International Journal of Coal Geology 154–155 (2016) 257–264

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International Journal of Coal Geology

journal homepage: www.elsevier.com/locate/ijcoalgeo

Inorganic matter in Victorian brown coals

Mihaela Grigore ⁎, Richard Sakurovs
The Commonwealth Scientific and Industrial Research Organisation (CSIRO) — Energy, Riverside Life Science Centre, 11 Julius Ave, North Ryde, NSW, 2113, Australia

a r t i c l e i n f o a b s t r a c t

Article history: A common method to quantify the mineral matter in coals is to remove the carbonaceous matter by low-
Received 21 November 2015 temperature oxygen plasma ashing (LTA) followed by X-Ray Diffraction (XRD) analysis. However, some low-
Received in revised form 12 January 2016 rank coals, such as Victorian brown coals (lignites), have low levels of mineral matter and contain significant
Accepted 13 January 2016
amounts of non-mineral inorganics (organically associated elements and salts dissolved in the coal pore's water),
Available online 14 January 2016
which form artifact phases during low-temperature ashing. The presence of these phases also lowers the concen-
Keywords:
tration of the low abundant mineral species in the ash below the detection limit of the XRD. Some of the non-
Brown coal mineral-matter components can be removed by leaching of the coal prior to ashing, but the leaching conditions
Mineral matter have to be chosen so that the mineral matter is not removed. In this study, sequential leaching was performed
Selective leaching on three Victorian brown coals (Hazelwood, Yallourn and Loy Yang) in order to increase the concentration of the
NH4-EDTA mineral species in the low-temperature ashes by removing the non-mineral inorganics. We introduced
SIROQUANT diammonium ethylenediaminetetraacetate (NH4-EDTA) solution into the leaching process, because of its potential
to extract ion-exchangeable cations without dissolving acid-sensitive mineral matter or contaminating the extract
solution with introduced metal cations. The leaching protocol was stepwise extraction by water, ammonium ace-
tate, NH4-EDTA, hydrochloric acid and nitric acid. Sequential leaching enabled quantification of the minerals that
occur in very small amounts in the coals. K-feldspar, pyrite, augite and kaolinite were the additional minerals quan-
tified in the leached coals beside quartz, plagioclase (calcian albite), marcasite and calcite, which were found in the
original coals. Most non-mineral inorganics, which produce large amounts of artifact phases in the low-temperature
ashes, were removed by water, ammonium acetate and NH4-EDTA. NH4-EDTA effectively removed significant
amounts of inorganic elements, which most likely occur in coordination complexes and would be extracted in con-
ventional leaching studies only by strong acids. This procedure makes it possible to discriminate between inorganic
elements that occur organically associated and mineral matter that is dissolved by strong acids.
Crown Copyright © 2016 Published by Elsevier B.V. All rights reserved.

1. Introduction
The mineral matter in a coal determines its utility in nearly all of its
commercial uses, so its quantification is important. X-Ray Diffraction
(XRD) has been used in many studies for identification and quantifica-
tion of mineral matter in coals (Hower et al., 2015; Huggins, 2002;
Koukouzas et al., 2009; Liu et al., 2015; Martinez-Alonso et al., 1992;
Miller and Given, 1987; Morgan et al., 1981; Ward, 2002). The analysis
of the mineral matter in coals is performed on the coal ashes prepared
at low temperatures (100–120 °C) in a radio-frequency oxygen plasma
asher (Gluskoter, 1965). This way the organic matter is removed from
the mineral matter with minimal alteration of the mineral species.
However, low-rank coals contain significant amounts of non-mineral
inorganics, which form artifact phases during low-temperature ashing
and these interfere in the quantification of the inherent mineral matter.
⁎ Corresponding author.
E-mail addresses: Mihaela.Grigore@csiro.au (M. Grigore), Richard.Sakurovs@csiro.au
(R. Sakurovs).
For instance, inorganic elements associated with the organic matter
react with organic sulfur to form sulfates (Dai et al., 2015; Ward,
2002; Ward et al., 2001). The formation of these artifact phases diminish
the concentration of the true minerals in the ash to a level where the
low abundant minerals cannot be detected by XRD. In Victorian
brown coals, which commonly have less than 2% inherent mineral
matter (Gloe and Holdgate, 1991), this problem is particularly severe.
The inorganic matter in the low rank coals, brown coals in particular,
consists of inorganic elements associated with the organic matter,
dissolved salts and other inorganic substances in the pore water
(Brockway et al., 1991; Dai et al., 2015; Li et al., 2010; Ward, 2002),
minerals that occur as crystalline discrete particles (true mineral
components) and mineraloids. The inorganic elements associated with
the organic matter occur as exchangeable cations attached to carboxylic
acids (carboxylate salts), phenols, chelates and other organometallic
complexes such as metalloporphyrins (Bonnett et al., 1987;
Branthaver, 1987; Filby and Vanberkel, 1987; Given and Miller, 1987;
Schafer, 1991; Ward, 2002).
Most of the sodium, calcium and magnesium in these coals are pres-
ent as carboxylates (Brockway et al., 1991; Schafer, 1991). Some sodium

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0166-5162/Crown Copyright © 2016 Published by Elsevier B.V. All rights reserved.
258 M. Grigore, R. Sakurovs / International Journal of Coal Geology 154–155 (2016) 257–264
may occur as sodium chloride (Perry et al., 1982). Iron and aluminum
could be present as complex ions bound by a single valency to carboxyl-
ate groups (Brockway et al., 1991). The exchangeable iron is usually
present in the ferrous form but it tends to be readily oxidized to the fer-
ric state on exposure to air. Cook and Cashion (1987) identified three
non-pyritic iron species in the Victorian brown coals using Mössbauer
spectroscopy. A poorly-ordered ferric oxyhydroxide as a dominant
phase, a ferrous humate that can precipitate as ferric oxyhydroxide
and a third species whose nature could not be confirmed, but believed
to be a Fe+2 compound. Aluminum hydroxide is also found in the
brown coals. The minerals identified in the Latrobe Valley coals are
quartz, clays (mainly kaolinite associated with illite, montmorillonite,
muscovite), silica, pyrite and/or marcasite (Perry et al., 1982).
Some of these species can be removed by selective leaching of the
brown coal. Selective leaching is commonly used to determine the rela-
tive abundance and modes of occurrence of the non-mineral inorganic
components and mineral matter (Dai et al., 2004; Davidson, 2000;
Finkelman et al., 1990; Grasset et al., 2010; Li et al., 2010; Liu et al.,
2015; Riley et al., 2012; Spears, 2013; Ward, 1992; Wijaya et al., 2011;
Zhang et al., 2008a,b). The most common reagents used in the leaching
protocols are water, ammonium acetate, HCl, HNO3 and HF. The soluble
species and the inorganic elements associated with carboxylic acids are
removed by water and ammonium acetate, respectively. However,
Matsuoka et al. (2002) found that ammonium acetate also dissolved
calcite. HCl extracts cations from chelates and clays, but also dissolves
carbonates, and Fe and Al hydroxides (Davidson, 2000; Miller and
Given, 1987). Sulfides, such as pyrite and marcasite, and silicates are
dissolved by HNO3 and HF, respectively.
Chelates such as EDTA and citric acid are used for extraction of metal
cations (transitional/heavy elements) from contaminated soils (Peters,
1999; Ritchie and Sposito, 1995). The pH of the solution and the
concentration of the chelant are two of the factors controlling the
metal cation uptake (Peters, 1999; Ritchie and Sposito, 1995).
Borggaard (1981, 1982) observed that amorphous iron oxide was
extracted by 0.01–0.2 M EDTA at pH 8–10 with negligible effect on the
crystalline iron-bearing minerals. He dissolved EDTA and ammonium
acetate in ammonia solution to obtain the selected pH. Disodium
ethylenediaminetetraacetate (Na-EDTA) 0.1 M was used by Wijaya
et al. (2011, 2012) for advanced removal of organically associated
inorganic elements in Victorian brown coals. However, the addition of
sodium can affect the mineral matter; Wijaya et al. (2011) reported
the formation of a Na-silicate believed to occur due to interaction of
Na from EDTA with aluminosilicates.
The aims of this study are to identify and quantify the mineral matter
and the nature of the inorganic elements that are organically associated
in three Victorian brown coals. Sequential leaching was carried out on
the coals to make possible quantification of the low abundance mineral
species and to improve discrimination between inorganic elements as-
sociated with different functional groups in coal. The leaching protocol
was water, ammonium acetate, diammonium ethylenediaminetetraac-
etate, hydrochloric acid and nitric acid. We introduced diammonium
ethylenediaminetetraacetate solution into the leaching process,
because of its potential to extract ion-exchangeable cations without
dissolving acid-sensitive mineral matter or contaminating the extract
solution and sample with introduced metal cations. The strong acid
leaching steps were included to enable quantification of the very low
abundance minerals that are not dissolved by HCl and HNO3.
2. Experimental
Three run-of-mine brown coals from the open-cut mines
Hazelwood, Yallourn and Loy Yang in the Latrobe valley, Victoria,
Australia, were selected for sequential leaching. These coals are
low-rank Tertiary coals (Gloe and Holdgate, 1991; Holdgate, 2005).
Gloe and Holdgate (1991) and Holdgate (2005) published detailed
geology of the Victorian brown coals. The coals were ground to less
than 212 μm. The leaching solutions used in this work were ultra pure
water (Milli-Q), 1 M ammonium acetate, 0.1 M NH4-EDTA buffered by
NH4OH to pH 9, 1 M hydrochloric acid and 2 M nitric acid. The NH4-
EDTA step was included between the ammonium acetate and HCl
steps to extract iron and other elements held in chelate complexes or as-
sociated with functional groups other than carboxylic groups. Also, the
high pH of the NH4-EDTA solution is expected to minimize the effect
of NH4-EDTA on the crystalline mineral matter. Using NH4-EDTA instead
of Na-EDTA eliminates the contamination of the supernatant liquor
with Na from the reagent. Although HCl and HNO3 dissolve some of
the mineral matter, they may also extract some of the inorganic ele-
ments organically associated if they were not removed by NH4-EDTA
leaching.
The ultimate and proximate analyses of the coals are shown in
Table 1. The moisture levels in the coals were determined according to
the Australian Standard AS 2434.1-1999 (Australia, 1999) in order to
calculate the coal mass on a dry basis. Inductively Couple Plasma-
Atomic Emission Spectroscopy (ICP-AES) was used for chemical analy-
ses of the coals and the supernatant liquids derived from each leaching
steps. The preparation method of coals for ICP-AES analysis consists of
two steps. The coals were oxidized at 815 °C then the resulting ashes
were dissolved with a mixture of hydrochloric, nitric and hydrofluoric
acids in 60 mL polypropylene bottles (Riley et al., 2012). The excess
fluoride was complexed with boric acid. The ash yields and ash analyses
are shown in Table 2.
The coals and the leaching solutions were loaded into 2 L Nalgene
polyethylene bottles and shaken at room temperature for 24 h. The
ratio of leaching solution to coal (dry basis) was 3.7. The leached coal
was washed three times with Milli-Q water after each filtration to re-
move the remaining supernatant solution from the coal. After every
leaching step aliquots of filtrate were taken for both pH determination
and chemical analysis, and a coal sub-sample was taken for mineralog-
ical and chemical analyses. The pH values of the filtrates and blank
solutions are shown in Table 3.
The mineralogical compositions of the coals were determined by
XRD analyses of the low-temperature ashes of the coals. The coals
were oxidized at approximately 120 °C using a radio-frequency oxygen
plasma asher (Gluskoter, 1965). Samples were oxidized until a constant
weight was reached. The time taken ranged from two months (original
brown coal) to less than one week for strong acid (HCl and HNO3)
leached brown coals. We believe that coal oxidation by oxygen plasma
was hindered by the presence of ion-exchangeable cations. The XRD
patterns were used for identification and quantification of the mineral
phases using Bruker Eva search/match software and SIROQUANT™
(Taylor, 1991). The proportion of the amorphous matter was
determined by spiking the ashes with known amounts of corundum.
The method has been described elsewhere (Ward and French, 2006).
Scanning Electron Microscopy in conjunction with Electron
Dispersive Spectroscopy (SEM–EDS) was used for analysis of mineral
matter and elements associated with organic matter in coals, and
mineral phases in the low-temperature ashes.
Table 1
Proximate and ultimate analyses of the original coals.
Hazelwood Yallourn Loy Yang
Proximate analysis (wt%, db)
Ash 2.9 2.0 0.80
Volatile matter 49.0 52.1 49.6
Fixed carbon 48.1 45.9 49.6
Ultimate analysis (wt%, db)
Carbon 67.8 64.4 69.4
Hydrogen 4.52 4.27 4.8
Nitrogen 0.74 0.74 0.71
Sulfur (total) 0.28 0.30 0.31
Oxygen (by difference) 24.1 27.8 24.2
 M. Grigore, R. Sakurovs / International Journal of Coal Geology 154–155 (2016) 257–264
Table 2
Ash analyses of the original coals (wt%).
Coal SiO2 Al2O3 Fe2O3 CaO
Hazelwood 1.6 11.5 20.8 26.2
Yallourn 7.0 1.6 41.0 7.2
Loy Yang 18.3 28.8 8.5 4.2
3. Results and discussion
The low-temperature ashes of the original coals are dominated by
sulfates, such as bassanite and hexahydrate, and amorphous matter;
the concentration of the inherent mineral matter such as quartz, calcian
albite (plagioclase), marcasite and calcite is very low — less than 1% in
the ash in the Hazelwood and Yallourn coals, and less than 8% in the
ash of Loy Yang coal (Table 4). The sulfates are mainly artifacts formed
during low-temperature ashing (Dai et al., 2012; Martinez-Alonso
et al., 1992; Ward, 2002): they are produced by reaction of organic sul-
fur with organically associated calcium and magnesium. The amor-
phous matter may consist of phases formed during ashing from the
non-mineral components and/or mineraloids. The presence of large
amounts of amorphous and crystalline artifact phases in the ash lowers
the relative concentration of the minor mineral species to below the
detection limit of the XRD.
Other mineral species in the original coals that were not detected by
XRD in the ashes of the coals were found by SEM–EDS analyses. The
additional mineral species were potassium feldspar, magnetite
(Fe3O4), ilmenite (FeTiO3), Fe-titanium oxide, titanium oxide, augite,
kaolinite, illite ((K,H3O)(Al,Mg,Fe)2(Si,Al)4O10[(OH)2,(H2O)]), dolomite
(Ca,Mg(CO3)2), pyrite, iron sulfate, barite (BaSO4), sphalerite (ZnS),
galena (PbS) and iron oxyhydrate. Their abundance in the coals varied
significantly. Barite, sphalerite and galena were found in trace amounts
in the coals whereas the other minerals were generally more abundant.
Feldspar, augite, magnetite, ilmenite, Fe-titanium oxide and titanium
oxide are common minerals in igneous rocks (Deer et al., 1962a,b,
1963) and most probably come from the nearby extrusive basaltic
lavas and tuffs (Durie, 1961; Gloe and Holdgate, 1991).
The presence of mineraloids in the coals was indicated by SEM–EDS.
Iron sulfide was mainly identified in Hazelwood coal and only trace
amounts of iron sulfide were found in the other coals. Although pyrite
has similar elemental composition to marcasite, it was distinguished
by SEM due to its typical framboidal texture, which consists of spherical
aggregates of euhedral crystallites. The morphology of iron sulfide
varies widely, from euhedral and subhedral crystals (Fig. 1a) to
anhedral texture with no well formed crystal faces (Fig. 1b). Iron sulfide
was largely associated with iron sulfate (hydrated) (Fig. 1), which was
possibly caused by oxidation of the iron sulfide (Brockway et al., 1991;
Gluskoter, 1977) during coal handling and storage. The iron sulfates
are fairly abundant and they were not detected by XRD even in the
leached coals by NH4-EDTA where their presence was confirmed by
SEM–EDS hence they are more likely to be amorphous. Techniques
such as Transmission Electron Microscopy (TEM) would be required
to assess their crystallinity.
Iron oxyhydrate is usually a weathering product of iron-bearing
minerals (Deer et al., 1962b) such as siderite, pyrite and magnetite
formed under oxidizing conditions. It can be crystalline (i.e. goethite)
and/or amorphous (i.e. limonite). However, limonite commonly
Table 3
The pH of the leaching solutions (ammonium acetate and NH4-EDTA) and the supernatant
solutions (water, ammonium acetate and NH4-EDTA).
pH Blank Hazelwood Yallourn
Water 4.07 4.00
Ammonium acetate 6.80 5.53 5.28
NH4-EDTA 9.04 6.00 6.02
259
MgO Na2O K2O TiO2 BaO SrO SO3 P2O5 Other oxides
11.9 2.0 0.30 0.17 0.05 0.18 24.8 0.04 0.46
22.9 4.1 0.58 0.08 0.04 0.13 14.8 0.01 0.56
13.4 8.5 0.57 0.54 0.10 0.07 17.1 0.05 0.1
precipitates in swamps, which is characteristic to the formation of the
Latrobe Valley coals (Gloe and Holdgate, 1991). SEM–EDS data indicate
the presence of different forms of iron oxyhydrate; the Fe:O ratios
varied in the EDS spectra of different particles (Fig. 2).
Silicon was not only present in minerals, but it was also observed in
the plant tissue derived material in the coals used in this study. Silicon
can form stable complexes with lignin in the cell walls and it can also
occur in nano-size particles of amorphous silica (Currie and Perry,
2007; Kolb and Liesch, 2008). Silicic acid in the plants under specific
conditions forms silica (Currie and Perry, 2007). Fig. 3 shows clusters
of silicon-rich material within the plant tissue. Although high-
magnification images suggest silicon is present in the plant tissue
derived material and not in discrete silica grains, its nature could not
be assessed by SEM.
Since additional mineral species were found in the coals by SEM
analysis but not confirmed by XRD in the low-temperature ashes of
the original coals, the removal of organically associated elements
would enable quantification of the less abundant mineral species by
XRD. Because some of these minerals were in very low abundance,
their quantitative analysis using SEM would require examination of a
large number of resin blocks (coal is mounted in resin blocks for SEM
analysis) in order to obtain a representative sample. Also, XRD can
distinguish between polymorph minerals such as rutile, anatase and
brookite which are polymorphs of TiO2.
Large amounts of inorganic elements were extracted from coals
during leaching. Their removal is indicated by the decrease of the
low-temperature ash yields of the leached coals as the leaching steps
progressed (Fig. 4). The decrease of the ash yields of the Loy Yang
leached coals is gradual, whereas the ash yields of Hazelwood and
Yallourn coals were reduced dramatically after ammonium acetate
and EDTA leaching. The differences between the ash yields of the coals
become very small after NH4-EDTA leaching, and only a slight reduction
of the ash yields of the coals is observed after the nitric acid leaching
step. This confirms that most of the inorganic material occurs as soluble
salts, carboxylates and organometallic complexes.
The mode of occurrence of the inorganic elements organically
associated is highly variable between the coals (Fig. 5). Generally, over
75% of Na, K, Mg and Ca were removed by water, ammonium acetate
and NH4-EDTA (Fig. 5). Iron and Al do not appear to be present as
extractable carboxylates since they were not removed by ammonium
acetate. The proportions of Fe and Al removed by NH4-EDTA range
from about 30% to 75%. Aluminum and Fe may occur in coordination
complexes with organic ligands, for instance Fe can form hydrated
octahedral complexes with carboxyl and hydroxyl groups, and possibly
phenol groups (Domazetis et al., 2008; Mathews and Chaffee, 2012).
Since NH4-EDTA extracted more Ca and Mg than ammonium acetate
did, it is possible that some Ca and Mg occur in coordination complexes
with mixed functional groups like Fe. Although the Si-bearing species
are typically silicates, quartz and silica, small amounts of silicon was
found as soluble species and apparently associated with carboxylic
acids. The Si released by water and carboxylic acids may come from
the plant tissue derived materials. SEM–EDS data also confirm that a
number of elements such as Na, K, Ca, Mg, Al and Fe were observed
associated with the organic matter.
Loy Yang
The first three leaching steps aimed to remove most inorganic com-
3.89 pounds with minimal effect on mineral matter. Carbonates, especially
5.48 calcite, were selectively dissolved by ammonium acetate in other stud-
6.23
ies (Matsuoka et al., 2002). In this work, there is no evidence that calcite
260 M. Grigore, R. Sakurovs / International Journal of Coal Geology 154–155 (2016) 257–264

Table 4
Mineral matter in the low temperature ashes of the original coals and their corresponding leached coals (LTA ash yield is expressed as wt% on a dry coal basis).

Mineral phase Chemical formula Original Water NH4OAc EDTA HCl HNO3

Hazelwood
LTA ash yield (wt%) 4.68 4.26 2.61 0.96 0.31 0.27
Quartz SiO2 0.3 0.2 0.3 1.1 3.9 4.0
Marcasite FeS2 0.5 0.6 0.8 2.7 5.5 5.2
Pyrite FeS2 0.6 1.3 0.9
Calcian albite (Na0.5 Ca0.5)Al1.5Si2.5O8 0.7 0.9
Augite (Ca,Na)(Mg,Fe,Al,Ti)(Si,Al)2O6 0.5
Bassanite CaSO4·0.5H2O 21.5 29.5 4.9
Anhydrite CaSO4 10.7
Hexahydrite MgSO4·6H2O 16.1 18.7 3.0
Jarosite KFe3(SO4)2(OH)6 0.8
Amorphous 61.6 51.0 80.3 95.5 88.7 87.7

Yallourn
LTA ash yield (wt%) 3.73 3.43 2.79 0.79 0.17 0.15
Quartz SiO2 0.8 1.0 1.3 4.2 21.6 23.8
Calcite CaCO3 0.2 0.2 0.2 0.6
Calcian albite (Na0.5 Ca0.5)Al1.5Si2.5O8 1.4 5.5 8.3
Augite (Ca,Na)(Mg,Fe,Al,Ti)(Si,Al)2O6 1.5 2.1
Bassanite CaSO4·0.5H2O 5.1 6.3 6.9
Hexahydrite MgSO4·6H2O 24.0 31.7 22.7 16.2
Jarosite KFe3(SO4)2(OH)6 3.5 0.4
Amorphous 69.9 60.8 69.3 74.0 71.0 65.7

Loy Yang
LTA ash yield (wt%) 1.43 1.21 0.98 0.61 0.32 0.17
Quartz SiO2 5.0 6.7 6.5 11.2 20.2 32.8
Calcian albite (Na0.5 Ca0.5)Al1.5Si2.5O8 0.5 0.4 0.7 1.3 1.8 3.4
Orthoclase KAlSi3O8 0.2 0.3 0.6 2.0
Kaolinite Al2Si2O5(OH)4 1.1 2.1 3.9
Calcite CaCO3 0.1 0.1 0.1 0.2
Augite (Ca,Na)(Mg,Fe,Al,Ti)(Si,Al)2O6 0.5 1.7
Bassanite CaSO4·0.5H2O 1.9 2.6 4.5
Hexahydrite MgSO4·6H2O 17.9 10.7 8.5
Amorphous 74.7 79.6 79.5 85.9 74.8 56.1

was affected by ammonium acetate and was still present in the coals
after NH4-EDTA leaching as shown by XRD analyses (Table 4). However,
trace amounts of calcite may have dissolved during ammonium
acetate leaching. Also, some iron oxyhydrate may have been dissolved
by NH4-EDTA. Borggaard (1982) found that amorphous iron oxide
was selectively extracted from a mixture consisting of iron-bearing
silicates, natural and synthetic crystallized iron oxides and amorphous
iron oxide by EDTA at a pH between 8 and 10. In this study, although
the pH of the NH4-EDTA liquor was not kept above 8 during the leaching
test, some of the amorphous iron oxyhydrate may have been removed
by NH4-EDTA.
In this work, including the NH4-EDTA leaching step before the strong
acids steps had two main advantages. It effectively removed elements
organically associated that only strong acids would have otherwise
released, making possible the detection of some of the less abundant
minerals by XRD, and it did not obviously affect these minerals. No
ammonium phases were identified in the XRD patterns of the low-
temperature ashes of the coals treated with NH4-EDTA. Wijaya et al.

Fig. 1. Backscattered Electron images of (a) euhedral to subhedral crystals of iron sulfide (bright white) rimmed by iron sulfate (light gray); (b) anhedral iron sulfide (bright white)
intergrown with iron sulfate (light gray).
 M. Grigore, R. Sakurovs / International Journal of Coal Geology 154–155 (2016) 257–264 261

Fig. 2. Backscattered Electron images of iron oxyhydrate particles and their corresponding EDS analyses (below the image). The Fe:O ratios are 1.7 and 1.6, respectively.

Fig. 3. (a) Backscattered Electron image of plant tissue showing clusters of silicon-rich material. The Si X-ray map of a selected area of the plant tissue is included; (b) High magnification of
silicon-rich material in a pore of the plant tissue (Secondary Electron image). The EDS analysis of the silicon-rich material is included.
262 M. Grigore, R. Sakurovs / International Journal of Coal Geology 154–155 (2016) 257–264
Fig. 4. Low temperature ash yields of the original and their corresponding leached coals
(expressed as wt% on a dry coal basis).
Fig. 5. The cumulative percentage of inorganic elements removed during leaching from
(a) Hazelwood coal, (b) Yallourn coal and (c) Loy Yang coal.
(2011) observed formation of a Na-silicate in the coals treated by Na-
EDTA, which was removed by diluted nitric acid.
The concentrations of the true minerals in the coal ashes
increased as the leaching steps progressed (Table 4). Some of the
minerals in the original coals identified only by SEM–EDS analysis
such as pyrite, augite, orthoclase and kaolinite were detected by
XRD in the ashes of the leached coals. The concentrations of these
minerals in the ashes of the original coals were below the detection
limit of the XRD. After water, ammonium acetate and NH 4 -EDTA
leaching, their concentration in the low-temperature ashes
increased enough to be detected by XRD. However, NH4-EDTA
extraction was insufficient in identifying minerals such as augite,
which were only detected by XRD in the ash after the coals had been
treated by hydrochloric and nitric acids. Nitric acid selectively removed
the iron sulfides. Marcasite was the least dissolved iron sulfide by nitric
acid, followed by pyrite. The anhedral iron sulfide was not found in the
coal treated with nitric acid.
The XRD data indicate that the other mineral phases found by SEM–
EDS in the original coals such as ilmenite, titanium oxide, illite, barite,
sphalerite and galena occurred in traces in the coals since they were
not detected by the XRD in the leached coals even by nitric acid. Their
abundance was therefore less than 15 mg per kg of coal, considering
the detection limit of the XRD of 1% and the low-temperature ash
yield of 0.15%.
Calcium and magnesium sulfates formed in the ashes of the coals
leached by water and ammonium acetate. Amorphous matter is the
dominant phase in all samples. Although some iron, aluminum and so-
dium are organically associated (Fig. 5) they did not form crystalline
phases in the low-temperature ashes. SEM–EDS analyses showed they
form amorphous complex sulfates containing various amounts of Mg,
Ca, Al, Fe along with, occasionally, very small amounts of Ti. The sulfates
may have been hydrated phases. The organically associated silicon or
silica from the plant tissues would also form amorphous phases in the
low-temperature ashes.
The concentrations of the mineral phases were recalculated on a coal
basis using the low-temperature ash yields to enable comparison
between coals (Table 5). There is some variation in the abundance of
the true minerals as the leaching steps progress. Heterogeneity of the
samples and errors associated with the ash yield determination
(particularly errors associated with the determination of moisture
content) would affect the recalculated values of the mineral phases.
Although amorphous matter was the most abundant phase in the
low-temperature ashes of leached coals (Table 4), the amount of amor-
phous phase generated by 1 kg of coal actually decreased as the leaching
steps progressed (Table 5). The amorphous matter in the ashes of the
acid treated coals may have consisted of mineraloids such as amorphous
silica and/or strongly bound inorganic elements to organic complexes
and phenols. The removal of the inorganic elements associated with
phenols requires strong basic solutions with pH N 10. Jarosite in the
ash of Hazelwood coal treated with nitric acid suggests the presence
of Fe organically associated in the coal that is not extracted even by HCl.
4. Conclusions
Our study on the mineral matter in the Victorian brown coals using
sequential leaching showed the following:
• Quantification of the minerals that occur in very small amounts in the
coals was enabled by sequential leaching. K-feldspar, pyrite, augite
and kaolinite were the additional minerals quantified in the leached
coals beside quartz, calcian albite, marcasite and calcite, which were
found in the original coals.
• Most non-mineral inorganics, which produce large amounts of artifact
phases in the low-temperature ashes, were removed by water, ammo-
nium acetate and NH4-EDTA. There was no evidence that mineral
matter was affected by these reagents.
 M. Grigore, R. Sakurovs / International Journal of Coal Geology 154–155 (2016) 257–264 263

Table 5
Mineral matter in the original coals and their corresponding leached coals expressed as g/kg on a dry coal basis.

Mineral phase Chemical formula Original Water NH4OAc EDTA HCl HNO3

Hazelwood
Quartz SiO2 0.14 0.08 0.08 0.11 0.14 0.12
Marcasite FeS2 0.23 0.23 0.21 0.26 0.20 0.16
Pyrite FeS2 0.06 0.05 0.03
Calcian albite (Na0.5 Ca0.5)Al1.5Si2.5O8 0.03 0.03
Augite (Ca,Na)(Mg,Fe,Al,Ti)(Si,Al)2O6 0.02
Bassanite CaSO4·0.5H2O 9.7 11.5 1.3
Anhydrite CaSO4 2.8
Hexahydrite MgSO4·6H2O 7.3 7.3 0.78
Jarosite KFe3(SO4)2(OH)6 0.02
Amorphous 28.8 19.8 21.0 9.2 3.3 2.6

Yallourn
Quartz SiO2 0.30 0.34 0.36 0.33 0.37 0.36
Calcite CaCO3 0.07 0.07 0.06 0.05
Calcian albite (Na0.5 Ca0.5)Al1.5Si2.5O8 0.11 0.09 0.12
Augite (Ca,Na)(Mg,Fe,Al,Ti)(Si,Al)2O6 0.03 0.03
Bassanite CaSO4·0.5H2O 1.9 2.2 1.9
Hexahydrite MgSO4·6H2O 9.0 10.9 6.3 1.3
Jarosite KFe3(SO4)2(OH)6 0.28 0.01
Amorphous 26.1 20.9 19.3 5.9 1.2 1.0

Loy Yang
Quartz SiO2 0.72 0.81 0.64 0.68 0.65 0.56
Calcian albite (Na0.5 Ca0.5)Al1.5Si2.5O8 0.07 0.05 0.07 0.08 0.06 0.06
Orthoclase KAlSi3O8 0.02 0.02 0.02 0.03
Kaolinite Al2Si2O5(OH)4 0.07 0.07 0.07
Calcite CaCO3 0.01 0.01 0.01 0.01
Augite (Ca,Na)(Mg,Fe,Al,Ti)(Si,Al)2O6 0.02 0.03
Bassanite CaSO4·0.5H2O 0.27 0.31 0.44
Hexahydrite MgSO4·6H2O 2.6 1.3 0.83
Amorphous 10.7 9.6 7.8 5.2 2.4 0.95

• NH4-EDTA effectively removed significant amounts of inorganic
elements, which most likely occur in coordination complexes and
would be extracted in conventional leaching studies only by strong
acids. This made possible discrimination between inorganic elements
occurring organically associated and mineral matter that is dissolved
by strong acids. Moreover, NH4-EDTA does not contaminate the coal
with metallic ions like Na-EDTA used in other studies.
• The mode of occurrence of the inorganic elements organically associ-
ated varied widely between the coals used in this study.
Acknowledgments
The authors would like to thank Dr. Louis Wibberley (CSIRO) and Dr.
Peter Scaife (CSIRO) for providing the coal samples.
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