Geoscience Frontiers 9 (2018) 863e875

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China University of Geosciences (Beijing)

Geoscience Frontiers
journal homepage: www.elsevier.com/locate/gsf

Focus Paper

Ambient nanoparticles/nanominerals and hazardous elements from coal

combustion activity: Implications on energy challenges and health
hazards
Binoy K. Saikia a, b, *, Jyotilima Saikia a, b, Shahadev Rabha a, b, Luis F.O. Silva c, Robert Finkelman d
a
Polymer Petroleum and Coal Chemistry Group, Materials Science and Technology Division, CSIR-North East Institute of Science and Technology, Jorhat, 785006,
Assam, India
b
Academy of Scientific and Innovative Research, CSIR-NEIST Campus, Jorhat, 785006, India
c
Research group in Environmental Management and Sustainability, Department of Civil and Environmental Engineering, Universidad de la Costa, Barranquilla,
Colombia
d
University of Texas at Dallas, Richardson, TX, USA

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

Article history: Coal is the most abundant fossil fuel in the world. Because of the growth of coal mining, coal-fired power
Received 15 August 2017 plants and coal-burning industries, the increase of the emission of particulates (coarse, fine or ultrafine)
Received in revised form is of great concern. There is a relationship between increasing human morbidity and mortality and
15 November 2017
progressive environmental air pollution caused by these types of particles. Thus, the knowledge of the
Accepted 25 November 2017
Available online 18 December 2017
physico-chemical composition and ambient concentrations of coal-derived nanoparticles will improve
Handling Editor: M. Santosh pollution control strategy. Given the current importance of this area of research, the advanced charac-
terization of this coal combustion-derived nanoparticles/nanominerals as well as hazardous elements is
Keywords:
likely to be one of the hottest research fields in coming days. In this review, we try to compile the existing
Coal combustion knowledge on coal-derived nanoparticles/nanominerals and discuss the advanced level of character-
Nanoparticles ization techniques for future research. This review also provides some of aspects of health risks asso-
Nanominerals ciated with exposure to ambient nanoparticles. In addition, the presence of some of the hazardous
Hazardous elements elements in coal and coal combustion activities is also reviewed.
Human health Ó 2018, China University of Geosciences (Beijing) and Peking University. Production and hosting by
Coal energy challenge Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/
licenses/by-nc-nd/4.0/).

1. Introduction generates substantial amounts of ultrafine/nanoparticles formed

Despite concerns about the environmental impacts of coal use,
in particular the contribution of CO2 to climate change, enormous
amounts of coal are still being burned annually to produce elec-
tricity, heat for industry and homes, coke for steel manufacturing,
and feed stock for synthetic gas and numerous chemicals. Pro-
jections indicate that coal use will continue to rise by 0.6% annually
through 2040 (www.iea.org).
Coal is a complex organic-rich sedimentary rock that is typically
enriched in S, As, Hg, Pb, Se, etc., elements that are potentially
harmful to the environment and human health. Coal combustion
* Corresponding author. Polymer Petroleum and Coal Chemistry Group, Materials
Science and Technology Division, CSIR-North East Institute of Science and Tech-
nology, Jorhat, 785006, Assam, India.
E-mail addresses: bksaikia@neist.res.in, bksaikia@gmail.com (B.K. Saikia).
Peer-review under responsibility of China University of Geosciences (Beijing).
primarily by mineral transformation during the high temperature
combustion process. Most modern coal-fired power plants have
sophisticated pollution control systems (electrostatic precipitators,
bag houses, flue gas desulfurization units, etc.) that capture much of
the particulates, sulfur dioxide, and trace elements liberated by coal
combustion. However, these pollution control systems are ineffi-
cient in capturing the finest particles like ultrafine particles
(Sambandam et al., 2014).
Generation of anthropogenic carbonaceous matter and mixed
crystalline/amorphous mineral ultrafine/nanoparticle by world-
wide coal-fired power plant represents serious environmental
problems due to their potential hazards (Ribeiro et al., 2013). Ul-
trafine particles and nanoparticles are similar term with 1 to
100 nm in size. Thus, the use of coal to produce energy increases
illness and death in the general population mainly because of air
pollution (Garcia et al., 2014; Agudelo-Castaneda et al., 2016;
Schneider et al., 2016). Moreover, coal burning in power plants also

https://doi.org/10.1016/j.gsf.2017.11.013
1674-9871/Ó 2018, China University of Geosciences (Beijing) and Peking University. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-
ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
864 B.K. Saikia et al. / Geoscience Frontiers 9 (2018) 863e875

produces other airborne pollutants such as coarse particulate Table 1

matter (2500 and 10,000 nm in size), sulfur dioxide, oxides of ni- The elements concentration determined in the four Assam coals (ppm: mg/kg ash
basis) (after Saikia et al., 2009).
trogen, carbon dioxide, acid gases (HCl, HF), and hydrocarbons
(PAHs) in addition to the emission of nanoparticles. Thus, each of Metal Ledo Bragolai Tikak Tipong World Indian US
the steps in the coal life cycle, starting from mining to trans- coal average average

portation in addition to coal combustion, generates nanoparticle Fe 6240 4582 3990 3576 e e e
Mg 424.35 603 752 928
contamination (Oliveira et al., 2012a, b, 2014; Ribeiro et al., 2013).
Bi 7 4.50 5.2 2.69 2e20
Exposure to emissions from coal-fired plants depends on factors Al 1315 632 1003.2 1825.4
such as temperature, precipitation, wind direction and speed, and V 64 58.72 76.2 58 2e100
topographical features of the local area (Hower et al., 2013; Wilcox Mn 14 13.40 35.2 65.50 5e300 100 100
et al., 2015). Emissions may be local or regional, causing health Pb 10 5 8.6 9.60 2e80 15 15
Cd 5 5 n. d. 4.04 0.1e65 1.3 1.3
effects to those living near or far from power plants. Several re- Cr n. d. n. d. 0.3 n. d. 0.1e60 70 15
searchers had clearly indicated the relationship between increasing Ni 5 1.50 1.6 9.60 0.5e50 45 15
human morbidity and mortality due to increasing air pollution Co 3 5 8.50 9.20 0.5e30 11 7
caused by ultrafine/nanoparticles (Suzuki et al., 2002; Chen et al., Cu 45 23 55 69.60 0.5e50 20 19
Zn 35 10 10 14 5e300 40 39
2004; Tatar et al., 2005; An et al., 2007; Effros, 2009; Rastogi
et al., 2009). Due to the greater surface area of a nano-material/ Note: n. d. e not detected.
nano-mineral (any material/mineral with single unit size is
<100 nm), they are more environmentally active with respect to
combustion purposes. Thus, there is an urgent need of reviewing
bio-uptake and associated health risks as compared to larger par-
the current status of research on coal combustion-derived nano-
ticles with the same chemical compositions (Gilmour et al., 2004;
particles and/or nanominerals, and their characterization tech-
Oberdorster et al., 2005; Xia et al., 2006a, b).
niques for the benefit of future researchers. The aim of this paper is
Nanoparticles carry considerable amounts of air toxics,
to critically review the existing knowledge on the properties of
including the largest fraction of polycyclic aromatic hydrocarbons
coal-derived nanoparticles/nanominerals and their available
(PAHs) by mass (Eiguren-Fernandez et al., 2003; Li et al., 2003).
advanced characterization techniques. The human health effects of
PAHs are found in gas-phase and as sorbet to aerosols in the
ambient nanoparticles and hazardous elements emitted from coal
ambient air. PAHs are known as mutagenic and carcinogenic in the
combustion activities are also given special emphasis in this paper.
animal system (Abdel-Shafy and Mansour, 2015). PAHs are gener-
ally emitted from residential heating, coal gasification and
liquefying plants, carbon black, coal-tar pitch and asphalt produc- 2. Characteristics of coal-derived ultrafine/nanoparticles
tion, coke production, catalytic cracking towers and related activ-
ities in petroleum refineries as well as motor vehicle exhaust. Airborne nanoparticles consist of over 95% of particulate matter
Estimated PAHs emission rate from coal is 0.95 mg/kg (Oros and when the number of particles is considered (Whitby, 1978;
Simoneit, 2000). Some PAHs such as anthracene (Ant), phenan- Kittelson, 1998; Oberdorster et al., 2005). It was found that the
threne (Phe), benzo(a)anthracene (BaA), and chrysene (Chry) were particles below 100 nm and below 300 nm contribute more than
found to be emitted from coal combustion (Harrison et al., 1996; 80% and 99% of the total number of particles irrespective of the
Saikia et al., 2016a, b). Coal tar pitch, a known Group-1 carcin- measurement locations and meteorological conditions (Heal et al.,
ogen contains about 200 PAH compounds, which are transported 2012). Nanoparticles emitted from coal combustion contain major
by wind and rainwater to nearby soil sediments, water and air, elements such as Al, C, Ca, Fe, Mg, Na, S, Si, and trace elements such
leading to increased cancer risk for human beings (Mahler et al., as As, Ba, Cd, Cr, K, Mo, Mn, Nd, Pb, Rh, Se, Ti, V, and Zn (Sambandam
2012). Many developed countries such as USA, Canada, etc. use et al., 2014). Swaine and Goodarzi (1995) reported that, based on
coal-tar-based sealcoat pavements which contains high PAHs. environmental relevance, the trace elements present in coal are in
Volatile PAHs in coal-tar-based sealcoat are released into the air and four groups: Group I elements (As, Cd, Cr, Hg, Se), which are known
other non-volatile PAHs get transported into the soil sediments and to be hazardous in some circumstances; Group IIA elements (B, CI, F,
water bodies due to abrasion and storm runoff. Mn, Mo, Ni, Pb); and Group IIB elements (Be, Cu, P, Th, U, V, Zn); and
Nanoparticles that are emitted from coal combustion as well as Group III elements (Ba, Co, Sb, Sn, Tl). The concentration of the
coal-handling activities are unintentional by-products, and in most elements present in the coal varies with ash yield, source areas and
cases, encapsulate several hazardous elements (Chen et al., 2005; geologic history (Gluskoter, 1975; Swaine, 1990). Saikia et al. (2009)
Giere et al., 2006; Hower et al., 2008). It is reported that coal also reported the presence of hazardous elements in few high
combustion activities also release aggregates of Fullerene (C60) in sulfur coals (see Table 1), which are regarded as Hazardous Air
terms of mass of C60 per mass of particulate matter (Tiwari et al., Pollutants (HAPs) in the 1990 Clean Air Act Amendments (CAAA)
2016; Saikia et al., 2016b). The gases generated from coal burning USA. Another study carried out by Baruah and Khare (2010) on trace
are also enriched volatile organic compounds, toxic and green- element concentration of high sulfur coals and their associated coal
house gases, organometallic compounds, and other gas compo- mine rejects showed that most of the hazardous elements are
nents (Hower et al., 2013; Ribeiro et al., 2013). Some researchers enriched in the coal mine rejects (see Table 2).
reported that the fly ash were generated from coal combustion Particulates emitted from coal combustion process whether
activity consists of finer-sized particles, ranging from 0.01 to they may be coarse, fine or ultrafine mainly originates from the
200 mm (Baba, 2002; Ribeiro et al., 2013). Due to their small size and heterogeneous nature of the mineral matter present in coal. During
larger surface area, these ash particles have a greater tendency to the coal combustion process, the highly volatile trace elements
absorb hazardous elements that are transferred from coal to waste such as As, Cd, Pb, Hg, Sn, Zn, Sb, etc., are likely to go into the air by
products during combustion (Gulec, 2001). So far, very few studies emission whereas, other elements like Cr, V, Zr, Mn, Co, Cu, etc., are
have been conducted on the emission of nanoparticles from coal retained in the ash and may also be responsible for soil and ground
combustion activities. Apart from use in electricity generation, coal water contamination (Saikia et al., 2009). A number of studies show
is also used in other industries like cement, steel, tea processing, that submicron (partial size <1 mm) and ultrafine coal fly ash par-
brick kilns, coke ovens as well as in household activities for ticles typically contain a large number of alkali and alkaline earth
 B.K. Saikia et al. / Geoscience Frontiers 9 (2018) 863e875 865

Table 2 transported to the surface (Covert et al., 1996a, b; Wiedensohler

Trace and potentially harmful elements (ppm) in coal and mine rejects of Meghalaya et al., 1996). The nucleation-mode particles of 3e10 nm size
(after Baruah and Khare, 2010).
range are formed by nucleation from the gas phase. The nucleation-
Elements Coal Mine rejects mode particles in the atmosphere grow by coagulation and vapor
MB MK MM MS MU ML MC MR1 MR2 condensation to become the aitken-mode (20e50 nm) and
Sb 6.0 13.4 6 22.7 6.0 19.7 21.8 12.6 11.1 accumulation-mode particles (30e300 nm), which may results in
As 1.0 1.2 3.0 1.2 1.0 1.0 1.0 1.3 25.9 atmospheric optical effects and, subsequently, climate change.
Cd 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.1 5.0
Cr 36.2 41.2 55.5 51.2 17.9 24.4 27.9 259 361
Co 10.5 12.3 15.0 9.9 11.8 3.0 11.5 22 20.9 3. Characterization techniques of ambient nanoparticles
Cu 2.8 13.4 6.4 3.6 6.1 8.4 40.0 23.6 32.9
Pb 6.1 12.0 6.5 13.7 2.4 4.9 7.4 149 98 To study the geochemical composition, size and distribution of
Mn 46.9 56.2 31.6 38.6 86.6 88.5 65.3 104 87 elements, and other properties of ultrafine/nanoparticles re-
Ni 2.8 4.6 4.1 4.5 2.0 2.4 9.8 36.4 58
V 60.8 70.3 74 71.4 18.8 34.1 48.5 50 55
searchers have used several instruments such as X-ray Diffraction
Zn 19.2 13.6 8.5 11.4 12.2 21.9 36.6 35.8 55 (XRD), High Resolution-Transmission Electron Microscope (HR-
TEM), Field Emission Scanning Electron Microscope (FE-SEM),
Atomic Force Microscopy (AFM), Raman Spectroscopy, Single Par-
ticle Mass Spectrometer, etc (Silva et al., 2009, 2010; Yehliu et al.,
metals such as Na, K, Mg, Ca, and transition metals such as Ti, Mn, 2011; Oliveira et al., 2014; Saikia et al., 2016a, b). Some of the
Fe, Co, Ni, Zn, V, Cr, Cu, and can be enriched in a number of met- advanced characterization techniques of coal combustion derived
alloids and other trace elements including Sb, As, Se, S, and Cl (Linak ultrafine/nanoparticles are discussed in the next several sections.
and Wendt, 1994; Seames and Wendt, 2000; Utsunomiya et al.,
2004). Utsunomiya et al. (2004) reported that trace elements 3.1. High-resolution transmission electron microscope (HRTEM)
such as Cd, As, La, Ce, Sr, etc., are present in the coal fly ash within a
range of 0.01e1.0 mm in size, which has the longest atmospheric HR-TEM is a powerful analytical technique in the study of
residence time (x100 days). The enrichment of metals in ultrafine nanoparticles and it has been extensively used to study the struc-
particles has also been observed in stack gas samples taken from ture, chemistry, size and morphology of atmospheric particles
coal-fired power plants (Yoo et al., 2005). Sui et al. (2007) observed (Utsunomiya et al., 2002; Lake et al., 2003; Mathis et al., 2004; Silva
enrichment of Ca, Cr, Cu, Fe, Mg, Mn, Pb, and Zn in the ultrafine et al., 2010). It provides good understanding of the detailed
particles generated from combustion of pulverized bituminous geochemistry of the potentially strong bio-reactive components of
Indian coal. Saikia et al. (2016a, b) studied the concentration of atmospheric particulate matter (Silva et al., 2009). TEM provides
potentially harmful elements in PM10 and PM2.5 samples around direct images and chemical information of nanomaterials at a
two tea processing industries in the Jorhat region of India. They also spatial resolution down to the level of atomic dimensions (<1 nm)
reported higher concentrations of hazardous elements (Ca, Cd, As, (Patri et al., 2006; Wang and Pui, 2011). Various analytical tech-
Hg, and Pb) in PM2.5 around tea processing industries using high niques can be coupled with TEM for different applications such as
sulfur coals. energy dispersive X-ray spectroscopy can investigate the chemical
Ultrafine/nanoparticles are formed by soot formation, vapor- composition of the nanomaterials (Patri et al., 2006; Wang and Pui,
ization of mineral matter, and inorganic ash (mineral matter) pre- 2011). Silva et al. (2009) used HR-TEM to study Fe-nanominerals
sent in the coals. These vaporized particles nucleate to form a large within coal fly ash (CFA). They found that Fe-nanominerals are in
number of nanoparticles, which then grow through condensation the size range of 10e100 nm in CFA (see Fig. 1). Figs. 2 and 3 show
and coagulation to form an accumulated mode of aerosols. Various the HR-TEM image of aerosol particles. HR-TEM can provide the
studies argued that nucleation-mode particles can be produced detailed shape of the nanostructure of individual particles in coal
aloft in the free troposphere cloud outflows and then they are and CFAs. The details of an HR-TEM image for carbon nanostructure

Figure 1. HR-TEM image and EDS spectrum showing very fine ordered hematite structures in fly ash particles (after Silva et al., 2009).
866 B.K. Saikia et al. / Geoscience Frontiers 9 (2018) 863e875
Figure 2. (a) Carbonaceous matter in the soot of aerosol. Rounded carbon particles
form a connected mass to form a larger particle. HRTEM of the carbonaceous matter
shows various degrees of crystallinity; from a small amount of rounded fringes (b) to
the very crystalline carbon (after Utsunomiya et al., 2002).
quantification (e.g. carbon nanotube; carbon nanoballs) was re-
ported elsewhere (Vander-Wal et al., 2004, Vander-Wal, 2005;
Yehliu et al., 2011). Utsunomiya et al. (2002) performed nanoscale
elemental mapping of the nanocrystallites with heavy elements by
using high-angle annular dark field scanning TEM (HAADF-STEM)
and STEM/EDS mapping.
Adachi and Buseck (2010) also used HR-TEM/EDS in their at-
mospheric study and reported that Fe was the most common
constituent (often associated with Cr, Mn, and/or Ti), followed by
Pb and Zn, which were frequently found together. Saikia et al.
(2015) extensively used HR-TEM to study the geochemistry and
nano-mineralogy of the sub-bituminous high sulfur coals of North
East India, mine overburden, and coal-derived fly ashes. The
mineralogical studies at nanoscale are termed as nanomineralogy.
However, the main limitations of this technique are that a high
vacuum and thin sample section (<50 nm) is required, specimens
can be damaged or even destroyed by an intense high-voltage
electron beam, the extensive preparation of thin specimens in-
creases the possibility of altering samples structure and makes TEM
analysis a very time-consuming process.
3.2. Field Emission Scanning Electron Microscope (FE-SEM)
Field Emission Scanning Electron Microscope (FE-SEM) is a very
useful tool for high-resolution surface imaging of nano-materials
(Yao and Kimura, 2007). Saikia et al. (2015) in their nano-
mineralogical study of coals and coal-residues from Assam (India)
performed FE-SEM analysis and detected a number of potentially
harmful nanominerals including hematite particles and ultrafine
hematite-containing Pb, As, and Mo in fly ash samples (see Fig. 4).
Silva et al. (2010) applied FE-SEM/EDS techniques to study coal fly
ash particles and observed that the particles primarily comprised of
<10 nm to >100 mm-diameter glassy aluminosilicates spheres.
During their study on composition and modes of occurrence of
minerals and elements in coal combustion products derived from
high-Ge coals, Dai et al. (2014) found variable contents of Fe, Ca, and
Mg, and limited amounts of K, Na, Ti, Mn, P, and F, and, in some
cases, trace elements in coal fly ash particles by using scanning
electron microscopy.
Riberio et al. (2013) performed the field emission scanning
electron microscopy with energy dispersive X-ray spectroscopy and
high-resolution transmission electron microscopy with energy
dispersive X-ray spectroscopy (HR-TEM/EDS) to study coal com-
bustion residues and integrated the results with that of time of
flight secondary ion mass spectrometry (ToF-SIMS) analysis and
physico-chemical analysis of ultrafine/nanoparticles present in the
coal fly ash samples. They reported the ultrafine glassy spheres
(z100 nm) and carbonaceous nanospheres (z50 nm) contain high
volatile elements (HVEs) such as As, Hg, Pb, Se and nanoparticles
with multiple nanominerals assemblages in the coal fly ash.
3.3. Atomic force microscopy (AFM)
Another excellent microscopic technique used to study nano-
particles and nanomaterials is Atomic Force Microscopy (AFM).
AFM allows for 3-D characterization with nanometer resolution. Shi
et al. (2015) performed analysis of morphological and mechanical
properties of coal combustion derived PM2.5 using atomic force
microscopy and revealed essential information about these parti-
cles such as surface roughness, stickiness, deformation, and elas-
ticity. Further, they performed scanning electron microscopy,
transmission electron microscope and energy dispersive X-ray
spectroscopy surveys to correlate these properties to the chemical
composition. They reported that the PM2.5 soot aggregates exhibit
the largest surface roughness; stickiness, and deformation (see
Fig. 5). Dwivedi et al. (2012) characterized the nano-scale particles
present in coal fly ash samples of the Harduaganj Thermal power
plant of India by using AFM and revealed the amorphous structures
with embedded quartz crystallites of average particle size and
roughness of 21 and 24 nm, respectively. However, the AFM cannot
provide any composition information of single particles.
 B.K. Saikia et al. / Geoscience Frontiers 9 (2018) 863e875 867

Figure 3. TEM-EDS images of PM2.5 (a, b, e, f) and PM10 particles (c, d, g, h) (after Saikia et al., 2016a, b).

3.4. X-ray diffraction (XRD) analysis
XRD is a primary tool for resolving the structure of crystalline
materials at the atomic scale (Cantor and Schimmel, 1980; Sapsford
et al., 2011). Silva et al. (2010) characterized a coal fly ash sample
which is composed of <10-nm to >100-mm diameter glassy
aluminosilicate spheres with the help of X-ray diffraction meth-
odology. X-ray diffraction revealed the presence of a number of
minerals including quartz, mullite, maghemite, wollastonite, etc.
Saikia et al. (2015) used low-temperature ash-XRD (LTA) to study
high sulfur Indian coal samples and observed that LTAs of the coal
samples have similar proportions of quartz, kaolinite, illite, and
pyrite, and, thus, bears similar overall mineral matter characteris-
tics (see Fig. 6). Table 3 demonstrated the quantitative X-ray
diffraction data for LTA of few high sulfur coal samples. Typically
XRD is used for characterizing crystalline size, shape, and lattice
distortion by long-range order, but is limited to amorphous mate-
rials (Zanchet et al., 2001; Sapsford et al., 2011).
868 B.K. Saikia et al. / Geoscience Frontiers 9 (2018) 863e875
Figure 4. (a) Ultra-fine hematite containing Pb, As, and Mo around agglomerate in
sample SCFA; (b) iron oxide (hematite) in sample SCFA; (c) anhydrite in sample NCFA
(SEM images) (after Saikia et al., 2015).
3.5. Aerosol mass spectrometry
Detailed analysis of the size-resolved mass concentration of
non-refractory components (organics, sulfate, nitrate, and ammo-
nium) in materials can be obtained by aerosol mass spectrometry.
Online mass spectrometers provide an important capability to
report on aerosol composition, size and their variations with high
time resolution (Laskin et al., 2012). Single particle aerosol mass
spectrometry provides real-time size and chemical composition
data for single aerosol particles. Lake et al. (2003), Phares et al.
(2003), and Tolocka et al. (2004) applied single particle mass
spectrometer for particle study. Lake et al. (2003) analyzed nano-
particles to an aerodynamic diameter of 45 nm and observed that
around 10% of sampled particles in an optimum range of
50e770 nm contained hazardous elements. However, wavelength
dispersive X-ray fluorescence (WD-XRF) spectroscopy could also be
used for determining bulk composition of size classified coal fly-ash
particles (Linak et al., 2007). Linak et al. (2007) found that the ul-
trafine fractions of each coal exhibit notably different bulk com-
positions compared to their coarse and fine fractions. The ultrafine
particles were enriched with elements including S, Cl, Na, K, V, and
P, and depleted in a number of relatively non-volatile elements
including Si, Al, Ca, Ti, and Mg (see Fig. 7).
Time of Flight Secondary Ion Mass Spectrometry (TOF-SIMS) is
generally used to measure the surface composition of materials and
the distribution of particular components on the surface of the
sample (Grams, 2007). Silva et al. (2010) used TOF-SIMS to study
the soot from the Ruth Mullins coal (USA) fire samples and
observed the presence of Li, Na, V, Mn, Fe, Cu, Ti, and As with lesser
amounts of Cr, Ni, Zn, and Ti in the Ruth Mullins soot. Saikia et al.
(2016a, b) also applied TOF-SIMS in their study on nanominerals
and fullerene aggregates of Northeast Indian high sulphur coal and
coal combustion resides. They observed TOF-SIMS peaks at 720
a.m.u (atomic mass units), 840 a.m.u, and 960 a.m.u corresponding
to the fullerene fragments of C60, C70, and C80 (see Fig. 8). To
characterize carbonaceous nanoparticles and ultrafine particles in
coal fly ash samples, Ribeiro et al. (2013) used TOF-SIMS and found
the presence of organic and inorganic compounds including Pb, Al,
and Si in the coal fly ash samples.
3.6. Spectroscopic techniques (Raman, ICP-MS and AAS)
Raman spectroscopic technique is used for nanoscale character-
ization of coal and coal residues. Patel et al. (2012) characterized soot
and compared it with graphite and carbon black and found that the
Raman spectra of carbon black and diesel soot exhibited several
similarities although some distinctive differences were there. Diesel
soot appeared to contain a larger proportion of graphene layer edges
in comparison to carbon black that had a higher proportion of ionic
impurities. Fig. 9 shows the Raman spectra of soot, carbon black and
graphite. Raman spectroscopic technique was utilized for mineral
identification of coal, overburden, and coal fly ash samples by Saikia
et al. (2015). They used standard Raman Spectrum 785 nm to identify
Ti-Oxides and Fe-hydr/oxides in the coal fly ash samples and 532 nm
to confirm the presence of jarosite, sphalerite and quartz in the coal
and coal mine overburden samples. They also identified multi-walled
carbon nano-tubes (MWCN) in the coal fly ash samples using the
standard Raman spectrum at 514 nm and 785 nm (see Fig. 10).
Ulyanova et al. (2014) also studied the fine structure of G and D bands
in various coals by using Raman spectroscopy.
ICP-MS and/or AAS allow the evaluation of average concentra-
tion of trace elements in bulk coal as well as coal combustion res-
idue samples. Utsunomiya et al. (2002) studied the presence of
trace elements in total suspended particulates with the help of
inductively coupled plasma mass spectrometry (ICP-MS) after
extraction of the filters in nitric acid. Their results indicated the
heavy enrichment of the hazardous elements such as Rh, Te, Pd,
etc., along with the trace quantity of uraninite. Saikia et al. (2016a,
b) and Baruah and Khare (2010) also performed AAS analysis of
aerosol samples emitted from use of high sulfur Northeast Indian
high sulfur coals and reported the higher concentrations of trace
 B.K. Saikia et al. / Geoscience Frontiers 9 (2018) 863e875 869

Figure 5. PM2.5 particles measured with AFM. (a) and (b) three dimensional topographic AFM images of similar PM2.5 particles with flat and rough surfaces respectively (on Silicon
substrate); the AFM is able to display the surface roughness with a precision of Angstroms (after Shi et al., 2015).

Figure 6. LTA-XRD patterns of Indian Coal samples showing presence of minerals (after Saikia et al., 2015).

metals such as Pb, Cr, Cu, Zn, Cd, etc., in fine particles than in the
Table 3 coarse mode aerosol.
Quantitative X-ray diffraction data for coal LTA samples (after Saikia et al., 2015). Miller et al. (2017) in their recent study reported that inhaled
Sample ALD Coal ATK Coal nanoparticles accumulate at sites of vascular disease. They had
(10.0% LTA) (19.5% LTA) used gold (Au) nanoparticles to evaluate particle translocation,
Quartz 28.1 25.7 permitting detection by high-resolution inductively coupled mass
Kaolinite 29.8 26.3 spectrometry (ICP-MS) and Raman microscopy. They exposed
Illite 28.1 31.2 healthy volunteers to nanoparticles by acute inhalation and
Pyrite 1.7 2.2
repeated sampling of blood and urine were done, which revealed
Jarosite 4.3 1.8
Sabieite e 8.8 that the gold was present in the blood and urine within 15 min to
Melanterite e 10.1 24 h after exposure. The concentrations were found to be enhanced
Gypsum 7.0 3.5 after inhalation of 5 nm (primary diameter) particles compared to
Bassanite 1.0 0.5 30 nm particles (Miller et al., 2017).
870 B.K. Saikia et al. / Geoscience Frontiers 9 (2018) 863e875
Figure 7. Bulk composition of size classified coal fly-ash particles determined by WD-
XRF analysis (after Linak et al., 2007).
3.7. Toxicity/cytotoxicity assessment of nanoparticles
Nanoparticles having different properties from those of their
bulk materials of the same composition show harmful interactions
with biological systems and may cause toxicity. Nanotoxicology is a
promising science which requires the understanding of the
physico-chemical properties of nanoparticles that have potential
adverse biological effects. Currently, nanoparticle toxicity assess-
ments are mainly focused on in-vitro studies due to the ease in
execution, control and interpretation of the experiments as
compared to the in-vivo. There are various in-vitro cytotoxicity as-
says for the assessment of nanoparticle toxicity such as lactate
dehydrogenase (LDH) leakage, 3-(4,5-dimethylthiazol-2-yl)-2,5-
diphenyltetrazolium bromide (MTT) assay, LIVE/DEAD viability
Figure 8. TOF-SIMS spectra showing C60, C70, and C80 fullerenes and their fragment molecules in feed coal (after Saikia et al., 2016a, b).
test, identification of cytokine/chemokine production, etc. How-
ever, in-vivo toxicity studies are more significant since direct
identification of the effect of nanoparticles toward the human body
can be achieved. But, standard procedures for the evaluation of
nanoparticle toxicity have not yet been outlined (Kong et al., 2011).
Saikia et al. (2016a, b) in their cytotoxicity assessment of ambient
nanoparticles using MTT assay found that increase in the dose of
particulate matter led to the decrease in the percentage of viable
cells by 60%e90%. In addition, they found that nanoparticles are
more toxic to human liver carcinoma cell line compared to human
lung carcinoma cell line and rat muscle cell line.
Nanoparticles generate Reactive Oxygen Species (ROS) and
Oxidative Stress based on their chemical compositions. Pujalte et al.
(2011) revealed that metallic nanoparticles such as ZnO and CdS
significantly increase the cell mortality in dose-dependent manner.
During their study on ROS and intracellular levels of reduced and
oxidised glutathione found that nanoparticles induce stress ac-
cording to their size, composition and solubility. ROS production
and stress induction indicates that nanoparticles also have neph-
rotoxic potential. Therefore, assessment of generation of ROS and
oxidative stress can be a valid mechanism to compare the toxicity of
nanoparticles (Xia et al., 2006a, b).
4. Health risk of ambient nanoparticles
The World Health Organization (WHO) (2011) had compiled air
quality data from 1100 cities in 91 countries and found that resi-
dents living in many urban areas are exposed to persistently
elevated levels of fine particle pollution. Globally, ambient PM2.5
was the fifth-ranking mortality risk factor in 2015 which caused 4.2
million deaths and 103.1 million disability-adjusted-life-years
(DALYs) in 2015, representing 7.6% of total global deaths and 4.2%
of global DALYs (Cohen et al., 2017). China and India each had the
highest absolute numbers of deaths attributable to PM2.5, ac-
counting together, 52% of the total global deaths and 50% of the
DALYs (State of Global Air, 2017). Chronic obstructive pulmonary
disease (COPD) is one of the major causes of human deaths, and it
has been estimated that 328 million people suffer from it (Lopez-
Campos et al., 2016). Epidemiological study revealed that expo-
sure to particulate pollution exacerbates the COPD situation (Ling
and Eeden, 2009). The World Bank in cooperation with the Chi-
nese government reported that about 750,000 people die
 B.K. Saikia et al. / Geoscience Frontiers 9 (2018) 863e875
Figure 9. Raman spectra of graphite, carbon black and diesel soot (after Patel et al.,
2012).
prematurely in China every year from air particulate pollution
(Freeman III and Lu, 2008). The annual safe limit for PM2.5 pollutant
is 10 mg/m3, according to the World Health Organisation (WHO,
2006). Studies reported that the population-weighted mean of
PM2.5 concentration in China is 60.44e71.99 mg/m3 which is three
times higher than the global population-weighted mean, high-
lighting a high health risk (He et al., 2017). The estimated average
PM2.5 concentration for population-weighted exposure increased
from 59 in 1990 to 73 mg/m3 in 2015 in India, which is almost four
times the safe limit (State of Global Air, 2017). Cohen et al. (2017)
approximated that air pollution levels in 2030 in India would
Figure 10. Multi-walled carbon nanotube (MWCN) with comparative detected using the standard Raman spectrum (in red color) at 514 nm and 785 nm of fly ash sample (after
Saikia et al., 2015).
871
need to turn down by 20%, to sustain per-person mortality (a
measure of a number of deaths in the population) at 2010 levels.
Epidemiological studies have reported that air particulate
pollution has been associated with excessive respiratory and car-
diovascular morbidity as well as mortality (Ko et al., 2007; Halonen
et al., 2009; Pan et al., 2014). However, particulate matters patho-
genicity is determined by their origin, size, composition, solubility,
and their ability to generate reactive oxygen species (Xing et al.,
2016). The human health hazards are mainly caused by the ultra-
fine/nanoparticles, because of their greater capacity to penetrate
into the respiratory and cardiovascular systems (Oberdorster et al.,
2005; Murr and Garza, 2009) and increased probability of inhala-
tion due to a longer residence time in the atmosphere (Kittelson,
1998). Due to the large surface area to volume ratio, nano-
particles have higher surface reactivity and have a considerable
effect on their properties (Paur et al., 2011). The association of
hazardous elements in ultrafine/nanoparticles are found to be
higher than that of coarse fraction. In some cases, the concentration
in these particles were found to be 50-times higher than in the fine
and coarse particles (Linak et al., 2007; Sui et al., 2007; Wang et al.,
2008). It was reported that these particles are inhaled deep into the
body leading to high deposition (more than 90%) in the alveolar
region or other respiratory tract regions followed by subsequent
entry into the blood stream (Oberdorster et al., 1995; Castellano
et al., 2009; Marra et al., 2010; Tsai et al., 2012). The molecular
mechanisms of cardiovascular disease caused by nanoparticles
comprises direct toxicity to cardiovascular system or indirect injury
by inducing systemic inflammation and oxidative stress in pe-
ripheral circulation leading to various cardiovascular disease such
as cardiac arrhythmias, hypertension, vascular dysfunction,
myocardial infarction, atherosclerosis, and ischemic stroke (Du
et al., 2016).
5. Energy challenge and coal
Energy is the key of the economic growth, development and
progress of a country. Thus, the challenge is to utilize energy re-
sources, ensure its security and respect environmental sustain-
ability. With global population growth and industrialization, the
energy demand is growing at unprecedented levels and will reach
the peak during 2030 (World Energy Scenarios, 2016). It is expected
872 B.K. Saikia et al. / Geoscience Frontiers 9 (2018) 863e875
Figure 11. Primary energy consumption by fuel (IEO, 2017).
that Energy demand will grow in the next decades by three billion
people currently without access to reliable energy, and an antici-
pated three billion new population by mid-century (Nocera, 2017).
To meet this future global energy need of six billion new energy
consumers, together with existing energy users, the expanded use
of fossil fuel is conflicting with a low-risk climate pathway; and yet,
those fuels often remain the most affordable and widely available.
More than half of our energy comes from fossil fuels such as coal.
Currently, coal provides 41% of global electricity generation, 70% of
steel production and 90% of worlds cement production (World Coal
Association).
According to International Energy Outlook (IEO 2016) coal will
remain the second-largest energy source worldwide-behind pe-
troleum-until 2030 and from 2030 through 2040, it would be the
third-largest after natural gas. According to IEO (2017), coal will
Figure 12. Energy consumption (%) by fuel in 2035 (IEO, 2017).
share 24% of world energy consumption in 2035 with an average
growth rate of 0.2% per year; from 3840 million tons of oil equiv-
alents (Mtoe) in 2015 to 4032 million tons of oil equivalents (Mtoe)
in 2035 (see Figs. 11 and 12). Worldwide consumption of coal
during 2016 was 3732 million tons of oil equivalents (Mtoe) with a
growth rate of 1.9% per annum (IEO 2017). At present, the number
of coal-fired power plants in the world is 1425 with total electricity
generating capacity of 1,219,721 MW. USA has the largest electricity
generating capacity 382,086.8 MW followed by India
(157,832.5 MW) and China (155,506 MW) (Global Energy Obser-
vatory). Therefore, scientists and researchers need to focus on the
development of sophisticated and reliable clean technologies to
continue the use of coal with reduced emission and health hazards
to meet environmental sustainability.
6. Conclusions
The combustion activity of coal emits various pollutants
including nanoparticles/nanominerals. The advanced level charac-
terization of those coal-derived nanomaterials is essential to know
their chemical composition at the nanoscale in order to minimize
their health hazards. The advanced level analytical techniques
including FESEM, HRTEM, AFM and Raman spectroscopy are the
best methodologies to achieve this goal. In coal power plants the
people who work are exposed directly to the coal fly ashes, which
contain nanoparticles as well as hazardous elements. Thus, there
are important incentives for studying the chemistry of nano-
particles and nanominerals emitted from coal combustion activities
to improve its adverse effects on the human health. This article
serves to demonstrate the importance of revisiting the coal com-
bustion activities and human health hazards from the nanoscience
point of view.
Acknowledgments
Authors are greatful to Director, CSIR-NEIST for his keen interest
to our research work. This work was carried out by partial financial
assistance of Ministry of Environment Forest and Climate Change
(MoEFCC), Govt. of India (GPP-0325). Authors express special
thanks to Prof. Santosh and reviewer for their suggestions to
improve the paper.
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Dr. Binoy K Saikia is Scientist in CSIR-North East Institute
of Science & Technology, India and Fellow of Geological So-
ciety of India. Educated in Don Bosco School, Sarupathar
(Assam, India), MSc (Chemistry) and Ph.D. (Chemistry)
from Dibrugarh University (India). Served as Scientific As-
sistant (Tezpur University) and Quality Control Officer (In-
dian Oil). Research field includes coal chemistry, coal
beneficiation, nano-mineralogy, value addition to low-
grade coal, and carbon nanomaterials. Published 65
research papers, 5 book chapters, edited 3 journal special
issues on coal chemistry related topics. Recipient of Dr. R
P Bhatnagar award for Mineral Beneficiation, Mineral Engi-
neering Association of India Award, and IIME-Coal Benefi-
ciation Award.
Ms. Jyotilima Saikia is a Ph.D. student of Academy of
Scientific and Innovative Research, CSIR-NEIST Campus,
Jorhat-785,006 India. B.Sc. (Zoology) from Cotton College
(India) and M Sc in Environmental Science from Tezpur
Central University (2012). Her research interests are ecol-
ogy, environment, environment education, aerosols and
air pollution. Perusing Ph.D. work in air quality and aerosol
emission from coal-based industries. Published 6 research
papers and presented few research papers in national/in-
ternational seminars. Expert in operating air quality moni-
toring equipments.
 B.K. Saikia et al. / Geoscience Frontiers 9 (2018) 863e875
Mr. Shahadev Rabha is Junior Research Fellow in CSIR-
North East Institute of Science & Technology, Jorhat,
Assam-785,006 (India). Educated in Tura Government Col-
lege (Meghalaya, India), B.Sc. (Botany) from Dudhnoi Col-
lege, and M.Sc. (Environmental Science) from Gauhati
University (Assam, India). He has qualified UGC-National
Eligibility Test (NET) in Environmental Science. His
research interests are environmental hazards, air pollution
and aerosol. Currently working in air quality and aerosol
nanoparticles emission from coal combustion activities.
Dr. Luis Felipe Silva Oliveira is Research Director in Cor-
poración Universidad de la Costa, Barranquilla, Atlántico,
Colombia. B.A. in Industrial Chemistry (Universidade do
Sul de Santa Catarina, Brazil), Ph.D. in Earth Science (Uni-
versidad de Santiago de Compostela, Spain) and Post-
doctoral (Institute of Environmental Assessment and Wa-
ter Research, Spain). Published around 183 research pa-
pers, participated in 15 research projects, supervised
11 M. Sc. and Ph.D. students. Associated with journal
editorial board including Science of the Total Environment
(Elsevier). His prime area of research is application, anal-
ysis, fate and risk of nanomaterials in the environment.
875
Dr. Robert B. Finkelman, Research Professor in the
Department of Geosciences at the University of Texas at
Dallas and Adjunct Professor at the China University of
Geosciences, Beijing. Retired in 2005 after 32 years with
the U.S. Geological Survey. Internationally recognized sci-
entist widely known for his work on coal chemistry and as
a leader of the emerging field of Medical Geology. Dr.
Finkelman has degrees in geology, geochemistry, and
chemistry. He has lectured and provided mentorship at
colleges and universities around the world. Most of Dr.
Finkelman’s professional career has been devoted to un-
derstanding the properties of coal and how these proper-
ties affect coal’s technological performance, economic by-
product potential and environmental and health impacts.
Dr. Finkelman is the author of almost 800 publications and has been invited to speak
in more than 50 countries. Dr. Finkelman has served as Chairman of the Geological So-
ciety of America’s Coal Geology Division; Chair of the International Association for
Cosmochemistry and Geochemistry, Working Group on Geochemistry and Health;
founding member and past Chair of the International Medical Geology Association;
President of the Society for Organic Petrology; member of the American Registry of Pa-
thology Board of Scientific Directors and is Past-Chair of the GSA’s Geology and Health
Division. He was a recipient of the Nininger Meteorite Award; recipient of the Gordon
H. Wood Jr. Memorial Award from the AAPG Eastern Section; a Fellow of the Geological
Society of America; and a recipient of the Cady Award from the GSA’s Coal Geology Di-
vision. Dr. Finkelman was also awarded a U. S. State Department Embassy Science
Fellowship for an assignment in South Africa and was a member of a National Research
Council committee looking at the future of coal in the U.S.