Journal Pre-proof

Nanoparticles from evaporite materials in Colombian coal mine

drainages

Luis F.O. Silva, James C. Hower, Guilherme L. Dotto, Marcos

L.S. Oliveira, Andrea L. Moreno

PII: S0166-5162(20)30584-X
DOI: https://doi.org/10.1016/j.coal.2020.103588
Reference: COGEL 103588

To appear in: International Journal of Coal Geology

Received date: 13 July 2020

Revised date: 26 August 2020
Accepted date: 26 August 2020

Please cite this article as: L.F.O. Silva, J.C. Hower, G.L. Dotto, et al., Nanoparticles
from evaporite materials in Colombian coal mine drainages, International Journal of Coal
Geology (2020), https://doi.org/10.1016/j.coal.2020.103588

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© 2020 Published by Elsevier.

 Journal Pre-proof 1

Nanoparticles from evaporite materials in Colombian coal mine drainages

Luis F. O. Silvaa,* felipeqma@hotmail.com, James C. Howerb,c, Guilherme L. Dottod,

Marcos L. S. Oliveiraa, Andrea L. Morenoa

a
Department of Civil and Environmental. Universidad de la Costa, CUC, Calle 58 # 55–

66, Barranquilla, Atlántico, Colombia.

b
University of Kentucky, Center for Applied Energy Research, 2540 Research Park

Drive, Lexington, KY 40511, USA

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c
University of Kentucky, Department of Earth & Environmental Sciences, Lexington,

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KY 40506, USA -p
d
Chemical Engineering Department, Federal University of Santa Maria – UFSM, 1000,
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Roraima Avenue, 97105–900, Santa Maria, RS, Brazil
*
Corresponding author.
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Abstract
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Ultrathin and nanometric materials (minerals and amorphous phases) are

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detected in transitory deposits of potential hazardous elements (PHEs), especially in

acidic coal mine drainages. The main goal of this work was to evaluate the occurrence

of PHEs in nanoparticles (NPs) in evaporative structures in coal mining areas with high

concentrations of PHEs. The precipitates were sampled in several coal mining areas in

Colombia, with the purpose of evaluating the geochemical and environmental

structures. In the present work, to better diagnose areas affected by coal mining, an

innovative analytical procedure is proposed to define the association between PHEs in

mine drainage sediments. The procedure includes the analytical study with X-Ray
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Diffraction (XRD) and advanced electron microscopy, before and after a series of

sequential extractions to separate amorphous, magnetic, and crystalline compounds. Of

the three main types of precipitates identified, the yellowish precipitates had the highest

amounts of PHEs while the white precipitates had only small amounts of PHEs and the

greenish precipitates contained TiO2 nanoparticles. The results from this study will be

usable for more than fifty countries that have coal mine drainages.

Keywords: Coal drainages; Massive minerals precipitation; River sediments;

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Environmental contamination.

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1. Introduction
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Water, sediment, and soil pollution is increasingly widespread worldwide (Peres

et al., 2018; Rodrigues et al. 2018; Dotto et al., 2011, 2012, 2015a,b, 2016). Legal and
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illegal coal mining companies in Colombia present several physical, biological,

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economic, environmental, hydrological, and geomorphic ramifications. Acharya and

Kharel (2020) reported the main hydrological impacts of mining, noting that the
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movement of the soil can modify the water flow paths, thus increasing runoff, erosion,
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leaching and drainage of contaminants, the underground void, and the base flow.

Billions of tons of coal rejects (soil and overburden moved in mining) are produced

annually in mining activities, thus compromising the soil, water, and atmosphere

(Adiansyah et al., 2015). Despite the fact that the US, Brazil, and some countries in

Western Europe use less coal than just a few years ago, the impacts of the mined areas

continue to be a factor at the global level.

Coal mine drainages (CMDs) differ from the acid-mine drainage of gold,

uranium, and all other sources due to the large amount of organic material present in
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water and sediments (Saikia et al., 2018; Dutta et al., 2019). Recent studies have shown

that nanoparticles (NPs) and ultra-fine particles (UFPs) present in rivers and CMDs

have a great capacity to adsorb PHEs as well as toxic organic compounds (Rodriguez-

Iruretagoiena et al., 2016; Civeira et al., 2016a, b). In addition, some authors have

shown that many secondary minerals crystallized in rocks from CMDs have a genotoxic

effect (Nordin et al., 2018), justifying the need for geochemistry studies to broaden the

knowledge of such compounds.

Several hydrated sulfates, selenates, and several amorphous aluminosilicates

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generate efflorescences in drains and rivers contaminated by coal mining as a result of

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water evaporation in times of drought (Nordin et al., 2018). The initial process,
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however, comes from changes in Fe-sulfide wastes in the presence of oxygen and water,
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which may vary according to different environmental conditions (Oliveira et al., 2018).

However, in recent years, only a few scientists have studied the precipitated efflorescent
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salts in CMDs (Sahai et al., 2017; Nordin et al., 2018; Silva et al., 2021), and this is the
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first study carried out in Colombia for this purpose in several areas of coal mining.

According to the US Environmental Protection Agency (EPA), the ecological

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problems of mine drainages are “surpassed only by global warming and the destruction
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of ozone". Therefore, the present study has global applications since it evaluates NPs

and UFPs in the sediments of CMD, a theme that until today has received little attention

from the scientific community.

This study reports the results of detailed sampling campaigns for precipitated

efflorescent compounds, complex mineralogical evaluations of NPs and UFPs related to

PHEs, and hydrogeochemical reactions to elucidate the sources and the cycle of

sulfates, iron, aluminum, and amorphous phases as well as their relationships with water
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quality of CMDs. The results of this study are expected to assist several countries in

their management and recovery plans for CMD sediments.

2. Studied Area

In the studied areas (Figure 1), unlike the Guajíra and Cesar region, where it

does not rain frequently, the rains tend to be intense during most of the year. Table 1, in

the supplementary material, shows the beginning of rains in the main coal mining

regions in Colombia. However, as there are multiple mining operations, most of which

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are illegal, the impacts on the rivers and drains of these regions are enormous. Figure 2

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illustrates some of the areas where the impacts are very visible. Considering the
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proximity to the population, the waters of the Valle del Cauca Department (Figure 2 A
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and 2B) have some of the worst impacts in Colombia; after all, the acid drainages and

rivers contaminate what was once drinking water for the population, in addition to civil
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structure of bridges, and other constructions due to contact with water containing high
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concentrations of salts (e.g. acid sulfates) and a lower pH (3) than in most areas studied.

No less striking are the coal mining areas in the Boyacá department (Figure 2C and 2D)
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where acidic waters end up killing vegetation and eliminating the possibilities of using
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rivers for bathing, food, and agriculture.

After several visits to the largest coal-mining region in Colombia, specifically

the areas of La Guajira and Cesar, no CMD or rivers with significant flows were found,

especially when compared to other mining regions in Colombia. This fact was also

possible thanks to previous studies in these areas (Oliveira et al., 2019; Silva et al.,

2020). Forty-eight precipitated efflorescent materials from Colombian CMD zones were

sampled in the 11 departments described in the supplementary material, with the

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exception of La Guajíra and Cesar. Special attention was paid to the departments

marked in the supplementary material.

3. Analytical Procedure

As reported by Civiera et al. (2016a, b), acid drainage sediments can contain

more than 90% amorphous material, making them complex to be studied by XRD and

advanced microscopes (AM). Therefore, initially the evaporites were analyzed with

lenses attached to a Leco-brand camera in order to identify larger crystals such as

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gypsum and quartz. After that, a portion of each sample was analyzed by XRD and AM.

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However, the amorphous phases were a complication that had to be considered.
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Therefore, several sequential extractions were performed with water (to extract the
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soluble phases), ammonium oxalate (to extract amorphous phases), and hexane (to

extract apolar phases). Such extractions have been previously reported by several
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studies (Ribeiro et al., 2010; Quispe et al., 2012; Silva et al., 2011a,b,c,d). After each
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extraction, each sample was analyzed again by XRD and AM, thus obtaining better

results. In each sampled precipitate, 95 particles were studied by AM. Even at this level
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of detail, it is possible to optimize resources and time with the analyses. A field-
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emission scanning electron microscope (FE-SEM) was used to study 15 10-20-µm

particles, 30 5-10-µm particles, 30 1-5-µm particles, and 30 100-1000-nm particles and

a high-resolution transmission electron microscope (HR-TEM) was used to study 45

particles smaller than 100 nm. Such a procedure does not require sample preparation

prior to analysis by advanced microscopy (AM) and X-ray powder diffraction (XRD).

These procedures in more realistic results and do not alter the nature of the sampled

Colombian coal rejects.

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The evaporite materials sampling methodology was recently reported by Silva et

al., 2021. It is an exhaustive sampling (due to the fragility of the samples) with plastic

spatulas that extract the evaporites directly into test tubes until reaching the laboratory.

The solid samples were analyzed with a Bruker X-ray diffractometer (model D8

DISCOVER) with NAP-LOCK X-ray optics to examine mineral and amorphous phase

occurrences (Ramos et al., 2017). Working conditions were as follows: slit fixed at 12

mm, Cu Kα monochromatic radiation, and 20-mA current at 40 kV. Samples were

scanned at a speed of 0.3° 2θ/min (5–65°). The ultra-fine and nano-particles (UNPs)

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samples with mixed compounds were studied by X-ray diffraction (Gasparotto et al.,

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2018) and advanced electron-beam (HR-TEM, 200 kV, and FE-SEM) equipped with a
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FE cathode and an energy omega filter for high accuracy of the assembly and atomic
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arrangement, fast Fourier transform (FFT), microbeam diffraction (MBD), selected area

electron diffraction (SAED), scanning transmission electron microscopy (STEM), and

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energy-dispersive X-ray spectroscopy (EDS) (Oxford Instruments INCA 4.09 software).

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The chemical components with high atomic numbers appear in the brightest areas of the

identified image and those with low atomic numbers in the dark-field areas. The
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AM/EDS reveal that the particulate matter (PM) has slightly diverse geochemical
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conformation (Rodriguez-Iruretagoiena et al., 2015). Before microscopic analysis, the

specimen holder was cleaned with an advanced plasma system (Gatan Model 950) to

minimize contamination. Even so, a blank was analyzed at the same time as the samples

in order to ensure that the samples did not contain impurities from the specimen holder.

The FE-SEM model Sigma 300 VP (Carl Zeiss, England) with field emission filament

(FEG- Field Emission Gun) of the Schottky type (tungsten filament covered with

zirconium oxide) and equipped with a Gemini column (Zeiss, England). The images

were obtained using the secondary detector (SE2) in high-vacuum mode (1x10-9 bar);
 Journal Pre-proof 7

working distance of 5 mm; opening of 20 µm; and magnifications of 1000X, 2500X,

and 5000X. The energy-dispersive X-ray spectrometer (EDS) spectra were generated by

the EDS X-ray detector (model Quantax 200-Z10, Bruker, Germany) equipped with a

10-mm2 quartz window and ESPRIT software. The EDS were obtained using the

secondary detector (SE2) in the variable-pressure mode, which consists of the insertion

of N2 gas in the sample compartment, allowing the variation of the partial pressure

between 1 and 133 Pa (1 Pa = 1x10-5 bar), working distance 8.5 mm, energy of 20 kV,

and opening of 60 µm (Cerqueira et al., 2011, 2012). In addition, HR-TEM equipped

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with EDS was utilized. The X-Ray diffraction (XRD) pattern after amorphous

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extraction of obtained samples were acquired with Cu-Kα radiation (λ =1.54 Å). Raman
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Spectroscopy was utilized to study the particles molecular organization (Dias et al.,
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2014a,b; Ribeiro et al., 2010).
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4. Results and Discussion

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Several authors claim that acid mine drainage water as well as CMDs water pose

global threats to water quality (Sun et al., 2019; Nordin et al., 2018). In the present
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study, several iron sulfides (Table 1) were detected in sampled CMDs; these materials
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were suggested by the literature of the last two decades as being responsible for the

formation of several by-products, including precipitated materials in CMD. Recent

CMDs studies have shown that the chemical composition of these waters is highly

complex and may vary temporally, after all they depend on the time of contact with the

Fe-sulfides, the amount of dissolved oxygen to oxidize the Fe-sulfides, the flow of the

CMD and rivers, among other diverse environmental and geological factors (Silva et al.,

2011a,b; Rodriguez-Iruretagoiena et al., 2016). In addition, geographical conditions,

such as the implications of climate and structure, are factors of great importance in
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terms of the pollution caused by CMDs in the region under study. The heavy rains

existing in the evaluated area dominate the river flows and drainages containing

dissolved contaminants, suspended in the water, and even precipitated in the sediments.

Previous Brazilian authors have reported the spillage of coal cleaning rejects in the

rivers and CMDs of the region of Santa Catarina State (Civeira et al., 2016a), which

further accelerates the formation of precipitated materials in CMD.

Both the results of the most abundant minerals by XRD and the results of

components by advanced microscopy (Table 1) proved that the most abundant

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compounds in the precipitated materials in Colombian coal drainages were aluminum,

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calcium, iron, magnesium, manganese, and potassium, in addition to many amorphous
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compounds composed of the same components and PHEs. It should be noted that on
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rainy days, a greater amounts of quartz and clays in contact with the evaporite materials

were detected by electron microscopy. This does not indicate that they were formed
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together, but that the quartz and the clays were washed away by the rains, thus reaching
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the regions where the evaporites were being formed on the rocks.

The geochemical configuration of the sampled evaporites of the Colombian

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CMDs results from the composition of the water in contact with coal wastes. Nordin et
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al. (2018) showed that the precipitates are highly toxic compounds, particularly because

most are formed by compounds highly soluble in water and also because they contain

high proportion of PHEs. In this study, it was possible to prove that the studied samples

contained numerous minerals that formed due to climatic conditions that varied within

and between sampled locations. Considering the great variety of minerals and

amorphous phases detected in this study, for a better understanding of the material, the

groups of evaporites were separated by colors accordingly: whitish on reddish rocks

(Figure 3), reddish with yellowish interiors (Figure 4), and greenish tones (Figures 5
 Journal Pre-proof 9

and 6) evaporites. In general, all sampled evaporites were highly variable as to the

occurrence of PHEs (e.g. As, Cd, Cr, Hg, and Se). However, color separation helped to

standardize a certain mineralogical sequencing containing amorphous materials.

Table 2 illustrates the main PHEs that were detected in the amorphous and

mineral phases present in the studied CMDs. Table 2 only demonstrates the importance

of certain compounds, it does not necessarily mean that every occurrence of the mineral

or amorphous phase had all of the PHEs in its structure. However, it serves to

demonstrate the importance of immobilizing several PHEs that have an affinity for

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certain compounds.

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4.1 Whitish-on-reddish-rocks precipitates
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For the group of whitish-on-reddish-rocks precipitates, the most frequent and

abundant mineralogenic phase was gypsum, detected by XRD in all study areas (Table
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1). Figure 3 illustrates the formation of gypsum on the reddish rocks of the CMDs
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containing iron sulphides by-products. In all the areas studied, both the XRD and the

photos using a magnifying glass on the gypsum crystals helped to prove that there were
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no other abundant minerals in the whitish group. However, when using electron
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microscopy, the less-abundant phases were detected, and in these the occurrences of

anhydrite, basanite, and, in smaller proportions, calcite were proven. This demonstrates

the need to use advanced microscopy, especially FIB-SEM/EDS, for a correct

evaluation and geochemical interpretation of the studied areas.

The amorphous phases that generate the whitish tone always contain Ca and

have been related to calcite and gypsum. This signals that they are products of the

dissolution of Ca-carbonates (Table 1) due to the sulfuric acid formed by the oxidation

and dissolution of Fe-sulfides. Previous studies of Colombian coal rejects did not detect
 Journal Pre-proof 10

such minerals when the wastes had no signs of oxidation and decomposition (Silva et

al., 2020; Oliveira et al., 2019). Similar results have been reported by several American,

European, and Brazilian authors studying areas of coal rejects and CMD (Sehn et al.,

2016; Ribeiro et al., 2010, Hower et al., 2013).

The majority of this group occurred on reddish rocks of the CMD. We show that

these whitish compounds are formed by the deposition of CMD water droplets on rocks.

Such drops when dehydrating can crystallize to form plaster and other minerals.

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4.2 Reddish-with-yellowish-interiors precipitates

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The group of reddish-with-yellowish-interiors precipitates was the group that
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contained the most PHEs. Its mineralogical formation, containing numerous minerals
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such as the abundant jarosite, coquimbite, goethite, hematite, and szomolnokite; minor

minerals such as halotrichite, ferrohexahydrite, melanterite, and rozenite; and less

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abundant phases and other trace phases such as natrojarosite and schwertmannite
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probably facilitated the adsorption of the PHEs. This fact was also confirmed by several

other studies in worldwide coal areas (Silva et al., 2011c; Saikia et al., 2018; Ribeiro et
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al., 2010).
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As seen on the surface of Figure 4A, there is a purple surface in which, when

analyzed by XRD and advanced microscopes, it was possible to confirm that it is an

assemblage of less-soluble minerals (i.e. goethite and hematite) compared to the

yellowish interior of the same formation of precipitates. Such yellowish formation was

the one that contained the highest concentration of soluble iron minerals such as jarosite

(Figure 4C), coquimbite, szomolnokite, halotrichite, ferrohexahydrite, melanterite,

rozenite, natrojarosite, and schwertmannite. However, it was the purple part that

contained the greatest proportion of PHEs. This is probably due to the fact that when
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dehydrating, the minerals of the successive formation form goethite and hematite, which

adhere to the PHEs that were present in the most hydrated minerals. Another

influencing factor is that hematite and goethite have large surface areas (Gredilla et al.,

2019; Hochella et al., 2008; Fernandez-Ortiz et al., 2017), facilitating the adsorption of

PHES. In almost all sampled areas, similar mineral associations were detected.

As mentioned above, this group of minerals was the most important in the

adsorption of PHEs. Therefore, they can be considered natural mitigators of PHE

solubilization and leaching. Several minerals such as goethite, gibbsite, hematite,

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jarosite, and other phases of iron and aluminum have been reported to be important

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since elements such as As, Cd, Co, Cr, Hg, Mo, Ni, Pb, Se, V, and U are frequently
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found incorporated in their structures (Oliveira et al., 2012a, b; Elwood-Madden et al.,
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2012). Therefore, PHEs adsorption may be the result of the association between PHEs

ions in these minerals and also in the amorphous phases detected in this study. The iron
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sulphate phases were mostly present in a complex relationship with As, Cr, Cd, Pb, Sc,
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and U. In view of these results, the importance of new studies proves especially using

FIB-SEM/EDS in future studies.

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In all the studied areas (with the exception of Guajira), the precipitation and
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dissolution of several amorphous and mineralogical phases around the roots of plants

that were on the margins of the CMD changed the characteristics of the soil, thus

modifying the absorption of water by roots, in addition to increasing the availability of

nutrients for plant growth. This reduces the amount of water that is contaminated in the

CMDs. In addition, the precipitation of Fe (III) / Fe (II) dissolved as hydr / oxides of

(i.e. goethite, hematite, magnetite) in abandoned areas of coal rejects contributes to the

reduction and immobilization of PHEs (Xie and Zyl, 2020). Relationships between plant

roots in coal mining areas also include several microbial activities in relation to organic
 Journal Pre-proof 12

compounds and inorganic chemical reactions. The data obtained in this study show the

good effects of several complex associations to increase the immobility of PHEs.

Therefore, the work of chemical reactions in the rhizosphere can provide information

for the management of future phytoremediation work to prevent PHEs from continuing

to contaminate rivers and drains in coal mining areas.

4.3 Greenish-tone precipitates

Among the three groups of precipitates in this study, the greenish-tone

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precipitates were the most fragile when collecting, and when they were on the rocks

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inside the sampled CMDs (Figure 5A) they often broke and fell into the acidic waters,
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dissolving instantly. Due to such difficulty in obtaining the samples at the sampling
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point, it was decided to deposit them directly in glass bottles (Figure 5A). After

completing the sampling campaigns, all samples were analyzed directly by XRD and
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advanced microscopies. Only thanks to this was the large number of minerals
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represented in Table 2 obtained, because otherwise many would have been lost and / or

altered during the collection and transportation of the samples. In total, more than 890
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amorphous particles were detected containing Al, Mg, Mn, O, S, K, among other
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elements (e.g. Figure 5B). These amorphous components may be responsible for

generating several of the crystalline phases found in CMDs (Table 2). Figure 5C

illustrates an example, among the various complex hydrated minerals, of pickeringite

(5C). Greenish-tone precipitates were composed in most areas studied by minerals of

Ca, Mg, Mn, K, Ti, and O, such as halotrichite, epsomite, bassanite, gypsum,

hexahydrite, pickeringite, gibbsite, and some clays (Table 2). In this group of

evaporites, not as many PHEs were detected by FIB-SEM/EDS; however, by observing

the PHEs of this group, it is possible to infer the occurrence of rutile and anatase.
 Journal Pre-proof 13

Toxicological studies report that such titanium dioxides have great effects on

microorganisms, plants, and other living beings (Nordin et al., 2018).

Considering that this study aims to identify precipitates formed in CDMs, an

attempt was made to study the precipitates formed during the dry season and with little

rainfall. Such collections were possible in Cesar, however, in Guajíra, not even CMDs

without water were detected. This fact may be associated with it being the region with

the lowest incidence of rainfall in Colombia. Most of the CDMs without or with very

little water have mineralogical organizations with very unusual minerals compared to

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CMDs that contain water all year round. Such mineralogical organizations contain

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gypsum, kaolinite, magnesioanthophylite (Mg4Fe3(Si8O22)(OH)2), and rosenbergite
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[AlF3•3(H2O)] (Figure 6) and other infrequent minerals in areas of intense rain.
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Recent studies have reported the occurrence of fullerenes and carbon nanotubes

in soils from coal mining and CMDs (Sanchis et al., 2015; Gredilla et al., 2019).
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However, in this study, such compounds were detected only in Colombian areas where
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previous authors (Oliveira et al., 2019; Silva et al., 2020) reported spontaneous coal

combustion. The interpretation for the studied areas is that such nanoparticles were
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deposited by the waters of the CMDs or rains/leaching processes, being deposited in the
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rocks where the greenish-tone precipitates were formed. Often, the identification of

fullerenes and nanotubes was only possible after FIB cuts since the nanoparticles were

inside the Al- and Fe-sulfate crystals. This highlights the importance of nanomineralogy

for thorough geochemical studies. After all, using only general techniques such as XRD,

spectroscopy, and chemical analysis including sequential extractions, it is not possible

to detect minority phases that are often more toxic than the majority phases present in

the environment.
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5. Conclusions

In this study the main coal mining areas of Colombia were studied. The water

resources of several regions where there is a greater amount of rain today are being

compromised, making it impossible to use by the population since it contains

contaminants that exceed all limits and recommendations of USEPA. The methodology

developed in this study for studies of precipitates in CMDs helps to understand phases

of great environmental importance and for human health. The minerals that make up

yellowish precipitates are the great adsorbents of PHEs, while the whitish precipitates

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hardly contained any PHEs, and the greenish ones contain only Ti dioxides which can

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be aggravating factors for the environment and human health. The intensities of rains
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were a major determining factor for the formation of the three groups of evaporites
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studied, especially since the driest region of Colombia (Guajíra) had virtually no

formation of precipitates, whereas in regions of intense rain the precipitates were

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formed in great abundance and in different hydrated forms. For further studies, it will be
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important to increase the use of FIB-SEM / EDS to provide more detailed and real

understandings about CMDs.

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Acknowledgments

All persons who have made substantial contributions to the work reported in the manuscript

(e.g., technical help, writing and editing assistance, general support), but who do not meet the

criteria for authorship, are named in the Acknowledgements.

We thank the CNPq.

Credit authorship contribution statement

 Journal Pre-proof 15

All persons who meet authorship criteria are listed as authors, and all authors certify that they

have participated sufficiently in the work to take public responsibility for the content, including

participation in the concept, design, analysis, writing, or revision of the manuscript.

Furthermore, each author certifies that this material or similar material has not been and will

not be submitted to or published in any other publication before its appearance in this journal.

Luis F.O. Silva: Conceptualization, Funding acquisition.

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Andrea Moreno, James C Hower, Guilherme L. Dotto, and Marcos L.S. Oliveira: Writing -

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original draft, Writing - review & editing.
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Conflict of interest
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The authors have not conflict of interest.

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Figure 1. Location of the main mineral areas of Colombian coal, as well as rainfall

indexes and illustrative photos of mining and their impacts.

Figure 2: Illustration of sampled areas of precipitate formation. (A and B) Valle del

Cauca Department; (C and D) Boyacá Department

Figure 3: Demonstrative photo of whitish-on-reddish-rocks precipitates; General XRD

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result; and gypsum photographed with the aid of a camera fitted with a

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magnifying glass to avoid altering the surface of the compounds.
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Figure 4. The XRD result shows the complexity of the reddish precipitates that contain
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yellowish phases below. (A) Highlight for the reddish surface that mainly contains

goethite, hematite, and Fe-amorphous phases; (B) Interior of the evaporites that
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mainly contain Fe, Al, and Ca-sulfates; (C) FE-SEM image of jarosite.
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Figure 5. Results and sampling and analysis scheme of greenish precipitates formed on

rocks inside CMDs. (A) Sampling for adequate characterization by XRD and
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advanced microscopies; (B) General EDS and picture of the amorphous phases;
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(C) Photo by FIB-SEM of pickeringite.

Figure 6: Photo of a CMD in dry season containing little or no water and the typical

XRD result containing complex minerals. The unidentified crystalline phase (s)

are quartz and some clays. Such phases were not identified because they do not

have a direct role in the geochemical formation of evaporites.

Table 1: A general view of amorphous phases and minerals detected by XRD (X) and

electron microscopies (x).

 Journal Pre-proof 34

ANTIO BOY CAU CORD CUNDINA NORTE SANTA VAL

QUIA ACA CA OBA MARCA DE NDER LE
SANTA DEL
NDER CAU
CA

Amorphous X X X X X X X X
phases

Minerals:
X X X X X X X X
Quartz, SiO2
X X
Chlorite,
X X
Na0.5Al6(Si,Al)8O2
X X X X X X X X

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0(OH)10.H2O

Illite, X X X X X X X X

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K1.5Al4(Si6.5Al1.5)
x x X
O20(OH)4 -p
Kaolilite,
Al2Si2O5(OH)4 x x x x
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Muscovite, x x x x x x x x
(Ba,K)Al2(Si3Al)
O10(OH)2
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x x

Marcasite, FeS2 x x
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Pyrite, FeS2 x x x x x

Sphalerite, ZnS x x x x x x x x
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Ankerite, x x x x x x x x
(Fe,Ca,Mg)CO3
x x x x x x x
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Calcite, CaCO3
x x x x x x x
Monazite, (Ce, La,
Th, Nd, Y)PO4 x x x X x x x x

Anhydrite, CaSO4 x X X X X

Alunogen, X X X X X X X
Al2(SO4)3.17H2O
x X x x x X x x
Barite, BaSO4
x x x x x x
Bassanite,
X X X X X X X X
2CaSO4·H2O
x x x x x x x
Coquimbite,
Fe2(SO4)3.9H2O x x x x x x x x
Epsomite, MgSO4
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. 7H2O x x x x x x

Ferrohexahydrite, x x
FeSO4 . 6H2O
x x x x x x
Hexahydrite,
MgSO4 . 6H2O

Gypsum, x x x x
Ca[SO4]·2H2O

Halotrichite,
x X X X X X x X
FeAl2(SO4)4•22(H
2O) x x x x x x
Jarosite, x x x x x x x x
KFe3+3(SO4)2(OH)

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6 x x x x x x x

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Melanterite, x x x x
FeSO4 . 7H2O
x x x
-p x x x
Natrojarosite,
NaFe3(SO4)2(OH)6 x x x x x x x x
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Pickeringite,
MgAl2(SO4)4•22(
H2O)
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Schwertmannite,
Fe3+16O16(OH)12(S
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O 4) 2

Szomolnokite,
FeSO4.H2O
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Rozenite, FeSO4 .
4H2O
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Hematite, Fe2O3

Goethite, Fe(OH)3

Gibbsite, Al(OH)3

Anatase, TiO2

Rutile, TiO2

Table 2: Main PHEs and their associations with minerals detected in CMDs sediments.

The chemical elements were detected by EDS at multiple points of each sample
 Journal Pre-proof 36

studied. In addition, SAED, MDB and HR image confirmed the crystalline

structure of several minerals, in addition to helping understand amorphous mixed

phases with minerals.

Compounds Potentially Hazardous Elements

Amorphous phases Al, Ag, As, Cd, Ce, Co, Cr, Cu, Ga, Ge, Hg, La, Li, Mn, Mo, Ni, Pb, Sb,
Se, Sn, Sr, Th, Ti, Tl, U, V, W, Zn
Minerals:

Clays
As, Cd, Co, Cr, Fe, Ge, Ni, Pb, Sb, REEs
Marcasite, FeS2

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Ag, As, Bi, Cd, Cu, Hg, Mn, Ni, Sb, Se, Sn, Ti, Zn
Pyrite, FeS2

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As, Au, Bi, Cd, Co, Cu, Ga, Ge, Hg, Mo, Ni, Pb, Sb, Se, Sn
Sphalerite, ZnS -p
Ag, As, Sb, Cu, Cd, Co, Cr, Fe, Ga, Ge, Hg, Mn, Mo, Ni, Sn, Se
Alunogen, Al2(SO4)3.17H2O
Al, As, Co, Cr, Cu, Hg, Mo, Pb, Se, Sb, Zn
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Coquimbite, Fe2(SO4)3.9H2O
Al, Cd, Ce, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, Pb, Sb, Se, Sn, Ti, U, V, W,
Epsomite, MgSO4 . 7H2O
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Zn

Ferrohexahydrite, FeSO4 . 6H2O

Al, Pb, Ti, Zn
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Hexahydrite, MgSO4 . 6H2O

Al, As, Sb, Cu, Cd, Co, Hg, Ni, Pb, Sn, Se, Ti, U, V, W, Zn

Halotrichite,
Al, Ti, Zn
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FeAl2(SO4)4•22(H2O)
Al, Cu, Cd, Cr, Hg, Li, Mn, Mo, Ni, Pb, Sn, Se, Sr, Ti, U, V, W, Zn
Jarosite, KFe3+3(SO4)2(OH) 6
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Al, As, Sb, Cu, Cd, Co, Cr, Ga, Ge, Hg, Li, Mn, Mo, Ni, Pb, Sn, Se, Sr,
Melanterite, FeSO4 . 7H2O
Ti, U, V, W, Zn

Pickeringite,
Al, As, Cu, Co, Hg, Ni, Pb, Sn, Se, Ti, U, V, W, Zn
MgAl2(SO4)4•22(H2O)
Al, Pb, Ti, Zn
Schwertmannite,
Fe3+16O16(OH)12(SO4)2 Al, Ag, As, Cd, Ce, Co, Cr, Cu, Ga, Ge, Hg, La, Li, Mn, Mo, Ni, Pb, Sb,
Se, Sn, Sr, Th, Ti, Tl, U, V, W, Zn
Rozenite, FeSO4 . 4H2O
Al, As, Co, Cr, Cu, Hg, Mo, Pb, Se, Sb, Zn
Hematite, Fe2O3
Al, As, Cd, Ce, Co, Cr, Cu, Hg, Mo, Ni, Pb, Sb, Se, Sn, Ti, U, V, Zn
Goethite, Fe(OH)3
Al, As, Cd, Ce, Co, Cr, Cu, Ga, Ge, Hg, La, Li, Mn, Mo, Ni, Pb, Sb, Se,
 Journal Pre-proof 37

Gibbsite, Al(OH)3 Sn, Sr, Th, Ti, U, V, W, Zn

Al, As, Co, Cr, Cu, Hg, Mo, Pb, Se, Sb, Zn

Highlights

 Coal drainage effluorescences precipitates and associated hazards were

studied in the Colombian coal areas.
 Prevention techniques and integrated management minimize AMD risks.
 Leaching of coal wastes are the principal reason for water contamination.
 Iron and aluminum chemistry precipitates organizers toxical elements seasonal

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pattern.

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Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6