar-powered fan inside the chamber ensured that the sample was well mixed during the measurement period. The small chambers were found to be unsuitable in some locations with high emission rates because their small coverage prevented them from fully enclosing some cracks often associated with intense spontaneous combustion. As well, many individual measurements were required to cover appreciable areas. To overcome these problems, large chambers with a triangular cross section and made from lightweight polycarbonate sheeting were used where necessary. The dimensions of the large chambers were 4 m long by 1 m wide, covering an area of 4 m2 or approximately 40 times that of the smaller chamber (Fig. 2). The total enclosed volume of these chambers was approximately 1200 L. The chamber shown in Fig. 2 was demountable, enabling it to be moved easily between test sites. These chambers were operated in a dynamic mode where ambient dilution air was drawn through the chamber at a known rate by a fan xed at one end of the chamber. The intake air was taken well away from emission fumes with a ow rate typically about 600 L min 1 so that the turnover (or residence time) of the air in the chamber was about 2 min. Concentrations of CH4 and CO2 were measured in the efuent from the chamber. This procedure maintained the gas concentrations within the dynamic range of the instruments and was used for areas with higher emission rates.

In both the small and large chambers, sample air was withdrawn from the chamber through a 6 mm diameter nylon sample line by a small Teon diaphragm pump at about 5 L min 1 and passed into a polyethylene manifold located inside a specially instrumented 4WD vehicle. The sample air in the manifold was analysed for CO2 with a Binos NDIR CO2 analyser (01000 ppm range; resolution 1 ppm) and CH4 with a Horiba ame ionisation detector CH4/NMHC analyser (0 50 ppm range; resolution 0.1 ppm). The instruments were calibrated daily by checking the zero with dry nitrogen and the span with appropriate reference gases (1050 ppm CO2 in nitrogen and 10 ppm CH4; BOC Gases Australia Pty Ltd). To cope with very high emission rates, a dilution system was used in which sample air was mixed with high purity nitrogen in known ratios via two calibrated mass ow controllers. For the small chambers at low emission rates, the rate of increase in concentration of CO2 and CH4 in the chamber was monitored over a period of approximately 10 min. The gas ux, F, (i.e. mass/unit area/ time) was calculated from Eq. (1). F= Ro Vc A 1

where Ro is the initial rate of increase in concentration, Vc is the volume of the chamber and A is the area covered by the chamber. For the large chamber operated in the dynamic dilution mode the emission ux was determined from Eq. (2). F= fd Cs Ca A 2

where Cs is the concentration of CO2 or CH4 in the chamber, Ca is the concentration of CO2 or CH4 in the dilution air, fd is the ow rate of the dilution air and A is the area of the chamber. On many occasions, the temperature of the ground was measured at the time of the emission ux measurements. A thermocouple probe was used to measure the temperature of the ground 50 to 100 mm below the surface. 3. Results Measurements of emissions were made at ve mines in the Hunter Valley and six in the Bowen Basin. Sites were selected to include mines both with and without spontaneous combustion in the spoil piles to capture some of the expected variation in emissions. Depending on

Fig. 2. Schematic diagram of the large chamber used to measure gas ux from spoil piles and other surfaces.

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J.N. Carras et al. / International Journal of Coal Geology 78 (2009) 161168 Table 2 Emissions from spoil with spontaneous combustion but no visible signs of gases venting CO2 (mg s 1 m 2) Number of measurements = 40 Minimum 0.0 Maximum 17.5 Arithmetic mean 2.5 RMS deviation 4.3 CH4 (mg s 1 m 2) 0.0 0.3 0.02 0.06 CO2-e (mg s 1 m 2) 0.0 20.4 3.0 4.1

the availability of access to spoil piles at each mine, chamber measurements were made on a range of different surfaces including bare spoil with and without spontaneous combustion, rehabilitated spoil, tailings and coarse reject dumps. Almost 200 individual measurements were made across the 11 mines. 3.1. Spoil piles Emission uxes were measured on a variety of surfaces that could be broadly grouped into three categories corresponding to particular areas of spoil: 1. Regions of spoil showing clear signs of active spontaneous combustion, such as cracks in the ground, discolouration, hot ground and venting of steam. 2. Areas where active spontaneous combustion was known to be present, but without obvious gas venting. These areas were typically adjacent to those with obvious venting but measurements were made on surfaces without visible cracks or ssures. 3. Areas of bare or rehabilitated (i.e. revegetated) spoil where there was no spontaneous combustion. Table 1 summarises the emissions in the rst category measured on spoil across all of the mines. Note that the CO2-e results shown in Table 1 (and subsequent tables) are not necessarily the sum of the CO2 and CH4 (times 21) because maximum CO2 and CH4 emissions did not always occur together. There was signicant variation in the measured emission rates, even for sites which were within only a few metres of one another. This is not surprising given the heterogeneity of the spoil pile and the factors described previously which give rise to the variability. As indicated in Fig. 1, the emission rates depend on a number of factors specic to the spoil pile being studied. Emission rates of CO2 varied by a factor of nearly 30, ranging from 33 to 963 mg s 1 m 2. Methane emissions were also highly variable but in all cases were much less than CO2. However, in some cases, CH4 emissions were signicant and were probably associated with oxygen-starved regions of strongly heating spoil. The maximum CH4 emission measured was 15.6 mg s 1 m 2. Because of its high global warming potential (about 21 times that of CO2), the contribution of the CH4 to the total emissions (i.e. CO2-e) at these high CH4 sites was of the same order as the CO2 contribution. The average CO2-e across all mines for the high emission active sites was 260 mg s 1 m 2. Temperatures just below the surface were often measured at the time the greenhouse emissions were measured. Perhaps not surprisingly, the surface temperatures in areas with active spontaneous combustion were substantially higher than ambient. In a number of locations, temperatures well above 100 C were recorded and, in general, these were associated with higher emission uxes. This relationship is discussed further below. The emission uxes measured on spoil affected by spontaneous combustion, but without obvious gas venting, are shown in Table 2. Emission rates from these sites were signicantly less than spoil with intense gas venting. At these sites, CH4 emissions were very low and in most cases CH4 was not detected. The low CH4 levels were probably due to the much lower emissions generally and do not
Table 1 Emission ux from spoil with spontaneous combustion and obvious signs of gas venting CO2 (mg s 1 m 2) Number of measurements = 41 Minimum 33 Maximum 936 Arithmetic mean 230 RMS deviation 201 CH4 (mg s 1 m 2) 0 15.6 1.0 3.5 CO2-e (mg s 1 m 2) 33 1116 260 290

Note that the CO2 and CH4 values do not necessarily correspond; hence the CO2-e may not be the sum of the CO2 and CH4 shown.

necessarily indicate a change in the nature of the emissions at these sites. The average CO2-e emission ux of 3.0 mg s 1 m 2 was an order of magnitude lower than those measured at sites with gas venting, illustrating the importance of cracks in the spoil pile to provide pathways for gases to be vented to the atmosphere from spontaneous combustion. Although the magnitude of these emissions was much lower than in areas with venting, the variability of the uxes was also large. Ground temperatures on these sections of spoil were usually lower than measured on the spoil with gas venting and very high temperatures (i.e. above 100 C) were not encountered. However, the temperatures were generally higher than on ground unaffected by spontaneous combustion, and as before, there appeared to be a broad correlation between higher temperatures and emission uxes. A summary of emissions measured in spoil which had no incidences of spontaneous combustion is provided in Table 3. As expected, emissions from spoil unaffected by spontaneous combustion were low. Only CO2 was detected; in no case was any methane found. Measurements were also carried out at a further four sites to assess the possible contribution of microbial activity and biological degradation on the emission uxes measured for the spoil piles with no spontaneous combustion. One site was at the CSIRO grounds at North Ryde in suburban Sydney where the chamber was applied to bare soil, grassed areas and ground with a natural covering of leaves. Another site was at a Hunter Valley coal mine where there has not been a history of spontaneous combustion in the spoil piles. The third and fourth sites were at two mines in the Bowen Basin, again in regions where there had not been any spontaneous combustion in the spoil piles. Table 4 shows a summary of the results measured at these locations. The results in Table 4 suggest that the emissions for the CSIRO grounds at North Ryde and for spoil with no history of spontaneous combustion are similar in magnitude. It is instructive to consider measurements by other workers on the emission rates of CO2 from normal soil and vegetation processes. For instance, Lofteld et al. (1992) measured the emission rate of CO2 and N2O from a beech forest soil. While their data showed a strong temperature dependence, the overall emission of greenhouse gases as CO2-e varied between about 0.03 and 0.15 mg s 1 m 2. In Australia, Wang et al. (1997) measured CO2 and N2O emission rates from legume pasture in rural NSW. They found similar overall emission rates to those of Lofteld et al. with values between about 0.02 and 0.2 mg s 1

Table 3 Emissions from spoil where there were no visible signs of spontaneous combustion CO2 (mg s 1 m 2) Number of measurements = 32 Minimum 0.0 Maximum 2.4 Arithmetic mean 0.4 RMS deviation 0.6 CH4 (mg s 1 m 2) 0.0 0.0 0.0 0.0 CO2-e (mg s 1 m 2) 0.0 2.4 0.4 0.6

Note that the CO2 and CH4 values do not necessarily correspond; hence the CO2-e may not be the sum of the CO2 and CH4 shown.

J.N. Carras et al. / International Journal of Coal Geology 78 (2009) 161168 Table 4 Average greenhouse gas emissions for natural surfaces and those with no history of spontaneous combustion Site North Ryde Hunter Valley Bowen Basin n 12 12 13 CO2 Flux (mg s 1 m 2) 0.12 0.15 0.08 CH4 Flux (mg s 1 m 2) 0.00 0.00 0.002 CO2-e (mg s 1 m 2) 0.12 0.15 0.14 RMS deviation 0.10 0.21 0.16

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m 2. These values are similar to those shown in Table 4 and will be considered further in the Discussion. 3.2. Reject and tailings A number of the mines visited had signicant reject and tailings dumps from coal preparation plants on site. Spontaneous combustion was present in some of these emplacements. Like the measurements made on spoil piles, emissions were measured on rejects with active spontaneous combustion, on material that was affected by spontaneous combustion but did not have pronounced outward signs, and on material in which there was no spontaneous combustion. The results for each category are summarised in Table 5. The emissions from rejects were, like the spoil material, also subject to substantial variability. However, the results clearly show that emissions are strongly dependent upon whether or not spontaneous combustion is present in the material, consistent with the categories used to group the spoil emissions. 3.3. Temperature effect In areas of spoil that were affected by spontaneous combustion, high emissions seemed to be associated with higher surface temperatures. Plotting these data suggested that there was a correlation between emission rate and temperature; however, there was considerable scatter in the results. Most of the measurements made during this study were made during the day when the ground was warmed by solar radiation. To further investigate the relationship between emission rate and ground temperature, a series of intensive measurements were made at a

single mine during winter and in the early morning to avoid solar heating. Temperature and emission measurements were made on spoil with active spontaneous combustion at closely spaced intervals within an area of approximately 20 24 m. This area enclosed an open crack in the ground, about 6 m long, through which hot gas was issuing. Temperatures were measured at ve or six locations within the footprint of the chamber to yield an average surface temperature. The results are shown in Fig. 3 as temperature and emission contours within the bounded region. The clustering of the temperature contours (grey lines) clearly indicates the position of the crack through which hot gases were emanating. The maximum temperature measured in the centre of the crack was 320 C, although this dropped away rapidly only a short distance from the edge of the crack. The temperature of the ground unaffected by spontaneous combustion was about 10 C. The emission rate prole of the test area is shown in Fig. 3 as black contours. Because of the very high temperatures over the centre of the crack, it was not possible to place the plastic chamber directly over the crack. Instead, emission measurements were made immediately to the side of the crack. Consequently, the maximum emissions shown in Fig. 3 are slightly offset from the temperature prole. Nevertheless, highest emissions are associated with the highest temperatures. Like the measurements made at other mines, signicant amounts of CH4 were associated with high emission uxes. These data were replotted in Fig. 4 where the emission ux is shown as a function of the average temperature of the ground covered by the chamber. From an emissions inventory standpoint, units of kg yr 1 m 2 may be more useful than mg s 1 m 2 for compiling annual mine site emissions data. Hence these units are also shown in Fig. 4. Although there is a substantial amount of scatter in the data, there is a denite trend of increasing emissions with increasing temperature. In this set of data, there are no emissions below about 10 C;

Table 5 Emissions from coal rejects CO2 (mg s 1 m 2) Category 1 high emissions Number of measurements = 9 Minimum 23 Maximum 264 Average 95 RMS deviation 69 Category 2 moderate emissions Number of measurements = 15 Minimum 0.1 Maximum 8.5 Average 3.1 RMS deviation 2.5 Category 3 low emissions Number of measurements = 47 Minimum 0.0 Maximum 11.0 Average 1.5 RMS deviation 2.8 CH4 (mg s 1 m 2) CO2-e (mg s 1 m 2)

0.0 4.7 0.8 1.4

23 287 111 92

0.0 0.2 0.03 0.1

0.1 9.4 3.8 3.2

0.0 0.0 0.0 0.0

0.0 11.0 1.5 2.8

Note that the CO2 and CH4 values do not necessarily correspond; hence the CO2-e may not be the sum of the CO2 and CH4 shown.

Fig. 3. Temperature and CO2-e emission contours measured on a 20 24 m section of spoil with active spontaneous combustion. Grey lines represent temperature (C); black lines correspond to emissions (mg s 1 m 2). The heavy black line shows the approximate location of an open crack in the ground.

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(1998) found the values u = 0.05 and v = 1.4 provided the best t to their data. The rate of oxidation can be described by the empirical expression: Q o = Af r C n exp E=RT exp q=RT 5

Fig. 4. Measured average emission rates (as CO2-e) as a function of average surface temperature.

however, this threshold temperature is strongly dependent on the ambient conditions. In the bulk of the measurements made during the day-time, for example, the temperature below which emissions were zero appeared to be around 20 C. 3.4. Emissions from low-temperature oxidation Carras et al. (1998) described in detail the processes responsible for the self-heating of coal spoil piles and have provided a basis for calculating the greenhouse gas emissions for low-temperature oxidation. A model for a one-dimensional process which describes the penetration of oxygen into spoil by the processes of diffusion and advection can be formulated with the following equation for oxygen conservation: e AC A2 C AC = De 2 vx + 1 es Q o At Ax Ax 3

where Qo, the rate of oxidation is expressed as g O2 g 1 coal s 1, A is a pre-exponential constant, f(r) is a function of the particle size, C is the concentration of oxygen, n is an exponent, E is the apparent activation energy, R is the gas constant, T is the temperature, is an empirical constant and q is the amount of oxygen that has reacted previously with the coal (Nordon et al., 1979). The rst exponential term ensures that the rate of reaction increases with temperature while the second exponential accounts for the reduction in rate as oxidation proceeds. Values for the oxidation rate have been measured by the authors for a range of Hunter Valley and Bowen Basin coals as part of their continuing research on spontaneous combustion. While the detailed oxidation data for each coal is different, the range of oxidation rate behaviour may be considered to be approximately the same for purposes of estimating the emissions of greenhouse gases, within the broad accuracy of the current approach. The amount of CO2 emitted during low-temperature oxidation, while different for different coals, typically lies between 15 and 25% of the oxygen taken up by the coal on a mass basis. Consequently, for the current purposes, the emission rate of CO2 can be written as: Q CO2 = 0:20Q o 6

By assuming steady state has been reached in Eq. (3) above and writing Eq. (5) in the simplied form yields: Q o = ACc mCexp E=RT 7

where s is the spoil density, t is time, Qo the rate of oxidation for coal or spoil, C is the concentration of oxygen, De is the effective diffusion coefcient of oxygen in the spoil pile and vx is the apparent airow in the x direction. In the above equation, is the pile voidage. This is a measure of the empty space within a spoil pile and is related to the swell factor for the spoil pile. The diffusion coefcient for spoil has been studied by Carras et al. (1998) who recommended an empirical expression similar to that developed by Troeh et al. (1982) for soils:  De = Do  e u v 1 u 4

where m is a factor to account for the particle size dependence and has been given values of 0.5 and 1 and A, the pre-exponential term in Eq. (5), has now been expressed as a linear function of the carbon content of the spoil (Cc). These equations can be solved to yield CO2 emission rates as a function of temperature and carbon content of the spoil. While each coal seam will have its characteristic values for each parameter, which must be obtained from detailed experiments, for the purposes of the current work the approach outlined above allows the overall magnitude of the emission from low-temperature oxidation to be calculated. A calculation of the rate of emission of CO2 from spoil of uniform material properties and undergoing low-temperature oxidation with

where Do is the diffusion coefcient of oxygen in air, is the air voidage and u and v are empirical constants. For values of for soils and spoil in the range 0.15 to 0.55, Troeh et al. (1982) and Carras et al.

Table 6 Calculated CO2-e emission rates (mg s 1 m 2) for spoil of different carbon contents and temperatures Carbon content of spoil Temperature (C) 15 27 1% 0.02 0.03 5% 0.03 0.07 10% 0.04 0.09 20% 0.06 0.13 30% 0.08 0.16 40% 0.09 0.19 50% 0.1 0.21 Fig. 5. Plot of estimated CO2 emission rate for low-temperature oxidation as a function of carbon content of the spoil showing the likely range of values for a given carbon content due to variations in coal rank, temperature of the spoil and particle size distribution.

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no restriction on the oxygen diffusion into the spoil yields the results shown in Table 6. The emission rates calculated from Table 6 are within the broad range of values measured on spoil piles and other natural surfaces without spontaneous combustion. For example, the average values for the North Ryde site and Hunter and Bowen Basin spoils are 0.12, 0.15 and 0.14 mg s 1 m 2, respectively (Table 4). The overall data from the calculations are shown in Fig. 5 where a range of emission rates for each value of carbon in the spoil pile has been plotted in order to show the variability to be expected due to variations in the temperature of the spoil, particle size distributions and rank of the coal and waste. 4. Discussion The results of the eld measurements show that although there is a substantial amount of variability, emissions can be grouped into three categories according to visible signs of spontaneous combustion. Based on these categories, emission rate ranges can be assigned to each category, as shown in Table 7. Since the data do not necessarily follow normal distributions, both the arithmetic mean and geometric mean (which applies to log-normally distributed data) are shown. The values in parentheses are the root mean squared (rms) deviations, indicating the degree of variability, while n is the number of measurements on which the averages were based. Note that the emission rates in Table 7 are expressed in units of kg yr 1 m 2. The variability in the results is reected in the high rms values, which are comparable to the mean values. In addition, there are large variations between the categories of spoil. The average emission rate of rst category is more than 85 times greater than the second. This indicates that once spontaneous combustion occurs, its impact on the emission rates is very marked, particularly when it progresses to the intense stage. However, counteracting this is the fact that at most coal mines spontaneous combustion is either absent or occupies only a small fraction of the spoil. A similar analysis of the data for rejects and tailings is shown in Table 8. The results shown here are generally consistent with those measured on spoil material and the emissions of the second two categories of each material type are broadly similar, allowing for the variability in the data. However, the emission rate from intense spontaneous combustion in reject material appears to be signicantly lower than in spoil. This may be due to differences in the structure of reject dumps compared to spoil piles. For example, the particle size ranges of rejects and tailings are much narrower than spoil. This is likely to allow reject material to pack more tightly than spoil thus restricting the ingress of air. Other factors such as the depth of the
Table 7 CO2-e emission rates for the Hunter Valley and Bowen Basin spoil according to type of spontaneous combustion Type of surface Active spontaneous combustion with marked surface signs. Large cracks with obvious signs of gas venting Smoke and steam Hot gases Surface discolouration Active spontaneous combustion with less obvious surface signs. Surface discolouration No large cracks Little smoke or steam Bare spoil, rehabilitated spoil with no spontaneous combustion The values in parentheses are the rms deviations. Emissions rate (kg yr 1 m 2) Arithmetic mean: 8200 (9147) Geometric mean: 5012 n = 41

Table 8 Combined emission rates for the Hunter Valley and Bowen Basin reject and tailings according to type of spontaneous combustion Type of surface Active spontaneous combustion with marked surface signs. Large cracks with obvious signs of gas venting Smoke and steam Hot gases Surface discolouration Active spontaneous combustion with less obvious surface signs. Surface discolouration No large cracks Little smoke or steam Bare reject or tailings with no spontaneous combustion The values in parentheses are the rms deviations. Emissions rate (kg yr 1 m 2) Arithmetic mean: 3500 (2900) Geometric mean: 2642 n=9

Arithmetic mean: 101 (98) Geometric mean: 58 n = 15 Arithmetic mean: 28 (9.5) Geometric mean: 6 n = 47

reject dump and the lower occurrence of ssures in this type of material may also contribute to differences in the nature of spontaneous combustion. An important nding of this work is that the measured emission rates from low-temperature oxidation are similar in magnitude to those obtained from some natural surfaces with microbial respiration. A comparison between the range of measurements from all surfaces where there was no spontaneous combustion and the calculations of emissions from low-temperature oxidation is shown in Fig. 6. The data are presented as box plots where the bottom and top limits of each box represent the 25th and 75th percentiles, respectively, and the horizontal line through the box indicates the median. The error bars show the 10th and 90th percentiles of the data. The ranges for the rst ve groups of data (i.e. previously published data for forest oor and pasture, background values at North Ryde, the Hunter and the Bowen Basin as well as the current calculations for spoil piles with no spontaneous combustion) are all similar and it is not possible based on the current data to separate them with any degree of certainty. For spoil and reject material, however, the range of measured values were signicantly higher than the other groups. Closer examination of the data in each of these groups shows that the

Arithmetic mean: 94.6 (129.3) Geometric mean: 38 n = 40 Arithmetic mean: 12.6 (18.9) Geometric mean: 7 n = 32

Fig. 6. Range of measured and calculated CO2-e emission rates for various sources without spontaneous combustion. Median values are represented as the horizontal lines in the boxes.

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range is heavily biased by a small number of large values (e.g. the value of around 250 kg yr 1 m 2 for reject). The median values, shown as lines in the boxes in Fig. 6, on the other hand, are much lower. Allowing for bias introduced by these high values, spoil and reject have emission factors similar to those of the other ve groups. The extent to which such emissions make a net contribution to the total greenhouse gas emission is an issue that needs to be resolved. In the current work we have shown that the greenhouse emissions from natural ground are of the same order as the emissions from the Hunter Valley and Bowen Basin spoil piles, without any spontaneous combustion. For bare spoil, rejects and tailings emissions are probably due to oxidising carbonaceous waste, but in rehabilitated revegetated ground, this seems unlikely. It is more likely that emissions from revegetated ground are a result of microbial activity. Isotopic analysis of the emitted CO2 would resolve this issue but such analyses were not carried out during this project. Although emissions from spoil without spontaneous combustion are low, the area covered by spoil surfaces at a coal mine is normally large. Therefore the actual value of the emission rate assigned to this material is crucial when estimating greenhouse gas emissions from individual mines. The signicance of this can be seen from a simple calculation. For 1 km2 of spoil, an additional emission rate of 0.1 mg s 1 m 2 CO2-e (3.2 kg yr 1 m 2) above background yields more than 3 kt additional CO2 per year. The results of this study provide a simple basis for estimating greenhouse emissions from individual coal mines that are affected by spontaneous combustion. In principle, all that is required is an estimate of the area of affected ground which corresponds to each category of emissions. The area is then multiplied by the appropriate emission factor. (The emission factors determined in this study were established with bituminous coals; coals of other ranks may yield different factors). In practice, however, estimating the area of affected ground may be quite difcult due to the large area of a typical open-cut coal mine and the difculty in accessing much of the terrain. Thus, ground based surveys will introduce a signicant source of uncertainty in addition to that inherent in the emission factors. An alternative and potentially more accurate method of assessing the area of ground affected by spontaneous combustion may be airborne or satellite-based remote sensing. The identication of a correlation between emission ux and surface temperature is important in this regard since it enables emission estimates for individual mines to be made using remote sensing to measure ground temperatures. This technique has been investigated by our group and will be the subject of a future paper. 5. Conclusions Direct measurements of greenhouse gas emissions were carried out at 11 coal mines in the Hunter Valley and Bowen Basin. Carbon dioxide was the main component of these emissions, but in areas of intense spontaneous combustion, large amounts of methane were also found. The measurements covered spoil piles and coal reject and tailings and, although subject to considerable variability, it was possible to classify the data into three broad categories according to the extent of spontaneous combustion: 1. Intense spontaneous combustion characterised by smoke and steam, major cracks, surface discolouration and obvious signs of gas venting. The emission factors apply to the intense emissions from the cracks and close vicinity. 2. Spontaneous combustion with less well pronounced signs, small cracks, surface discolouration and occasional or whisps of smoke or steam. 3. No sign of spontaneous combustion.

The scatter observed in the results is to be anticipated given the inhomogeneous nature of spoil pile material and variable permeability of surfaces. Emissions from spoil were generally similar to those from reject and tailings, however, in areas affected by intense spontaneous combustion, emissions were somewhat lower in rejects than in spoil. This may be due to the structure of reject dumps being more effective at preventing ingress of air. The emission rates of greenhouse gases from spoil piles where there is no spontaneous combustion, but only low-temperature oxidation of coal and coal waste, are similar to the emission rates due to biological activity from vegetated surfaces. Further research is required to quantify the degree to which spoil piles that have no spontaneous combustion contribute to the anthropogenic atmospheric CO2 burden. Acknowledgements The authors are grateful to all those at the participating mines for their assistance during the eld measurement campaigns and for providing subsequent data. We are also indebted to Ferenc Szemes, Ludo Bernaudat and Tony Lange who helped conduct much of the eld work at the mine sites. This work was partially funded by the Australian Coal Association Research Program. References
Bainbridge, N.W., Carras, J.N., Daly, C.R., Fitzsimmons, M.K., Sagha, A., 1994. Application of a mathematical model of self-heating to spoil piles from open-cut coal mines. Proceedings of the 3rd International Conference on Environmental Issues and Waste Management in Energy and Mineral Production. Curtin University of Technology, Perth, WA, pp. 129135. Carras, J.N., Young, B.C., 1994. Self-heating of coal and related materials: models, applications and test methods. Progress in Energy and Combustion Science 20, 115. Carras, J.N., Maitra, A., Roberts, O.C., Sagha, A., Szemes, F., 1998. The self-heating of spoil piles from open-cut coal mines. A eld trial of y ash grouting and an assessment of cover materials. ACARP C3055 Final Report, vol. 1. Australian Coal Association, Brisbane Qld, p. 157. IPCC, 2007. In: Eggleston, S., Buendia, L., Miwa, K., Ngara, T., Tanabe, K. (Eds.), 2006 IPCC Guidelines for National Greenhouse Gas Inventories. Published IGES, Japan. Prepared by the National Greenhouse Gas Inventories Programme, (in ve volumes), (available from http://www.ipcc-nggip.iges.or.jp/public/2006gl/index.htm). Kuenzer, C., Zhang, J., Tetzlaff, A., van Dijk, P., Voight, S., Mehl, H., Wagner, W., 2007. Uncontrolled coal res and their environmental impacts: investigating two arid mining regions in north-central China. Applied Geography 27, 4262. Lofteld, N.S., Brumme, R., Beese, F., 1992. Automated monitoring of nitrous oxide and carbon dioxide ux from forest soils. Soil Science Society of America Journal 56, 11471150. Nordon, P., Young, B.C., Bainbridge, N., 1979. The rate of oxidation of char and coal in relation to their tendency to self-heat. Fuel 58, 443449. Pone, J.D.N., Hein, K.A.A., Stracher, G.B., Annegarn, H.J., Finkleman, R.B., Blake, D.R., McCormack, J.K., Schroeder, P., 2007. The spontaneous combustion of coal and its by-products in the Witbank and Sasolburg coalelds of South Africa. International Journal of Coal Geology 72, 124140. Stracher, G.B., Taylor, T.P., 2004. Coal res burning out of control around the world: thermodynamic recipe for environmental catastrophe. International Journal of Coal Geology 59, 717. Troeh, F.R., Jabro, J.D., Kirkham, D., 1982. Gaseous diffusion equations for porous materials. Geoderma 27, 239253. Wang, Y.P., Meyer, C.P., Galbally, I.E., 1997. Comparison of eld measurements of carbon dioxide and nitrous oxide uxes with models simulations for a legume pasture in southeast Australia. Journal of Geophysical Research 102 (D23), 2801328024. Wang, H., Dlogogorski, B.Z., Kennedy, E.M., 2003. Coal oxidation at low temperatures: oxygen consumption, oxidation products, reaction mechanism and kinetic modelling. Progress in Energy and Combustion Science 29, 487513. Walker, S., 1999. Uncontrolled Fires in Coal and Coal Wastes. IEA Coal Research, London. 72 pp. Williams, D.J., Sagha, A., Lange, A.L., Drummond, M.S., 1993. Methane emissions from open-cut mines and post-mining emissions from underground coal. Report to the Department of Environment, Sports and Territories, CSIRO Investigation Report CET/IR173. CSIRO Australia.