Boyd, Robert John. "Trace elements in coal from Colinsville, Bowen basin, Australia : in-ground mode of occurrence and behaviour during utilisation." Thesis, 2004. https://researchonline.jcu.edu.au/1417/1/01front.pdf.
Abstract (sommario):
Analysis of samples gathered during delineation of a coal resource is becoming
increasingly sophisticated as various organisations attempt to predict and understand the
technological behaviour of the mined product. Analysis to determine the concentration
of trace elements in coal is becoming more prevalent, and not just merely for academic
curiosity. Increased environmental awareness has impelled the need to consider potential
negative impacts on the ecosystem caused by liberation of trace elements from coal
during utilisation.
The aims of this thesis are to: 1) Determine the concentration of trace elements in coal
seams mined to supply the Collinsville pulverised fuel combustion plant at the
Collinsville open cut, Northern Bowen Basin, Australia; 2) Determine the mineralogy
and, using graphical relationships, the likely mode of occurrence of trace elements in the
sampled pits; 3) Determine the mode of occurrence of trace elements in the pulverised
fuel of the Collinsville power plant using the USGS sequential leaching method, and
contrast the results with the same analysis for an unrelated fuel from another coal fired
power utility (Mitsui Mining’s Omutu City plant, Kyushu, Japan); 4) Examine the
partitioning behaviour of trace elements in the Collinsville power utility, and contrast the
results with the partitioning behaviour of trace elements in the Mitsui combustion utility
to assess the influence of trace element mode of occurrence on partitioning behaviour; 5)
Examine the mobility of trace elements from solid ash waste from the Collinsville power
utility, and compare with the mobility of trace elements from the Mitsui power utility
solid waste to assess the influence of mode of occurrence on the leachability of trace
elements and; 6) Determine the partitioning behaviour of trace elements in carbonisation
of Bowen seam coal at the Bowen coke works and compare with the partitioning
behaviour of the same elements in combustion.
Lithotype logging of coal exposed in the highwalls of the Blake Central, Blake West and
Bowen No.2 pits was undertaken. Of particular note was the presence of dull heat
affected coal toward the roof of the Blake Central pit seam, toward the floor of the Bowen No.2 pit seam, and the presence of bed-parallel intrusions within the seam in the
Blake West pit. In the Blake West pit seam, the intrusion caused thermal alteration of the
coal to coke over a 60cm zone immediately adjacent to the intrusion with a further 1.10-
1.25m zone of dull heat altered coal beyond the coked zone. In the Blake Central, 4.5m
of dull heat-affected coal occurred near the roof of the seam. In the Bowen No.2 pit,
1.2m of heat-affected coal occurred near the floor of the seam. Beyond the heat affected
zone, lithotype logging of the Blake seams noted a number of rock partings, but no
convincing dulling upward cycles due to progressive drying of the mire, noted in other
studies of Permian coal, were found. No partings were found in the Bowen seam and
only one convincing dulling upward cycles was logged. In part the absence of dulling
upward cycles is due to heat alteration of the coal, but the numerous influxes of sediment
laden water into the Blake seam mire also acted to terminate any significant dulling
upward cycles by raising both nutrient levels and the water table.
Following lithotype logging, channel sampling of the pits resulted in a total of 76
samples, 25 from the Blake Central pit, 36 from the Blake West pit and 15 from the
Bowen No.2 pit. The channel sampling intervals were determined approximately by coal
lithotype interval, with some amalgamations to restrict sample numbers. The channel
samples were analysed for proximate analysis, coal petrography and vitrinite reflectance
(selected samples) and for major and trace elements using XRF and INAA.
The lithotype logs, proximate analysis data and coal petrography were integrated to infer
the depositional environment of the Blake and Bowen seams. The generally high ash
yield, common stone bands, low sulphur content of the coal and rare pyrite in the Blake
seam suggests the depositional environment was a Class 3 topotelmitic peat with a
variable water table. The moderate ash yield, the absence of common stone bands,
sulphur contents of ~2% and the moderate pyrite content of the coal in the Bowen seam
suggests the depositional environment was a Class 2 topotelmitic peat with a high water
table. The igneous intrusions have caused extensive alteration of vitrinite to semi-coke, a
general decrease in the volatile matter content and an increase in the vitrinite reflectance
[Ro(max)] toward the intrusion.
Mineralogy was calculated from major and trace elements using normative analysis,
calibrated by XRD analysis of low temperature ash from selected samples. The
mineralogy of the Blake seam samples is dominated by kaolinite, with subordinate
quartz, illite, feldspar, and siderite, and minor concentrations of pyrite, gorceixite,
goyazite and anatase. The mineralogy of the Bowen seam samples is dominated by
kaolinite, with subordinate quartz, illite and pyrite, and minor concentrations of siderite,
gorceixite, goyazite and anatase/ rutile/ iron oxides.
The concentration of trace elements in the channel samples was determined by INAA and
XRF. The INAA and XRF concentrations of iron and uranium show a reasonable
statistical relationship suggesting the two analysis methods are consistent with each other.
The concentration of trace elements in the Blake and Bowen seams is generally low
compared to world average ranges for coal and to crustal averages. Only gold, copper,
hafnium, thorium and ytterbium were found to be above the world coal average range in
the Blake seam. Only gold and copper were found to be above world coal average range
in the Bowen seam coal.
Trace element mode of occurrence was inferred using graphical relationships between
normative mineral and trace element concentrations. In the Blake seam, arsenic, possibly
chromium, copper, mercury, nickel and lead were inferred to be associated with pyrite.
Bromine, cobalt, selenium, and zinc appeared to be organically bound. Cerium, caesium,
europium, lanthanum, rubidium, and scandium showed a graphical relationship with
illite. However, cerium, europium, lanthanum and scandium, along with hafnium,
lutetium, neodymium, samarium, terbium, thorium, uranium and vanadium also showed a
graphical relationship with gorceixite or gorceixite plus goyazite. It was inferred the
latter group of elements are associated with monazite or zircon. In addition to the REE
phosphate mode of occurrence, some rare earth elements also showed an affinity for kaolinite. Thorium and uranium were also inferred to be associated with feldspars.
Antimony, tantalum and ytterbium were found to be dominantly associated with
kaolinite.
In the Bowen seam, arsenic, cobalt, possibly chromium, copper, mercury, molybdenum,
nickel, lead, antimony, selenium and zinc showed a graphical relationship with pyrite.
The elements cerium, hafnium, neodymium, rubidium, samarium, tantalum, thorium,
uranium and tungsten all showed significant graphical relationships with the anatase/
rutile/ FeO grouping of minerals. It is inferred that the relationship is due to the presence
of monazite, zircon, xenotime, REE phosphates, tungstates or other trace minerals, the
distribution of which mirrors the distribution of the anatase/ rutile/ FeO grouping.
Uranium and thorium were inferred to be associated with REE phosphates and zircon
respectively, plus illite. The elements bromine, europium, lanthanum, terbium and
vanadium were inferred to be associated with illite. A mixed illite/ heavy mineral suite
mode of occurrence is inferred for samarium, tantalum, thorium and uranium. The
elements caesium, lutetium, scandium, and ytterbium were inferred to be associated with
kaolinite.
The effect of igneous intrusions on the concentration of a number of minerals and trace
elements was also examined. The presence of semi-coke or an inferred distance of heat
alteration was used to distinguish heat affected and unaffected samples. Depletion or
enrichment of minerals and elements was inferred using ply thickness weighted average
concentration figures for altered and unaltered samples and trends of concentration
change toward the intrusion. Some consistent changes in the concentration of trace
elements and minerals were found across all three pits sampled. The minerals siderite
and pyrite are depleted in the heat affected zone, but goyazite is enriched, particularly
toward the margins of the heat affected zone. The elements bromine and strontium (the
latter mirroring the goyazite trend) are concentrated in the heat affected zone. The
elements cobalt, mercury, manganese (mirroring the pyrite trend), nickel and possibly
arsenic and zinc are depleted in heat affected samples from all three pits sampled. The
inconsistent behaviour of some other trace elements (molybdenum, chromium and possibly selenium) in response to the igneous intrusion appears to be the result of
different modes of occurrence of trace elements between pits.
Samples of pulverised fuel were collected from the Collinsville and Japanese (Mitsui)
pulverised fuel utilities. The concentration of major and trace elements was determined
by INAA, XRF and (for the Collinsville sample) ICP-MS & ICP-AES. INAA analysis
suggests gold, cerium, cobalt, europium, hafnium, lanthanum, lutetium, molybdenum,
neodymium, scandium, selenium, samarium, strontium, tantalum, thorium, tungsten and
ytterbium are at the upper end or above the world average concentration range in the
Collinsville pulverized fuel. Only gold, hafnium and thorium are at the upper end or
above the world coal concentration range in the Japanese pulverized fuel.
Sequential leaching of the pulverised fuels was undertaken according to the USGS
protocol. The sequential leach data was interpreted to infer trace element mode of
occurrence in the pulverised fuel. A number of significant differences in the mode of
occurrence of antimony, arsenic, chromium, cobalt, nickel, selenium, uranium and zinc
were found between the two combustion plants studied. The element vanadium had
almost identical modes of occurrence in fuel from both plants studied.
A comparison of trace element mode of occurrence determined for the Collinsville power
utility pulverised fuel by sequential leaching with mode of occurrence determined for the
in-ground feed coals using graphical methods showed a reasonable level of agreement. It
is concluded that the use of two methods of determining mode of occurrence provides
better definition of mineral type in some cases. For example a siderite mode of
occurrence could be determined using graphical relationship whereas the sequential leach
data gave only a carbonate mode of occurrence. Further, the sequential leach data solved
the problem of parallel graphical relationships. For example, galena was determined to
be the mode of occurrence of lead from the sequential leach data, whereas graphical
relationships indicated a pyrite mode of occurrence because of the relationship with
sulphur. Combustion of coal occurs in three phases, namely devolatilisation, combustion of the
volatile matter, and combustion of the residual char. Mineral matter may be excluded
from the residual char particles due to desegregation and separation in the milling
process, or included within the char particle. During combustion, trace elements partition
between the bottom ash, the fly ash, and flue gas (lost up the stack). The concentration of
trace elements in ash samples from the Collinsville and Mitsui power utilities was
determined by INAA and XRF. The partitioning behaviour of the trace elements is
examined by calculating relative enrichment values for the trace elements. Generally the
partitioning behaviour and classification of trace elements in this study matched those
found in previous published studies for a given element.
The relative enrichment trends of elements exhibiting significant differences in mode of
occurrence between the two combustion plants sampled (ie antimony, arsenic, chromium,
cobalt, nickel, selenium, uranium and zinc plus vanadium) were examined to determine
the control of mode of occurrence on the partitioning behaviour. It is hypothesised that
the relative volatility of a particular element in combustion reflects the temperature at
which the host mineral or the organic matter thermally decomposes. Thus organically
bound elements should be more volatile than pyrite associated elements, which should be
more volatile than carbonate associated elements, which should be substantially more
volatile than silicate associated elements. Other factors that may influence partitioning
behaviour such as the major element chemistry of the ash, plant design and operating
conditions, and temperature variations within the combustion chamber were discounted
as significantly influencing relative enrichment differences for the two combustion plants
studied. It is concluded that element mode of occurrence has a strong influence on the
relative volatility of a given element, and that comparison of sequential leach results from
two pulverised fuel utilities has the potential allow prediction of the relative volatility of
trace elements in combustion. Some complications may arise due to exclusion of some
mineral grains and localised variations in the oxidation state within the combustion zone.
Solid combustion wastes (fly ash and bottom ash) are commonly disposed of in landfill
and impoundment facilities. Unless the landfill is impermeable to water, disposal of solid wastes in such fashion allows interaction with the hydrogeological system and could lead
to detrimental environmental impacts. Leaching of indicative “total waste” composites
made up by blending fly ash and bottom ash samples from each power utility in an 80/20
proportion was undertaken using the TCLP protocol. The concentration of trace elements
in the leachates was compared to recreational water and drinkwater guideline values. The
concentration of barium, manganese, and selenium in the Collinsville leachate exceeds
both the recreational and drinkwater guideline concentrations. The concentration of
nickel in the Collinsville leachate was found to exceed the recommended drinkwater
concentration, but is below recreational water guideline value. The concentration of
boron and selenium in the Mitsui leachate was found to exceed both the recreational and
drinkwater guideline values. The concentration of barium in the Mitsui leachate was
found to exceed the drinkwater standard. The concentration of an element in the ash
sample was found to be a poor indicator of the mobility of the element.
Elements that showed substantial differences in mode of occurrence in the pulverised fuel
(ie antimony, arsenic, chromium, cobalt, nickel, selenium, uranium and zinc plus
vanadium) were examined to assess the influence of mode of occurrence on the
leachability of the element from solid combustion waste. It is concluded that, where the
difference in element mobility between the two composite ash samples is significant,
mode of occurrence does exert some control on the proportion of a trace element in the
ash that can be mobilised by the TCLP protocol. In particular, trace elements present in
coal associated with silicates appear substantially unavailable for mobilisation by the
TCLP protocol.
The concentration of trace elements in samples of feed coal, coke and breeze from the
Bowen coke works was determined by INAA and XRF. A new index (the CRE index)
was developed to characterise the enrichment or depletion of trace elements in the coke
and breeze. Coke is classified as enriched (Class 1), neither enriched nor depleted (Class
2), depleted (Class 3) or highly depleted (Class 4). Breeze was classified as enriched
(denoted “e”), neither enriched nor depleted (denoted “a”) and depleted (denoted “d”). Comparison of the partitioning behaviour of trace elements in combustion and
carbonisation was undertaken by comparing the RE and CRE data. It is concluded that
all but the most volatile elements (sulphur, selenium, arsenic and tungsten) are
substantially retained in the coke. The substantial retention of trace elements in coke is
likely due to the lower temperature at which carbonisation occurs compare