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Leaching of hazardous elements from Mozambican coal and coal ash

Carlos A. Marove, Pawit Tangviroon, Carlito B. Tabelin, Toshifumi Igarashi

PII: S1464-343X(20)30112-6
DOI: https://doi.org/10.1016/j.jafrearsci.2020.103861
Reference: AES 103861

To appear in: Journal of African Earth Sciences

Received Date: 18 September 2019

Revised Date: 22 April 2020
Accepted Date: 22 April 2020

Please cite this article as: Marove, C.A., Tangviroon, P., Tabelin, C.B., Igarashi, T., Leaching of
hazardous elements from Mozambican coal and coal ash, Journal of African Earth Sciences (2020), doi:
https://doi.org/10.1016/j.jafrearsci.2020.103861.

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 Leaching of Hazardous Elements from Mozambican Coal and Coal
Ash
Carlos A Marove1, Pawit Tangviroon 2*, Carlito B Tabelin3, Toshifumi Igarashi4

1 National Institute of Mines, Department of Mining Technology, Praça 25 de Junho n° 380, Caixa Postal 4605,
Maputo-Mozambique
2 Laboratory of Resources, Environment, and Remediation, Division of Sustainable Resources Engineering, Faculty
of Engineering, Hokkaido University, Sapporo 060-8628, Japan
3 Laboratory of Mineral Processing and Resources Recycling, Division of Sustainable Resources Engineering,
Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Japan
4 Laboratory of Groundwater and Mass Transport, Division of Sustainable Resources Engineering, Faculty of
Engineering, Hokkaido University, Sapporo 060-8628, Japan

*E-mail: tangviroon.p@gmail.com Tel: +81-(0)11-706-8191 ORCID: 0000-0002-7325-5632

Abstract
Large-scale coal mining is being carried out in Tete province, Mozambique.
This area is also being planned to become a large coal fired power production hub
serving electricity to neighboring countries in southern Africa. Thus, huge amounts
of coal will be burned, resulting in the generation of a large quantity of coal ash.
High concentrations of hazardous elements are often released from coal and coal
ash causing negative impacts to human health and the environment. Therefore, it is
important to understand the possibility of hazardous elements leaching. Aqueous
batch leaching experiments under ambient conditions were conducted using six
coal samples and their ash. Most of the coal leached very low concentrations of
hazardous elements. However, an absence of carbonate minerals gave rise to higher
acidity levels. This resulted in elevated leaching concentrations of manganese and
iron, regardless of their contents. Burning coal resulted in higher contents of
hazardous elements in the ash. However, leaching concentrations of most of the
elements from the ash samples were still lower than the environmental standards.
Chromium and manganese were enriched in slightly acidic leachates regardless of
their contents while higher arsenic than the permitted level was leached from the
ash containing the highest arsenic content that generated neutral pH leachate.
These findings highlight a possibility of hazardous elements contamination from
Mozambican coal and coal ash. Therefore, the storage of coal and disposal of coal
wastes and ash in Tete Province should be done carefully and monitored to avoid
the contamination in the region.

Keywords: Coal, coal ash, hazardous elements, batch leaching, Tete, Mozambique
 1 Leaching of Hazardous Elements from Mozambican Coal and

2 Coal Ash
3 Abstract
4 Large-scale coal mining is being carried out in Tete province,
5 Mozambique. This area is also being planned to become a large coal fired power
6 production hub serving electricity to neighboring countries in southern Africa.
7 Thus, huge amounts of coal will be burned, resulting in the generation of a large
8 quantity of coal ash. High concentrations of hazardous elements are often
9 released from coal and coal ash causing negative impacts to human health and
10 the environment. Therefore, it is important to understand the possibility of
11 hazardous elements leaching. Aqueous batch leaching experiments under
12 ambient conditions were conducted using six coal samples and their ash. Most
13 of the coal leached very low concentrations of hazardous elements. However, an
14 absence of carbonate minerals gave rise to higher acidity levels. This resulted in
15 elevated leaching concentrations of manganese and iron, regardless of their
16 contents. Burning coal resulted in higher contents of hazardous elements in the
17 ash. However, leaching concentrations of most of the elements from the ash
18 samples were still lower than the environmental standards. Chromium and
19 manganese were enriched in slightly acidic leachates regardless of their contents
20 while higher arsenic than the permitted level was leached from the ash
21 containing the highest arsenic content that generated neutral pH leachate. These
22 findings highlight a possibility of hazardous elements contamination from
23 Mozambican coal and coal ash. Therefore, the storage of coal and disposal of
24 coal wastes and ash in Tete Province should be done carefully and monitored to
25 avoid the contamination in the region.
26
27 Keywords: Coal, coal ash, hazardous elements, batch leaching, Tete,
28 Mozambique
29
30
31
32
33
34
35
36
37
38
39

1
 1 1. Introduction
2 Coal is a combustible black or dark-brown sedimentary rock that is
3 formed underground from plant by peat formation during the early stage
4 (peatification). The combined effects of heat and pressure over millions of years
5 then transfer peat into coal (coalification) (Alpern and de Sousa 2002). It
6 contains most of naturally occurring chemical elements, and some of the
7 elements are toxic (Orem and Finkelman 2003). These toxic elements are
8 present in a wide variety of contents and forms, depending on different geologic
9 and geochemical processes that have occurred during peat and coal formation.
10 As a result, their existence in coal is specific to where they are found. Coal ash,
11 a by-product from coal combustion, is more enriched with several harmful trace
12 elements compared to its parent coal state due primarily to the depletion of
13 organic matter in coal during combustion (Fernandez-Turiel et al. 1994; Meij
14 1994; Baba et al. 2003; Jankowski et al. 2006). Heating and cooling during coal
15 combustion cause complex changes of coal particles, including char formation,
16 melted inclusion agglomeration, and volatile-element vaporization and
17 condensation (Clarke 1993; Jone 1995; Querol et al. 1995). These result in a
18 phase redistribution in the ash compared to the parent coal state. When coal and
19 coal ash come in contact with water, their hazardous constituents can be leached
20 or dissolved out, and contaminate surface water, groundwater, and soil in
21 different proportions (PSR 1995; Baba et al. 2003). This can lead to
22 environmental hazards and ecological risk, when hazardous elements are
23 present in sufficient quantities (Campbell et al. 1978; Meij 1994; Finkelman and
24 Peggy 1999; Gulec et al. 2001; Georgakopoulos et al. 2002; Baba et al. 2003;
25 Baba and Kaya 2004).
26
27 Coal mining is the fastest growing industry in Mozambique where the
28 greatest quantity is being excavated in Tete Province. This area is considered as
29 one of the largest coal deposits in the world, with an estimated coal reserve of
30 more than 37.6 billion metric tons (INAMI 2019). Additionally, two large
31 coal-fired power plants are going to be built in this area (ENRC Mozambique
32 2019; Ncondezi Coal Company Mozambique 2019). As a result, a large amount
33 of coal ash will be generated. This area is located in one of the most
34 environmentally sensitive areas since it is surrounded by rivers, which are used
35 by the local community for domestic, municipal, fishery, livestock raising, and
36 irrigation purposes. Therefore, leaching of hazardous elements from coal and
37 coal ash could cause huge problems for the local community. Consequently, it is
38 extremely important to understand the leaching of toxic trace elements from

2
 1 both Mozambican coal and coal ash in order to avoid the contamination.
2 Leaching studies have been conducted on coal (Wang et al. 2008;
3 Equeenuddin et al. 2010) and coal ash (Silva et al. 2010; Izquierdo and Querol
4 2012). However, because of the complex interactions of many factors,
5 prediction of the leaching characteristics of coal and coal ash remains site
6 specific. In other words, there is no universal formula for the determination of
7 leaching concentrations of hazardous elements in coal and coal ash. Therefore,
8 the evaluation of coal and its ash in Tete Province should be conducted to
9 understand the possibility of hazardous element leaching into the surrounding
10 environment. Findings from this study will be useful in evaluating the
11 environmental impacts of hazardous elements from both coal and coal ash and
12 will aid in increasing understanding of the risks involved in the storage of coal
13 and disposal of coal waste and coal ash in Tete Province. Moreover, this study is
14 also applicable on a global scale since the coal mined from Tete has been
15 exported to many countries around the world.
16
17 2. Materials and Methods

18 2.1 Sample Collection and Preparation

19 Bituminous coal samples were collected from stockpiles at two major
20 coal mining sites, Moatize (C1, C2, and C3) and Benga (C4, C5, and C6), both of
21 which are located in Tete Province, Mozambique. All samples were randomly
22 taken using shovels. They were then air-dried under ambient conditions for 1
23 week, crushed using a mortar and pestle, sieved through a 2 mm aperture screen,
24 and finally stored in air-tight containers to minimize their exposure to moisture
25 prior to use. Particle sizes of less than 2 mm were chosen according to the
26 Japanese standard for the leaching test of contaminated soils (JLT-13 1973).
27 These samples represent the coal from each coal seam that has recently been
28 reached and is being mined on each site. Samples C4, C5, and C6 belonged to
29 three different coal seams on Benga site, namely C, D, and E, respectively. In
30 contrary, on Moatize site, coal samples were obtained from two separate coal
31 seams in which C1 was in Souza Pinto seam, and C2 and C3 were a member of
32 Chipanga seam. Two samples, C2 and C3, were taken from the same coal seam
33 at different depths. The Chipanga seam is very thick, and thus, it is divided by
34 the mining company into 3 layers, called Top Chipanga, Middle Chipanga, and
35 Bottom Chipanga. At the time of sampling, the Top Chipanga has already been
36 mined off. Therefore, only the Bottom and Middle Chipanga were sampled and
37 named as C2 and C3, respectively.
38

3
 1
2 Coal ash samples denoted as A1, A2, A3, A4, A5, and A6 were prepared
3 by combusting C1, C2, C3, C4, C5, and C6, respectively. In preparation, about 2 g
4 of each coal sample (< 2 mm) were put in a crucible and combusted in a
5 computer-controlled ashing furnace (Ishizuka Denki Seisakusho, Japan). The
6 procedure involved slow heating of the sample to 500°C for 3 h followed by
7 continuous burning at the same temperature for 1 h. After this, the temperature
8 was increased rapidly to 815°C and maintained at this temperature for two more
9 hours. Finally, the furnace was cooled down to room temperature prior to the
10 sample removal (Zue 2014). Excluding the step of air-drying, the ash samples
11 were prepared following the same procedure as the coal pieces.
12
13 The current employed combustion protocol is one of the standard
14 methods for proximate analysis of coal and coke published by Japanese
15 Standard Association (JSA) (JIS M 8812 2006). The process leads to a complete
16 expulsion of all water and volatile organic compounds (VOCs) and complete
17 combustion of the organic carbon in the coal. This standard heating procedure
18 has been selected to burn the coal samples to tentatively evaluate the leaching
19 characteristic of their ash since we still do not know the type of combustion that
20 Tete power plants will adopt.
21
22 2.2 Solid Sample Characterization
23 Fine particles, with a diameter less than 50 µm, of the coal and ash
24 samples were prepared for chemical and mineralogical analyses. The analyses
25 were conducted using X-ray fluorescence spectrometer (XRF) (Spectro Xepos,
26 Rigaku Corporation, Japan) and X-ray diffractometer (XRD) (MultiFlex,
27 Rigaku Corporation, Japan). Loss on ignition (LOI) was determined by
28 measuring the weight loss of the oven-dried sample after heating it inside a
29 furnace (Ishizuka Denki Seisakusho, Japan) at 750°C for 1 h (JIS A1226 2014).
30
31 2.3 Leaching Tests
32 Batch leaching experiments were conducted for all coal and ash samples
33 under ambient conditions using a mixing speed of 200 rpm, liquid to solid ratio
34 of 1:10, and leachant as 18 MΩ·cm deionized water (Milipore Milli-Rx 12α
35 system, Merck Millipore, USA). Leaching durations lasted 6, 24, and 168 hrs.
36 All experiments were performed using 250 mL Erlenmeyer flasks and a
37 lateral-reciprocating shaker (EYELA Multi Shaker MMS, Tokyo Rikakikai Co.
38 Ltd., Japan). After the predetermined leaching time, the pH, electrical

4
 1 conductivity (EC), and oxidation reduction potential (ORP) of the leachates
2 were measured followed by centrifugation (Sigma 3K30 Laboratory Centrifuge,
3 Sigma, Germany) at 3,000 rpm for 20 mins. The supernatants were then filtered
4 through 0.45 μm Millex® sterile membrane filters (Merck Millipore, USA).
5 Each filtrate was divided into two equal portions. One of the two was acidified
6 with 1% Nitric acid (HNO3) to pH < 2. The other portion was kept as a
7 non-acidified sample. Both portions were finally stored in air-tight containers at
8 4°C prior to chemical analysis.
9
10 2.4 Chemical Analysis
11 The acidified samples were used to determine concentrations of heavy
12 metals while dissolved concentrations of coexisting ions were quantified using
13 the non-acidified filtrates. Metals and metalloids having concentrations higher
14 than 0.1 mg/L were determined using an inductively coupled plasma atomic
15 emission spectrometer (ICP-AES) (ICPE-9000, Shimadzu Corporation, Japan).
16 Hydride vapor generation technique was applied to quantify arsenic (As) having
17 concentration less than 0.1 mg/L. This determination technique has a detection
18 limit of 0.1 µg/L (Niedzielski and Siepak 2003). In preparation, 30 mL of the
19 sample was mixed with 15 mL of 12 M hydrochloric acid (HCl), 2 mL of 20%
20 potassium iodide (KI) solution, and 1 mL of 10% ascorbic acid (C6H8O6)
21 solution. The mixture was then diluted to 50 mL with deionized water and
22 allowed to react at room temperature for at least six hours before analysis. The
23 coexisting ions were analyzed by cation and anion chromatographs (ICS-60 and
24 ICS-1000, Dionex Corporation, USA). Alkalinity was determined by titration of
25 a known volume of leachate with 0.01 M sulfuric acid (H2SO4) until pH reached
26 4.8.
27
28 2.5. Geochemical Modeling
29 PHREEQC, one of the most widely used geochemical models, was used
30 to calculate the stability of minerals or chemical species that may affect the
31 mobility of various chemical constituents from the samples (Parkhurst and
32 Appelo 1999). All calculations were done based on thermodynamic properties
33 taken from the THERMODEM database (Blanc et al. 2012).
34
35 3. Results and Discussion
36
37 3.1 Properties of Coal and Coal Ash
38
39 3.1.1 Mineralogy
40 The X-ray diffraction patterns of all coal samples are shown in Fig. 1.
41 The most dominant minerals were found to be quartz. In all coal samples, a
5
 1 minor proportion of pyrite (FeS2) was detected. The presence of FeS2 can lead
2 to a formation of acidity once this coal is exposed to the atmosphere and may
3 induce leaching of many metals and metalloids (Rose and Cravotta 1998;
4 Tabilin et al. 2017a, b). However, most sulfur constituents including FeS2 are
5 transformed into oxide constituents (e.g. hematite (Fe2O3) and sulfur oxides
6 (SOX)) at high temperatures during burning of the coal (Querol et al. 1995;
7 Stanislav and Vassileva 1996; Silva et al. 2011). Consequently, no FeS2 but
8 Fe2O3 was detected in the ash samples (Fig. 2). Similar to coal, quartz was also
9 identified as the major mineral phase in all ash samples. Another silicate
10 mineral (muscovite) remained after heating as it is not sensitive to
11 transformation during high-temperature heating (Ward 2016). Common
12 secondary minerals, including anhydrite and hematite were observed in the ash
13 in different proportions. The formation of anhydrite may be attributed to the
14 dissociation of dolomite and the oxidation of FeS2 during combustion (Stanislav
15 and Vassileva 1996; Mudd and Kodikara 2000; Ward 2016).
16
17 3.1.2 Chemical compositions and LOI
18 The chemical compositions and LOI of the coal and ash samples are
19 given in Tables 1 and 2, respectively. Table 1 also contains ash yield. Regardless
20 of the source, the content of silica (SiO2) was the second to LOI and the highest
21 in coal and coal ash, respectively. These results agree with the fact that quartz
22 was the dominant mineral in both coal and coal ash. The values of LOI in ash
23 samples became zero regardless of their original LOIs in coal. This is attributed
24 to the fact that the operating temperature of currently employed ashing process
25 (815°C) was higher than that of LOI determination (750°C). In other words,
26 volatilizable, combustible, and decomposable constituents at 750°C in ash were
27 already volatized, combusted, and decomposed at ashing temperature of 815°C,
28 and therefore, the same weight of ash was observed before and after LOI
29 determination of ash (LOI = 0). Ash yield ranged from 12.5 to 52.5 wt% with
30 the average value of 27.7 wt%. The majority of coal, including C1, C2, C4, and
31 C5 had a high ash content (>20%), which is one of the common characteristics
32 of Mozambican coal (Vasconcelos 2009). Except selenium (Se), all of trace
33 elements were more concentrated in ash than those in coal. By taking ash yield
34 into consideration, the results indicate that large portion of Se was lost while the
35 rest of the elements were partly volatilized or were condensed and deposited
36 back onto ash surface during the combustion process. This is confirmed by the
37 fact that Se has the highest volatility (Huang et al. 2004; Lopez-Anton et al.
38 2007) and the lowest recondensing temperature (< 500°C) (Noda and Ito 2008)

6
 1 amongst all present trace elements.
2
3 3.2 Leaching Test
4
5 3.2.1 Leaching of coal
6 Figures 3(a) and (b) show the values of Eh and pH of coal leachates. In
7 all samples, Eh ranged between positive 360-560 mV, indicating an oxidative
8 leaching condition. An acidic pH (pH 3.5-4.8) was observed in the leachates of
9 C3 while those of the other coal samples were about neutral to slightly alkaline
10 (pH 7.5-9.2), regardless of the contact time. The variation of pH could be
11 mainly controlled by two mechanisms, including oxidative dissolution of sulfide
12 minerals and dissolution of carbonate minerals (Tabelin et al. 2012a, b; Tabelin
13 et al. 2017a, b). The most abundant sulfide and carbonate minerals found in coal
14 are pyrite and calcite/dolomite, respectively (Stanislav and Vassileva 1996).
15
16 The overall reaction representing the oxidation of pyrite (Chandra and Gerson
17 2010) is generally given as:
18
19 FeS2 + 3.75 O2 + 3.5H2O Fe(OH)3 +2 SO42- + 4 H+ (1)
20
21 In reaction 1, protons (H+) are generated. This contributes to the production of
22 acidity. However, the produced H+ can be consumed by the acid dissolution of
23 calcite (reaction 2) and dolomite (reaction 3) (Lui and Dreybrodt 1997;
24 Pokrovsky and Schott 2001).
25
26 CaCO3 + H+ Ca2+ + HCO3- (2)
27 CaMg(CO3)2 + 2H+ Ca2+ + Mg2+ + 2 HCO3- (3)
28
29 This assumption is supported by the relationship between the molar
30 concentrations of conservative ions from dissolution products of carbonate and
31 sulfide minerals (Fig. 4). The leachates from C3 were rich in sulfate (SO42-) but
32 less rich in calcium (Ca2+) and magnesium (Mg2+), with respect to the trend of
33 C1, C2, C4, C5, and C6. This suggests that the acidic pH of C3 resulted from a
34 lack of neutralizer (carbonate minerals). Moreover, a positive correlation
35 between these dissolution products of each sample suggests a simultaneous
36 occurrence of the dissolution reactions even though sulfide and/or carbonate
37 minerals were not detected in some samples.
38

7
 1
2
3 Table 3 represents the leaching concentrations of some hazardous
4 elements. The leaching contractions that exceeded the environmental standard
5 are noted in bold and a dash is for ones below the instrument detection limit.
6 Most elements were released in very low concentrations. However, the leaching
7 concentration of manganese (Mn) exceeded the environmental guideline in the
8 leachates of C2, C3, C5, and C6. Among them, C3 caused the greatest concern
9 because Mn was excessively leached. In addition, iron (Fe; 13.6-14.1 mg/L)
10 was also over the permitted level (0.3 mg/L) in C3. The mobility of these two
11 elements appeared to be unrelated to the contents of the respective elements in
12 the coal (Table 1). For example, C3 did not contain the highest solid contents of
13 Mn and Fe but released them in the highest concentrations. Therefore, it can be
14 implied that the leachability of hazardous elements from coal samples depends
15 significantly on the leaching conditions. In other words, the highest acidity of
16 C3 plays an important role in the enrichment of Fe and Mn because of the
17 following mechanisms: first, the higher acidity induces less precipitation of Fe
18 oxy-hydroxide/oxide and more dissolution of readily available Fe
19 oxy-hydroxide/oxide in coal (Stumm and Lee 1961; Schwertmann 1991; Gupta
20 and Gupta 2005), and second, the depletion of Fe oxide could lead to higher
21 mobility of numerous heavy metals and metalloids since these oxide minerals
22 are known to have high affinities toward a number of elements of environmental
23 concern, including Mn (Gadde and Laitinen 1974; Millward and Moore 1982).
24 Moreover, Mn is reported to be mostly associated with carbonate minerals in
25 coal in which the solubility is inversely proportional to the pH (Querol et al.
26 1995). As a result, most of the heavy metals and metalloids, including Mn, were
27 leached more in C3 because of its acidic leachate.
28
29 3.2.2 Leaching of ash
30 The levels of Eh and pH in the leachate of the ash samples are shown in
31 Figs. 5(a) and (b). The Eh of the leachates of all ash samples were in a positive
32 region, confirming that the experiments were conducted under oxic conditions.
33 The coal ash of A1 and A2 yielded an alkaline pH (pH 9.6-11.6) while the
34 remaining samples produced pH around neutral to slightly alkaline (pH 6.2-8.3)
35 when mixed with water. The change in pH might be predominantly governed by
36 the following mechanisms: (1) hydrolysis of oxides of alkaline and alkaline
37 earth metals formed during the coal combustion process as shown in reactions 4
38 and 5, and (2) dissolution of sulfur dioxide (SO2) and sulfuric acid (H2SO4)

8
 1 sorbed onto the particle surface during coal burning (reactions 6 and 7) (Talbot
2 et al. 1978; Roy and Griffin 1984; Roy and Berger 2011).
3 AO + H2O A2+ + 2OH- ; A represents Ca and Mg (4)
+ -;
4 M2O + H2O 2M + 2OH M represents Na and K (5)
+ 2-
5 2SO2 + O2 + 2H2O 4H + 2SO4 (6)
+ 2-
6 H2SO4 2H + SO4 (7)
7
8 Figure 6 illustrates the relationship between the concentrations of the cations
9 (Ca2+, Mg2+, Na+, and K+) and anions (SO42-). The units reported in Fig. 6 were
10 transformed from mmol/L to meq/L. A reference 1:1 dashed line demonstrates
11 equal generations of hydroxide (OH-) and H+ by hydrolysis of metal oxide and
12 dissolution of H2SO4, respectively. The samples A1 and A2 leached more cations
13 than SO42-, indicating a higher production of hydroxide (OH-) (reactions 4 and
14 5) than that of H+ (reactions 6 and 7). This supports the appearance of alkaline
15 leachates from A1 and A2. The leachates of A4-A6 are located along the 1:1 line,
16 illustrating the balance generation of H+ and OH-. This confirms the neutral to
17 slightly alkaline pH of the water-ash system of A4-A6. However, an
18 inconsistency appeared in sample A3. Even though the data of sample A3 is
19 above the straight line, its pH was even lower than that of A6. This might be a
20 result of a high buffering capacity of the A3 leachates, which can be proven
21 using the measured alkalinity (Fig. 7). The alkalinity of A3 was the third-highest
22 following A1 and A2. The higher alkalinity with lower pH indicates a higher
23 buffering capacity of A3 than that of A6. Therefore, a slightly alkaline and stable
24 pH was observed in A3 regardless of the relationship in Fig. 6.
25
26 The results of the leaching tests of hazardous elements are shown in
27 Table 4. Five elements, including As, B, cobalt (Co), chromium (Cr), Mn, and
28 zinc (Zn), were leached at a level above the instrumental detection limit. Dashes
29 in the table represent elements with concentrations lower than the detection
30 limit of ICP-AES, while numbers in bold indicate elements that exceeded the
31 permitted value. Arsenic concentrations in the A3 leachates were in the range of
32 77 and 82.1 µg/L which exceeded the environmental guideline for drinking
33 water. Although A3 ash was very rich with As (Table 2), no As-rich mineral
34 phase was detected (Fig. 2). This suggests that most of the As was associated
35 with amorphous minerals, particularly as a condensed phase on the ash surface
36 (Clarke 1993). Therefore, As is expected to be easily leachable in the water-ash
37 system. Moreover, in the pH range of A3, oxyanionic-forming characteristic of
38 As displays high mobility supporting its enrichment (Izquierdo and Querol

9
 1 2012; Tabelin and Igarashi 2009; Tabelin et al. 2010; Tabelin et al. 2012c, d;
2 Tabelin et al. 2014; Tamoto et al. 2015; Tabelin et al. 2017c, d; Tangviroon et al.
3 2017; Tangviroon and Igarashi 2017). In the case of Cr, although higher
4 contents of Cr were found in ash A1, A3, and A6, much higher concentrations
5 were leached out from A4 and A5. This suggests that the solid content is not the
6 only indicator, but also the conditions of the leachate (pH and Eh) are also
7 parameters that affect the mobility of the metal. These play an important role in
8 determining the mobility of the elements of concern.
9
10 PHREEQC simulations showed that at pH and Eh conditions of samples
11 A4 and A5, Cr3+ existed in higher amount than Cr6+. Trivalent chromium
12 typically exhibits cationic adsorption properties where its adsorption increases
13 with increasing pH (Richard and Bourg 1991). Therefore, Cr is relatively
14 mobile in the leachates of A4 and A5, compared to others. Many researchers
15 have also reported that the dissolved Cr3+ enhances Mn leaching via reductive
16 dissolution of manganese oxide (Eary and Rai 1987; Weaver and Hochella
17 2003). This can possibly explain the enrichment of Mn, which simultaneously
18 occurred with Cr in samples A4 and A5.
19
20 3.2.3 Comparison of coal and ash
21 Calcium, Mg2+, and SO42- were the most abundant constituents in the
22 leachates from both coal and ash samples. The release of these ions accounted
23 for more than 80% of the total dissolved ions. However, different leaching
24 mechanisms were observed due to the alteration of minerals during ashing. In
25 coal samples, the dissolution of carbonate minerals was expected to be the main
26 source of Ca2+ and Mg2+, while SO42- was released by the oxidation of sulfide
27 minerals. The occurrence of these reactions is consistent with the variation of
28 pH in coal leachates. On the other hand, in the case of ash samples, apart from
29 the hydrolysis of secondary metal oxides and dissolution of H2SO4 as previously
30 mentioned in section 3.2.2, dissolution of anhydrite (CaSO4) were also likely to
31 contribute to the enrichment of the major ions. This assumption was made since
32 anhydride is relatively soluble in water (Klimchouk 1996) and available in all
33 ash samples.
34
35 Figure 8 shows the electrical conductivity (EC) of the coal and ash
36 samples. The overall EC values of the coal were significantly lower than that of
37 the ash, indicating a higher overall leachability of ash. This could be attributed
38 to the ashing process that gives rise to a higher surface area and the higher

10
 1 amounts of condensed species on the ash surface. Boron, Mn, and As were
2 released in most of the coal samples and their ash in different proportions
3 (Tables 3 and 4). Boron and As were leached more in all ash samples when
4 compared to their parent coal states. According to Clarke (1993) these two
5 elements have been proven to be easily volatilized from coal and condensed
6 back onto the surface of ash, promoting leachability. This evidence also
7 supports the above assumption. However, Mn did not behave in the same way
8 as B and As. This is due possibly to a very low volatility of Mn together with
9 the formation of Mn oxide from manganese carbonate after ashing, making it
10 harder to mobilize from ash regardless of its content (Biernacki and
11 Pokrzywnicki 1999). Therefore, the enrichment of chemicals does not appear to
12 be an accurate indicator of the leachability in both coal and ash samples since it
13 is also controlled by many other factors, such as chemical compositions and
14 leaching conditions.
15
16 4. Conclusion
17 Batch leaching experiments were carried out using six samples of coal
18 and their respective ash. The ash samples were prepared in the laboratory using
19 the standard combustion protocol provided by JSA. The LOI values in all ash
20 became zero after burning regardless of the initial LOI of their parent coal.
21 Generally, leaching concentrations of hazardous elements from coal and coal
22 ash samples were lower than their permitted levels. However, As, Cr, Mn, and
23 Fe had concentrations that exceeded the environmental standard. The
24 concentration of Mn exceeded the drinking water guideline in C2, C3, C5, and C6.
25 However, in C2, C5, and C6, Mn was released at a level of slightly higher than
26 the standard value and thus had very low impacts on the environment. Sample
27 C3 produced strongly acidic leachate, induced by the absence of carbonate
28 minerals. This resulted in the enrichment of Fe and Mn even though the
29 contents of both elements in C3 were found to be the second lowest among all
30 coal samples. On the other hand, the ash contained higher solid contents of
31 hazardous elements than that of their parent coal. However, the leachability of
32 hazardous elements from ash was found to be controlled by the mode of
33 occurrence of elements and leaching conditions. The leachates of A1, A2, and A6
34 had concentrations of hazardous elements lower than environmental guideline
35 for drinking water. In contrast, the concentrations of As leached from the A3
36 sample was over the permitted level, caused by a high surface-association of As
37 and pH conditions of the ash-water system of A3. The weakly acidic leachates of
38 A4 and A5 contributed to higher leaching concentrations of Cr3+ and Mn

11
 1 regardless of their solid contents. Based on the results, the elements of concern
2 in coal were Fe and Mn, while, in ash, As, Cr, and Mn should be considered.
3 Therefore, continuous monitoring of the above mentioned metals and metalloid
4 should be done by considering many factors, such as solid content, solid
5 composition, leaching concentration and, pH since the leachate quality of both
6 coal and ash samples depends not only on the solid content and mineralogy but
7 also the leaching conditions. Regarding the current employed ashing process, an
8 extension for the near future is the use of the same ashing temperature(s) and
9 procedure(s) as those in the actual process(es) to get more accurate results on
10 the leaching of ash after the final decision on the type(s) of power plants has
11 been made.
12
13 5. Acknowledgement
14 The authors would like to acknowledge the coal companies for all supports
15 during sample collection and Japan International Cooperation Agency (JICA)
16 for providing us with the research grant.
17
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19
Table 1 Chemical compositions and LOI of coal samples
Coal samples
Parameter
C1 C2 C3 C4 C5 C6
LOI
61.31 63.5 81.89 44.25 64.5 76.67
(wt%)
Ash yield
29.12 35.15 12.73 52.52 24.07 12.46
(wt%)
Major
elements
(wt%)
SiO2 14.16 15.14 6.31 25.66 12.19 6.03
Al2O3 5 5.89 2.87 9.75 4.7 2.39
Fe2O3 0.32 3.93 0.51 0.8 1.16 0.5
MgO 0.17 0.69 0.02 0.15 0.06 <0.01
CaO 1.09 2.44 0.08 3.32 0.27 0.62
K 2O 0.36 0.64 0.14 0.9 0.54 0.23
P2O5 0.28 0.07 0.02 0.93 0.07 0.16
SO3 1.01 1.58 3.03 0.94 1.19 1.01
TiO2 0.57 0.44 0.13 0.65 0.36 0.22
Trace
elements
(mg/kg)
As <0.8 2 2.3 <1.3 <0.7 <0.5
Co <5.4 34.8 7.2 <11 <8.8 <4.9
Cr 73.3 41.5 11.9 73.3 41.9 30.9
Cu 22.7 21.1 9.5 33.2 20.3 11.8
Mn 36.6 259 32.6 57.8 81.4 25.5
Ni 25.7 31.7 12.3 31.1 23.9 19.6
Pb 16.9 15.4 4.9 26.6 14.1 10.4
Se 1.4 <0.5 0.8 1 0.4 <0.2
V 87.9 42 17.2 24 43.1 23.9
Zn 10.9 44.7 17.9 25.9 32.6 26.4
Table 2 Chemical compositions and LOI of coal ash samples
Ash samples
Parameter
A1 A2 A3 A4 A5 A6
LOI
0 0 0 0 0 0
(wt%)
Major
elements
(wt%)
SiO2 48.62 43.07 49.55 48.85 50.63 48.37
Al2O3 20.74 19.03 22.31 20.45 22.4 22.75
Fe2O3 1.16 10.15 7.16 1.44 3.87 2.71
MgO 1.37 3.15 0.33 0.53 0.8 0.7
CaO 3.75 6.73 0.67 6.2 1.03 4.41
K 2O 1.25 1.72 1.5 1.71 0.28 1.69
P2O5 1 0.25 0.06 1.75 0.28 1.45
SO3 0.55 2.98 0.24 0.11 0.13 0.15
TiO2 1.7 1.08 1.57 1.23 1.32 1.32
Trace
elements
(mg/kg)
As <2.3 2.4 15 <2.2 <2.1 <2.4
Co <15 82 90 <20 28.1 <26
Cr 198 106 169 143 131.1 169
Cu 78.5 57.7 102 61.2 70.7 65.1
Mn 130 690 485 104 305 139
Ni 64 71.3 126 50.7 64.7 80.4
Pb 58.9 48.2 69.3 52.1 49 64
Se 0.8 <0.7 <0.8 0.8 <0.7 <0.8
V 135 61 147 29.1 137 109
Zn 40.3 118 95.5 56.3 109 106
Table 3 Concentrations of elements in coal leachates (unit in mg/L except pH unless
mentioned)
Coal samples WHO
Element
C1 C2 C3 C4 C5 C6 guideline*
As (µg/L) 0.1-0.2 0-0.33 0-1.12 1.15-2.8 0.1-0.31 0-0.16 10 (µg/L)
B - - 0-0.07 - - - 2.4
Cd - - 0-0.002 - - - 0.003
Cu - - 0-0.013 - - - 2
Fe - - 13.6-40.1 - - - 0.3
Mn 0.002-0.007 0.01-0.24 0.44-2.13 0.005-0.007 0.15-0.24 0.13-0.14 0.1
Pb - - 0-0.0024 - - - 0.01
Zn - - 0.04-0.11 - - - 3
*World Health Organization, 2011

Table 4 Concentrations of elements in coal ash leachates (unit in mg/L except pH unless
mentioned)
Coal ash samples
Element Guideline
A1 A2 A3 A4 A5 A6
As (µg/L) 0.35-0.67 0.83-0.88 77.6-82.1 2.0-2.67 1.87-2.44 4.23-5.61 10 (µg/L)*
B 0.01-0.09 0-0.05 0.84-1.03 0.18-0.22 0.09-0.11 0.21-0.25 2.4*
Co - - - - 0-0.013 0-0.01 0.05**
Cr - - - 0.05-0.09 0.11-0.30 - 0.05*
Mn - - 0-0.04 0.16-0.19 0.41-0.53 - 0.1*
Zn - - - 0.04-0.08 0.16-0.30 - 3*
*World Health Organization, 2011

**Task Force on Water Quality Guidelines of the Canadian Council of Ministers of the Environment, 2008
 Q
Q
M K K, Q
K Gt K Gt
P P K Q KQ K Q P
Intensity (arbitrary units)

K C6 Legend
M Q K, M K, Q
K K
M PP Q KQ Q Q-Quartz
K P C5
K
Q K, M K, Q K-Kaolinite
M M K PP Q Q
K KK K K P C4 M-Mica (Muscovite)
Q K
K Q K K, Q
Q Gt-Goethite
PP K Q KK K P C3
K
K, M K, D K, Q P-Pyrite
Q K D
M K M PP Q KQ Q S P
K
C2 D-Dolomite
K
Q K, D K, Q
K K, M S-Siderite
M K M D Q
Q Q K
PP K P
C1

20 40 60
CuKα (2θ in degrees)

Fig. 1 X-ray diffraction patterns of coal samples

Q
Intensity (arbitrary units)

Q, I
M IH H Q
M Anh QQ Q Q Q Q H
H A6
Q Q Q
M H Q
M Anh H H Q Q Q Q Q
H Legend
Q
A5
M I H Q Q-Quartz
M Anh H Q, I QQ Q Q Q Q
H A4
Q Q M-Mica (Muscovite)
Q Anh Q
M H H Q Q
M Anh Q Q H HH H-Hematite
A3
Q Q Anh
Anh
M H Q Q Anh-Anhydrite
M M Anh H H Q M Q HH
Q H
A2 I-Illite
Q
H Q Q
M Anh Q Q Q Q
M Anh Q Q H A1

20 40 60
CuKα (2θ in degrees)

Fig 2 X-ray diffraction patterns of coal ash samples

 (a)

(b)

Fig. 3 Bar chart showing (a) Eh and (b) pH of coal leachates at three different mixing times

Fig. 4 Comparison between the molar concentrations of conservative ions formed by acid and
neutralization reactions in coal
 (a)

(b)

Fig. 5 Bar chart showing (a) Eh and (b) pH of coal ash leachates at three different mixing times

Fig. 6 Comparison between the molar concentrations of conservative ions formed by H+ and OH-
production reactions in ash (A = Ca and Mg, M = Na and K)
Fig. 7 Alkalinity of the leachates of ash samples at three different mixing times

Fig. 8 Comparison between electrical conductivity of coal and their ash

Highlights

1. Leaching properties of hazardous elements from coal and coal ash are difference.
2. Coal ash has higher leachability than its parent coal.
3. Leachate with lower pH promotes the mobility of some hazardous elements.
4. There is a possibility of hazardous element contamination from coal and coal ash.
Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: