TYPE Original Research

PUBLISHED 09 May 2023

DOI 10.3389/feart.2023.1181984

Basic characteristics and

OPEN ACCESS environmental impact of iron ore
EDITED BY
Lijie Guo,
Beijing Mining and Metallurgy
tailings
Technology Group Co., Ltd., China

REVIEWED BY Changlong Wang 1, Jianlin Jing 1, Yang Qi 1, Yongxiang Zhou 2*,

Lin Chi,
University of Shanghai for Science and
Kaifan Zhang 1, Yongchao Zheng 3, Yuxin Zhai 4 and Feng Liu 5
Technology, China 1
Collaborative Innovation Center for Intelligent Regulation and Integrated Management of Water
Shuhua Liu, Resources Jointly Built by Provinces and Ministries, School of Civil Engineering, Hebei University of
Wuhan University, China Engineering, Handan, China, 2Faculty of Architecture, Civil and Transportation Engineering, Beijing
*CORRESPONDENCE University of Technology, Beijing, China, 3State Key Laboratory of Solid Waste Reuse for Building Materials,
Yongxiang Zhou, Beijing Building Materials Academy of Science Research, Beijing, China, 4Technical Center, China Railway
[email protected] Construction Group Co., Ltd., Beijing, China, 5Construction Development Co., Ltd., China Railway
Construction Group, Baoding, China
RECEIVED 08 March 2023
ACCEPTED 06 April 2023
PUBLISHED 09 May 2023

CITATION
Wang C, Jing J, Qi Y, Zhou Y, Zhang K, Introduction: In our study, various test methods were adopted to explore the
Zheng Y, Zhai Y and Liu F (2023), Basic mineralogical characteristics, grindability, particle morphology, particle size
characteristics and environmental impact distribution, and environmental leaching toxicity of iron ore tailings (lOTs).
of iron ore tailings.
Front. Earth Sci. 11:1181984. Methods: The methods include petrographic analysis, X-ray diffraction (XRD),
doi: 10.3389/feart.2023.1181984
scanning electronic microscopy (SEM), synchronous thermal analyzer (DSC-TGA),
COPYRIGHT
electron probe X-ray microanalyser (EPMA), and synthetic precipitation leaching
© 2023 Wang, Jing, Qi, Zhou, Zhang,
Zheng, Zhai and Liu. This is an open- Procedure (SPLP).
access article distributed under the terms
of the Creative Commons Attribution Results: The results show that the used IOTs contained 14.54% iron which was
License (CC BY). The use, distribution or mainly stored in magnetite and pyrite. The content of iron silicate accounted for
reproduction in other forums is 11.82% of the total iron content. Most of it existed in silicate minerals, including
permitted, provided the original author(s)
and the copyright owner(s) are credited grunerite and hornblende. A small amount of iron was contained in biotite, chlorite
and that the original publication in this and augite. Besides, the grindability of lOTs was much better than that of
journal is cited, in accordance with granulated blast furnace slag (GBFS). After grinding for 140 min, the mass
accepted academic practice. No use,
distribution or reproduction is permitted fraction of lOTs particles with the particle size less than 5 um was 44.19%.
which does not comply with these terms. These particles could be used to fill in the voids in the cement-powder-
packed structure. lOTs also contained a large number of submicron and
nanoscale particles.

Discussion: With great strength and environmental friendliness, the composite

cementitious material (CCM) prepared from lOTs can be well applied to the
building material field and environmental remediation.

KEYWORDS

iron ore tailings (IOTs), mineralogical characteristics, grindability, Particle size

distribution, particle morphology, composite cementitious material (CCM)

1 Introduction
Peak carbon dioxide emissions and carbon neutrality are the main development goals of
all countries in the world (Nielsen et al., 2019; Yan et al., 2020). Cement manufacture, as one
of the traditional industries with heavy energy consumption and emission, generates 5%–8%
of the global CO2 emissions per year (Turner and Collins, 2013; Mo et al., 2017). To save
resources and reduce the emission of CO2, various industrious solid wastes have been
adopted to replace cement as the supplementary cementitious material, including granulated

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Wang et al. 10.3389/feart.2023.1181984

TABLE 1 Particle size distribution of IOTs.

Sieve size/mm +1.0 0.45–1.0 0.30–0.45 0.15–0.30 0.074–0.15 0.043–0.074 −0.043

Meter sieve/% 5.61 22.21 13.10 28.69 20.60 5.62 4.17

Cumulative sieve/% 5.61 27.82 40.92 69.61 90.21 95.83 100

sustainable development of the concrete industry. IOTs can be used as

the mineral admixture or alkali-activated cementitious material, and
some can also replace ordinary Portland cement (OPC) (Zhao et al.,
2014). Li et al. (2010) prepared CCM containing 30% clinker, 34%
GBFS, 30% IOTs and 6% gypsum, whose mechanical properties are
equivalent to OPC. Cheng et al. (2016) found that IOTs after
mechanical activation had pozzolanic activity and could be used as
SCM for concrete. Ling et al. (2021) used IOTs as the CCM to prepare
environment friendly ultra-high performance concrete (UHPC),
which facilitated the development of long-term compressive
strength and the improvement of pore structure, thus ensuring the
durability of UHPC. Cheng et al. (2020) prepared concrete with strong
permeability resistance and good freeze-thaw resistance by replacing
part of OPC with IOTs after mechanical grinding. The technology of
preparing high-strength structural materials with IOTs has been
FIGURE 1
studied in recent years. It aims to produce high value-added
SEM image of IOTs.
products from very fine-grained tailings. Zheng et al. (2010)
reported that IOTs can be used to prepare high-strength structural
materials with IOTs content of 70% and compressive strength of more
blast furnace slag (GBFS) (Zhao et al., 2015), fly ash (FA) than 100 MPa. For the high-strength structural material prepared
(Gunasekara et al., 2020), and silica fume (Campos Teixeira with IOTs, superfine grinding technology was further required to
et al., 2020). Some researchers have founded that (Soliman and process some ground IOTs, so as to generate some submicron and
Nehdi, 2013; Ghafari et al., 2016; Meng and Khayat, 2018), adding nanoscale IOTs particles. This process gives full play to the IOTs’
appropriate amount of cementitious material can not only reduce filling effect, bonding effect, and nanometer effect during the
the consumption of cement, but also improve the workability, preparation of building materials. However, there are not many
mechanical properties, volume stability and durability of the research results at home and abroad. In this case, fully utilizing the
concrete. With the wide application of the supplementary refinement effect of ground IOTs is of great importance to
cementitious material (SCM) in the concrete industry, a large systematically study the physical and chemical characteristics and
number of industrial by-products are rapidly consumed. To grindability of IOTs. Lawrence et al. (2003) found that inert quartz
ensure the sustainable development of this industry, it is powder could facilitate the early hydration of OPC, because it could
necessary to find SCM which are more accessible and more promote the process of heterogenous nucleation, and the finer the
economical. quartz powder, the more it attributed to heterogenous nucleation.
Iron ore tailings (IOTs) are the industrious solid waste discharged Therefore, it is concluded that the incorporation of small amounts of
by concentrating mills after processing iron ores and selecting low-activity ultrafine admixtures into UHPC has the potential to be an
“valuable components” (Yao et al., 2020). In China, 600 million important means of improving concrete properties. Besides, for non-
tons of IOTs are discharged every year and the IOTs deposition lime aerated concrete and foam cement products, it is also necessary to
has reached 5 billion tons. However, the utilization efficiency across ultra-finely grind some siliceous raw materials to improve the pore
China is generally low, only 7% (Chen et al., 2021). In this case, large- structure of the products. Therefore, systematically exploring the
scale harmless utilization of IOTs has attracted much attention. physical and chemical characteristics, grindability and basic
Currently, IOTs are mainly used for IOTs recleaning (Wang et al., characteristics of very fine-grained IOTs after grinding is the basis
2018; Yuan et al., 2020; Yuan et al., 2020; Zhai et al., 2020) and mine for the overall utilization of such IOTs in the field of building
filling (Onitiri and Akinlabi, 2017; Qiu et al., 2017; Coura et al., 2021), materials.
or used as the building material (Menders et al., 2019; Li et al., 2020; To solve the above problems, X-ray diffraction (XRD), scanning
Zhang et al., 2022) and soil conditioner (Santana et al., 2020; Castro e electronic microscopy (SEM), synchronous thermal analyzer (DSC-
Silva et al., 2021; Cui et al., 2021). IOTs are rich in SiO2 and Al2O3 TGA), and electron probe X-ray microanalyser (EPMA) were
whose chemical composition is similar to that of cement (Han et al., adopted to explore the mineralogical characteristics of IOTs,
2017) and the physical properties are similar to those of natural sands including the size composition, chemical composition, chemical
(Huang et al., 2013). If IOTs can be adopted to prepare composite phase composition, mineralogical phase composition, and
cementitious material (CCM), it will increase the utilization of IOTs, microstructure. On this basis, SEM and particle size analysis were
reduce its deposition, and lower the production cost, thus ensuring the used to study the particle morphology and particle size distribution

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TABLE 2 Chemical phase composition of IOTs (mass fraction, %).

Classification Magnetite Pyrrhotite Carbonate iron Sulfide iron Hematite and limonite Silicate iron Total
Iron content 1.08 0.36 0.49 0.39 0.40 11.82 14.54

Iron distribution rate 7.43 2.48 3.37 2.68 2.75 81.29 100

TABLE 3 Radioactive test results of IOTs (mass fraction, %).

Sample Specific activity of Internal exposure index External exposure index Test results
radionuclides (Bq·kg−1)
226 232 40
IOTs Ra Th K 0.0 0.1 Qualified

5.1 6.3 113.2

Note: Internal exposure index =CRa/370 + CTh/260 + CK/4,200, external exposure index = CRa/200; uncertainty of measurement results (1σ) ≤20%.

TABLE 4 PDF card number and peak value corresponding to IOTs XRD pattern in Figure 3.

Mineral phase PDF card number 2Theta

Quartz 46–1,045 20.7°, 26.6°, 40.2°, 59.8°, 68.3°

Plagioclase 09–0456 27.9°, 29.8°, 33.9°, 50.1°, 53.2°

Chlorite 29–0854 5.8°, 12.4°, 18.6°, 25.1°, 36.5°, 44.9°, 47.4°, 54.8°

Hornblende 23–1,046 28.5°, 29.1°, 38.4°, 45.7°

Calcite 72–1937 22.8°, 35.7°, 39.4°, 77.6°, 81.4°, 83.8°

Grunerite 17–1,622 9.7°, 32.3°, 55.3°, 66.6°, 67.7°, 75.6°, 79.8°

Biotite 80–1,106 19.5°, 21.9°, 27.2°, 34.6°, 42.3°, 61.4°

Augite 23–1,046 30.3°, 41.7°, 56.2°, 64.6°, 73.4°

Magnetite 88–0315 21.2°, 31.7°, 32.9°, 48.3°

Pyrite 29–0724 27.9°, 29.7°, 33.8°, 50.1°, 53.1°

characteristics of IOTs. Besides, specific surface area (SSA) was 2.2 Test methods
chosen as the evaluation index to compare the grindability of IOTs
and GBFS. Finally, we adopted synthetic precipitation leaching 2.2.1 Sampling method of raw materials
procedure (SPLP) to test the leaching behavior of heavy metals IOTs were taken from the middle of the IOTs pond by cutting
in solidified body, so as to provide technical support for the the vertical section of the pit walls. The cutting depth was 1.2 m and
utilization of IOTs. the total weight of the samples was 640 kg. After mixed thoroughly,
the samples were divided into 8 parts by the method of coning and
quartering, and then sent back to the laboratory. Before the test, each
2 Test materials and methods pile of 80 kg IOTs was further divided into piles of 5 kg by the
method of coning and quartering as the test samples.
2.1 Test materials
2.2.2 Test of grinding characteristics
The IOTs used for our study was provided by Haoyang Mine Firstly, IOTs and GBFS were dried in oven (CS101-3E) at 105°C for
Co., Ltd., in Ling Qiu county in Shanxi Province. The GBFS was 24 h to make moisture content less than 1 wt%, and then ground with
offered by Qian’an Steel Co., Ltd., with the particle size of the SMΦ500 mm × 500 mm 5 kg small ball grinder (W·L−1) at the speed
0.30–2.5 mm and the grain size rate reaching 92.0%. For the of 48 r min−1. The grinding media consisted of several steel balls and a
42.5 OPC, the initial setting time is 118 min and the final setting steel forging. The loading mass of the grinding media should be 100 kg.
time 190 min, which meets the requirements of Chinese National The steel balls added up to 40 kg, in which the Φ70 mm balls took up
Standard GB 175-2007 Common Portland Cement. Phosphogypsum 19.7%, the Φ60 mm balls 33.1%, the Φ50 mm balls 29.6%, and Φ40 mm
(PG) is a kind of gray powder whose particle size is between 5 μm balls 17.6%. The Φ25 mm × 30 mm steel forging weighed 40 kg. The
and 150 μm, density is 2.56 gˑcm−3, and the SSA is 640 m2ˑkg−1. The grinding periods were chosen at 20 min, 40 min, 60 min, 80 min,
main mineral components are CaSO4·2H2O and CaSO4·1/2H2O. 100 min, 120 min and 140 min in order to obtain different SSA.

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Wang et al. 10.3389/feart.2023.1181984

analyzer). The XRD pattern was obtained by a D/Max-RC

diffractometer (Japan) with Cu-Kα radiation, voltage of 40 kV,
current of 150 mA and 2 θ scanning ranging between 10° and 90°.
And the wavelength was 1.5406 nm. SEM observation was performed
to analyse the mineral phase and the hydration products of the paste
™
samples using a Zeiss SUPRA 55 scanning electron microscope
coupled with a Be4-U92 energy spectrum. Leica DM4 P polarizing
microscope was adopted for the petrographic analysis of IOTs.
Netzsch STA 409 was used to heat the solidified powder from
25°C to 1,000°C at the heating rate of 10°Cˑmin−1 under N2, so as
to explore the thermal decomposition rule of IOTs. IOTs were
scanned with the JXA-8100 Electron probe microanalyzer (EPMA)
to analyze the surface elements and their contents. SPLP was
conducted to test the leaching behavior of heavy metals in
solidified body, thus confirming the environmental safety. During
SPLP, the leach liquor was prepared by adding 60%/40% (mass
fraction) of sulfuric acid/nitric acid and diluting appropriately with
deionized water, in order to adjust the pH to 4.20 ± 0.05 (Li and Chi,
2017) The leach liquor and solidified powder (0.075 mm) were mixed
according to the ratio of 20:1, and shaken for 18 h in a gyrate shaker.
Then, the screened mixture (0.45 μm) was put into Prodigy
7 Inductively coupled plasma emission spectrometer (ICP-OES) to
analyze the concentration of Cr, Ni, Cu, Cd, Pb, Zn, As, and Hg (Zhu
et al., 2017).

3 Results and discussion

3.1 Mineralogical properties of IOTs
3.1.1 Physicochemical properties of IOTs
The square hole screens with the screen size of 1.0 mm,
0.45 mm, 0.30 mm, 0.074 mm and 0.043 mm were used for the
screen analysis of IOTs. The analysis results are displayed in Table 1.
It can be seen that IOTs have large particle size, mainly between
0.074 mm and 1.0 mm. The grain size rate reaches 84.60%. Figure 1
shows that most of the IOTs are the particles with the size of tens of
microns to hundreds of microns, and they are irregular or angular
particles. As for the chemical composition of IOTs, inorganic
components are the main content. The Fe2O3+FeO content is
19.59% and total Fe (TFe) content reaches 14.54%, which exceeds
FIGURE 2 the minimum grade of some iron ores mined in China. In the
The microstructure of IOTs. (A) Hbl-hornblende (single tailings, the content of SiO2 is 54.41%, Al2O3 7.99%, CaO+MgO
polarizing light); (B) Gru-grunerite (orthogonal slice light); (C) Qz-
12.41%, and Na2O+K2O 1.81%. For the harmful elements, S content
quartz (single polarizing light); (D) Aug-augite (single polarizing light);
(E) Bt-biotite (single polarizing light); (F) Cal-calcite (orthogonal is as high as 0.104% while P content is relatively low (0.052%). The
slice light); (G) Pl-plagioclase (orthogonal slice light); (H) Chl-chlorite contents of other harmful elements are small, too. Among the
(single polarizing light); (I) Mag-magnetite (reflected light) and Py-
components of IOTs, the ratio of basic oxides to acid oxides is
pyrite (reflected light).
(CaO+MgO)/(SiO2+Al2O3) = 0.199 < 0.5, indicating that IOTs are
acid tailings. To determine the occurrence state of iron in the
samples, iron chemical phase analysis was conducted. The results
2.3 Property characterizations are shown in Table 2. We can see that the iron in IOTs is mainly in
the form of silicate iron and the distribution rate of iron is 81.29%.
According to Chinese National Standard GB/T 19,077- Then come the magnetite and carbonate with the iron distribution
2016 Particle size analysis - Laser diffraction methods, the particle rate of 7.43% and 3.37%, respectively. In this case, the IOTs used for
size distribution of ground IOTs were analyzed through MASTER our study are the tailings with high silicate iron. The radioactivity
SIZER 2000 (a laser particle size analyzer with the analysis range of index of the IOTs meets the requirement of Chinese National
0.02 μm–2,000.00 μm) with ethanol as the dispersant. The SSA of Standard GB/T 6566-2010 Limits of radionuclides in building
IOTs was measured by SSA-3200 (a dynamic specific surface area materials (See Table 3).

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Wang et al. 10.3389/feart.2023.1181984

FIGURE 3
XRD pattern of IOTs.

Quartz. It is one of the main rock-forming minerals. With the

granular structure, it belongs to the stable mineral and is resistant to
weathering (Figure 2C).
Augite. It is black green. See the two sets of pyroxene-type
cleavage joints which are nearly orthorhombic in Figure 2D.
Biotite. It is in the form of pseudohexagonal plate and fully
cleavaged. It is brown with a slightly greenish tinge. There are
opaque darkening edges around its phenocryst (Figure 2E).
Calcite. It has rhombic cleavage and paralleled twin striations.
As the main mineral in calcareous rocks, it is widely distributed in
sedimentary and metamorphic rocks (Figure 2F).
Plagioclase. With polysynthetic twin and complete cleavage, it is
a tabular or columnar crystal (Figure 2G).
Chlorite. It has a layered structure with different shades of green.
The color is getting darker with the increasing iron content
FIGURE 4
(Figure 2H).
DSC-TGA curve of IOTs.
Magnetite and pyrite. With the cataclastic structure, they exist in
the form of microgranular particles with the size of 3–4 μm
(Figure 2I). They are filled with gangue minerals and are
extremely refractory. Pyrite is pale yellow and it is a ubiquitous
3.1.2 Structure and composition of IOTs mineral that can occur in a variety of deposits. Magnetite is a
3.1.2.1 Petrographic analysis brownish-gray mineral with no pleochroism.
To determine the material composition, structure, mineral
composition, particle size, embedded features, and symbiotic 3.1.2.2 XRD analysis
relationship of IOTs, a polarizing microscope was used to To determine the phase composition of IOTs, XRD was
observe the optical property differences of different minerals, adopted to analyze the samples. The results are shown in
thus identifying the minerals. The observed results are shown in Figure 3.
Figure 2. From Figure 2, we can see that the metallic minerals According to the XRD results in Figure 3, the main mineral
identified in IOTs include pyrite and magnetite. There are 8 kinds of components of IOTs are quartz, plagioclase, chlorite, biotite,
gangue minerals (high content: quartz, hornblende, grunerite, and hornblende, grunerite, augite, calcite, magnetite, and pyrite. The
plagioclase; low content: biotite, chlorite, calcite, and augite). Here corresponding PDF card number and peak value are listed in
are the characteristics: Table 4. Based on the material balance principle (Huang et al., 2019;
Hornblende. With strong pleochroism and absorbency, it is one Ren et al., 2021; Yu et al., 2021), we used the linear programming
of the main rock-forming minerals in igneous rocks and program LINPRO (Faghihi et al., 2019; Bam et al., 2020) to calculate the
metamorphic rocks. The color is dark green (Figure 2A). content of each mineral phase: quartz (40%), hornblende (21%),
Grunerite. It is a dark greenish-brown and columnar mineral grunerite (21%), plagioclase (9%), and others (9%). In hornblende
with complete cleavage. It can turn into limonite and mainly exists (Al3.2Ca3.4Fe4.02K0.6Mg6NaSi12.8O44(OH)4), the iron content is 12.73%,
in transmutative iron-bearing rock series (Figure 2B). while the iron content is 39.03% in grunerite (Fe7Si8O22(OH)2). Thus,

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FIGURE 5
EPMA images of IOTs.

the total iron content of amphibole accounts for 10.87% of the IOTs. of IOTs, with a wide temperature range from 52°C (initial weight loss
According to the chemical phase analysize results in Table 2, the content temperature) to 780°C (final weight loss temperature) and above. In
of silicate iron in IOTs is 11.82%, which indicates that most of the iron the TGA curve, there are three obvious weight loss phases during the
of IOTs exists in silicate mineral amphibole. Only a small amount of heating of IOTs.
iron is contained in biotite, chlorite, and augite. In the first phase, the temperature range is 52°C–175°C and the
weight loss rate is 0.28%. This phase mainly corresponds to the
3.1.2.3 DSC-TGA analysis removal of the physically absorbed water in IOTs. Since the IOTs
Figure 4 is the DSC-TGA curve of IOTs. It can be seen that with used for the analysis have been dried at 100°C, a large amount of
the increase of temperature, the TGA curve shows a decline trend. It water in IOTs has been removed. The endothermic peak of 76.5°C in
means that continuous weight loss occurs during the heating process this temperature range represents the removal of the remaining

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TABLE 5 Quantitative analysis results of chemical elements detected by EPMA. lower left corner of the scanned area. In the scanned area, the Ca
content is also low while the Na content is relatively high which is
Chemical element Mass ratio (%) Atomic ratio (%)
scattered in IOTs particles. The reason is that there are plagioclase-
Si 16.622 37.075 type minerals in IOTs (Figure 2G). Mg is concentrated near the
Ca 4.523 7.851
middle of the scanned area. The content of Ti is not high. Fe is
concentrated in two brighter regions in the CP secondary image,
K 0.243 0.365
where the O content of larger particles is higher, indicating that they
Na 0.921 2.558 may be magnetite particles (Figure 2I). Al is distributed dispersively.
However, the Al content is relatively higher in the particles containing
Ni 0 0
Al and K. Mn and Ni are present in trace amounts in the scanned area,
S 0.239 0.341 and the content of Mn is slightly higher than that of Ni. The Si content
Mg 4.256 16.36 is high, and the color intensity is higher in the scanning area (red and
pink). Considering the distribution of O, we can find that the scanned
Ti 0.099 0.121
area has a high content of quartz (Figure 2C). The two harmful
Fe 8.937 16.112 elements, P and S, are distributed sporadically in the scanned area and
their contents are low. The quantitative analysis results of the elements
Al 5.559 9.52
in Table 5 also confirm the EPMA analysis results, which are similar to
Mn 0.206 0.22 the analysis results in Table 6.
P 0.031 0.054

O 3.11 9.423
3.2 Grinding characteristics of IOTs
Total 44.746 100
3.2.1 Grindability
The grinding energy consumption of GBFS is a well-known
parameter in the field of building material. The energy consumption
physically adsorbed water. In the second phase, the temperature required for the one-time treatment of GBFS powder with the SSA of
range is 175°C–400°C and the weight loss rate is 0.36%. A wide and 400 m2 kg−1 or more is about 80 kW h·t−1 for a large industrial ball
flat exothermic peak appears at 307.9°C, mainly referring to the mill. However, that for the advanced vertical mill is 50–60 kW h·t−1.
exothermic process of magnetite and pyrite at around 350°C. During Therefore, in our test, the grindability of GBFS was used as a
this process, part of magnetite is oxidized to hematite and pyrite is reference to study the grindability of IOTs. The IOTs and GBFS
oxidized to magnetite. In the third phase, the temperature range is were ground in different batches by the SMΦ500 mm × 500 mm
400°C–780°C and the weight loss rate is 0.32%. A sharp exothermic experimental ball mill, and we compared the difference in the SSA of
peak appears at 466.7°C while an endothermic peak occurs at their powder after grinding for the same time. Figure 6 shows the
576.4°C. The exothermic peak mainly corresponds to the SSA of IOTs and GBFS at different grinding time.
exothermic process where part of magnetite in IOTs is oxidized It can be seen that the grindability of IOTs is much better than
to hematite at the temperature between 400°C and 500°C. The that of GBFS. Specifically, after grinding for 70 min, the SSA of GBFS
endothermic peak refers to the endothermic process at the curie is 400 m2 kg−1 while that of IOTs is 756 m2 kg−1. After grinding for
point temperature of magnetite (around 560°C) and the 120 min, the SSA of GBFS is 515 m2 kg−1 while that of IOTs powder
endothermic process where α-quartz in IOTs is transformed into is 1,041 m2 kg−1. Besides, the SSA increase rate of IOTs is greater
β-quartz. The DSC-TGA analysis of the dried IOTs is basically than that of GBFS. In other words, with the extension of grinding
similar to the iron phase analysis of IOTs. time, the SSA increment of IOTs is greater than that of GBFS. This is
represented by the increasing slope of the curve of IOTs powder in
3.1.2.4 EPMA analysis Figure 6. It further confirms that IOTs have better grindability
Figure 5 shows the EPMA analysis results, including the compared to GBFS.
distribution of K, Ca, Na, Mg, Ti, Fe, Al, Mn, S, Ni, P, and O. Figure 7 shows the SEM images of IOTs and GBFS after grinding
The element names are shown below each image. The scanning for 120 min. It can be directly seen that the fineness of IOTs at the
result of each element is represented with a colored tape, and the same grinding time (Figure 7A) is much smaller than that of GBFS
color density increases from bottom to top. In Figure 5, CP means (Figure 7B). The SSA of IOTs after grinding for 120 min and
the secondary electronic image. 140 min are 1,041 m2 kg−1 and 1,059 m2 kg−1, respectively. Then,
Figure 5 shows that there is no Ni in the scanned area. The the SSA of IOTs remains relatively stable with the increase of
content of K is low, and most of it exists around the particles in the grinding time. So it is of little significance to extend the grinding

TABLE 6 Chemical composition of IOTs (mass fraction, %).

Composition SiO2 Al2O3 Fe2O3 FeO MgO CaO Na2O K2O SO3 P2 O 5 LOI
Content 54.41 7.99 8.94 10.65 5.85 6.56 1.18 0.63 0.26 0.12 3.41

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materials (Jindal, 2019; Sharma et al., 2022). The physical filling

effect of mineral admixtures can effectively improve the
compactness and fluidity of the fresh cement slurry, and reduce
the porosity of the hardened slurry, thus improving its mechanical
properties (Jiang et al., 2020; Ji et al., 2021). To give the full play of
the physical filling effect, the mineral admixtures must have a
suitable particle size and reasonable particle size distribution.
Therefore, the core problem is to use the close packing principle
of particles to obtain a dense filling structure of cement-based
materials (Sun and Zhang, 2021; Wang et al., 2021). Chen et al.
(2004) found that there are a large number of voids less than 5 μm in
the cement powder packed structure, and adding into the powder
with the particle size less than 5 μm could fill the voids among the
cement particles, thus obtaining a closely packed structure. Figure 8
shows that, the particles with the size of less than 5 μm account for
around 46.37% in the IOTs ground for 100 min, while those account
FIGURE 6
for 51.75% in the IOTs ground for 140 min. With a great number of
SSA of IOTs and GBFS at different grinding time.
particles whose size is less than 5 μm, ground IOTs can be used to fill
the voids in the cement powder packed structure, so as to make the
structure more closed. The closely packed structure can reduce the
time to improve the fineness of the powder after grinding for water-cement ratio of the initial slurry, and significantly improve the
140 min. mechanical properties and durability of the final cement-based
materials (Lange et al., 1997; Peng et al., 2009). The reactive
3.2.2 Particle size distribution of IOTs powder concrete with high strength and durability is also
A laser particle size analyzer (LPSA) was used to analyze the produced based on this principle (Richard and Cheyrezy, 1995).
particle size distribution of IOTs at different grinding time. The It can be expected that adding such inert particles can reduce water
results are shown in Table 7; Figure 8. It can be seen that with the to a certain extent. The research team’s previous research on using
extension of grinding time, the particle size distribution range of IOTs as mineral admixtures has shown that due to IOTs (Zhao et al.,
IOTs narrows and gradually concentrates towards the small particle 2016; Wu et al., 2018). Most of the powder particles themselves exist
size value. When the grinding time increases from 20 min to in the form of polygonal irregular shapes. Compared to GBFS, the
140 min, D50 (median diameter) of IOTs powder decreased from “interlocking function” between particles is stronger when they exist
12.51 μm to 3.31 μm, and D90 decreased from 40.61 μm to 17.16 μm inside the mortar specimen. Under the standard curing conditions
D90 represents the particle size when the cumulative particle size of high water binder ratio (0.48) and low water binder ratio (0.34) for
distribution percentage reaches 90%. At the early stage of grinding, 180 days, the main role of IOTs in the mortar blocks is the physical
the particle size distribution of IOTs powder changed greatly. After filling effect, regardless of the initial or late hydration period. No
grinding for 120 min, D50 and D90 only changed slightly with the secondary hydration reaction of IOTs as mineral admixtures has
increase of time, corresponding to the change of SSA. been found. However, for the cementitious material products
In the concrete industry, mineral admixtures are an important accepting high temperature steam or autoclave curing and mixed
component to improve the performance of concrete. Especially, they with ground IOTs, a large amount of crystalline silica in the IOTs
have better physical and chemical filling effects on cement-based can participate in the hydration reaction at a high temperature. In

FIGURE 7
SEM images of IOTs and GBFS after grinding for 120 min (A) IOTs; (B) GBFS.

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Wang et al. 10.3389/feart.2023.1181984

TABLE 7 Characteristic particle size of IOTs at different grinding time. and a certain number of submicron particles less than 1 μm appear.
Besides, they have arc-shaped edges, indicating the good sphericity.
Grinding time/min D50/μm D90/μm
This shows that with the extension of grinding time, the sphericity of
20 12.51 40.61 IOTs particles and the smoothness of the edges are both increased.
60 8.94 27.27
In Figure 9D, flocculent weak agglomeration appears for the
particles ground after 140 min. It can be clearly seen that
80 7.66 23.85
nanoscale particles exist in the IOTs after ultrafine grinding.
100 4.41 20.92 Their morphology tends to be spherical and the edges are
smooth. With large surface energy, these nanoscale particles can
120 3.53 17.68
agglomerate each other, or can be adsorbed on the surface of coarser
140 3.31 17.16 particles. Therefore, ultrafine grinding of IOTs can not only generate
a large number of submicron particles, but also obtain nanoscale
particles with good sphericity. Figure 9E shows the particle size
interval distribution curve of IOTs at different grinding time. As can
be seen from the Figure 9E, as the grinding time progresses, the
average particle size of IOTs also presents a regular decline with the
change of grinding time. The range of particle sizes of IOTs with
peak particle sizes gradually shifts towards fine particle sizes, while
the peak particle sizes gradually decrease, gradually concentrating in
the direction of small particle sizes, and the proportion of fine
particle size components in the particle group gradually increases.
After 20 min of grinding, the particle size decreases rapidly. With the
extension of grinding time, the particle size of IOTs decreases gently.
When grinding for 100–140 min, the particle size decreases slowly,
indicating that there is a weak agglomeration phenomenon during
mechanical grinding of IOTs. At this point, the weak bond is broken,
making it more difficult for the stronger high-energy bond to break,
increasing the fracture energy, and therefore reducing the grinding
efficiency. This can also effectively illustrate the change rule in
FIGURE 8 Figures 9A–D. The spherical shape of FA is one of the reasons why it
Cumulative distribution curves of IOTs at different grinding time.
plays an important role in the concrete industry. Adding spherical
FA to concrete can effectively improve the fluidity of slurry, thereby
improving the workability and mechanical properties of concrete.
this situation, the ground IOTs can not only realize physical filling, Therefore, when the IOTs after ultrafine grinding are applied as an
but also further exert its chemical filling effect. Meanwhile, Figure 6 inert filling component to concrete, the good particle sphericity will
shows that to obtain the GBFS with the SSA of 400–500 m2 kg−1 contribute to exerting the filling effect. In addition, with the rapid
which is more widely used in the field of building material, the GBFS increase of lattice distortion and surface energy of some submicron
needs to be ground by an experimental ball mill for 90–120 min. and nano IOTs particles generated by grinding, the ground IOTs
However, at least 100 min is required to obtain the IOTs, 40% of have certain volcanic ash reactivity. When they are applied as
whose particles have a size of less than 5 μm. It can be preliminarily mineral admixtures to cement-concrete systems, these submicron
predicted that when a large industrial mill is used, the energy and nanoparticles can undergo volcanic ash reaction, which will
consumption for grinding IOTs is close to that for grinding further improve the strength and durability of concrete (Cheng et al.,
commonly used GBFS. This indicates that, in terms of 2020; Gunasekara et al., 2020; Ji et al., 2021).
technology requirement and energy consumption, it is feasible to
apply the ground IOTs with a large number of ultrafine particles to
the field of concrete. 3.3 Environmental impact of IOTs
Figure 9 shows microstructure and particle size distribution of
IOTs at different grinding time. In Figure 9A, most of the coarse At present, the application in the field of concrete is one of the
particles in IOTs ground for 20 min have irregular shapes. The size focuses on IOTs research, while the leaching of heavy metals is still
of some IOTs particles rapidly decreases to less than 5 μm after less concerned. As the iron and steel waste, IOTs contain heavy
grinding, while some large particles are about 15 μm in size and they metals including Cr, Zn, Cu, Ni, Pb, Cd, Hg, and As (Zhang et al.,
are mainly flaky and irregular polygonal blocks with sharp edges and 2018; Young et al., 2021; Sarathchandra et al., 2022), which are easy
corners. Figure 9B shows that after grinding for 60 min, the large to migrate and transform in the environment. This poses a potential
particles in the IOTs are still clearly visible with the size reduced to threat to the environment. In our test, SPLP was conducted to
about 10 μm. The edges and corners of the particles tend to be separately test the leaching toxicity of each raw material for
smooth, and the irregularity decreases. From Figure 9C, we can find preparing the CCM and that of the CCM hardened OPC paste.
that most of the IOTs particles after grinding for 100 min have the The raw materials included IOTs, OPC, and PG. The IOTs with the
size of below 10 μm. The powder particles are significantly refined, grinding time of 40 min and the SSA of 658 m2 kg−1 were assumed as

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Wang et al. 10.3389/feart.2023.1181984

FIGURE 9
Microstructure and particle size distribution of IOTs at different grinding time. (A) 20 min; (B) 60 min; (C) 100 min; (D)140 min and (E) Interval distribution curves.

TABLE 8 The leaching concentrations of heavy metals from some raw materials and mortar blocks of CCM after 28-day curing age (μg/L).

Materials Cu Pb Zn Ni Cd Cr As Hg
IOTs-1 18.42 0.77 54.47 0.6275 0.3641 0.793 2.1047 —

IOTs-2 20.23 0.92 72.14 1.1384 0.4818 0.964 2.9382 —

OPC 5.637 1.36 30.39 0.4538 0.5421 0.948 1.8525 0.04356

PG 26.161 0.16 37.71 0.0110 0.0908 1.176 0.6716 0.00224

CCM-1 12.368 0.52 33.93 0.5702 0.3518 0.684 1.3845 0.02711

CCM-2 16.581 0.84 46.82 0.9428 0.4903 0.825 1.6604 0.03326

Limiting value 100 5 100 5 1 5 5 0.1

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Wang et al. 10.3389/feart.2023.1181984

IOTs-1. Those with the grinding time of 80 min and the SSA of containing IOTs have good application prospects in the field
887 m2 kg−1 were assumed as IOTs-2. The mix proportion of CCM of building materials and environmental remediation.
was OPC: IOTs: PG=27:12:1. The CCM prepared with IOTs-1 was
denoted as CCM-1, while that prepared with IOTs-2 was
represented by CCM-2. The two kinds of CCM are the samples Data availability statement
with better performance and more application value. The results are
shown in Table 8. Although the leaching of heavy metals is detected The original contributions presented in the study are included in
from the raw materials in an acidic environment, the leaching the article/supplementary material, further inquiries can be directed
concentrations are still far lower than the standard evaluation to the corresponding author.
value stipulated in Chinese National Standard GB 5085.3-2007.
In addition, the hydration and solidification of CCM can further
reduce the risk of heavy metal leaching. Therefore, it is expected that Author contributions
even if IOTs are incorporated in the CCM system, the
environmental risk coefficient of its application is still very low, JJ proposes method and writes manuscript; CW and YXZ propose
compared to the limit value specified in Chinese National Standard and participates in design research and reviews paper; YQ, KZ, YCZ,
GB 5085.3-2007. YuZ, and FL participate in design research and reviews paper. All the
authors approved the final version of the manuscript.

4 Conclusion
Funding
This study systematically explores the physical and chemical
properties, grindability, and basic characteristics of extremely fine The authors gratefully acknowledge financial support by the
particle iron ore tailings (IOTs), providing the basis for the National Key Research and Development Program of China (No.
comprehensive utilization of such IOTs in the field of building 2021YFC1910605), the Natural Science Foundation of Hebei
materials. The following conclusions are obtained: Province (E2020402079), State Key Laboratory of Solid Waste
Resource Utilization and Energy Conservation (SWR-2023-007),
1) The IOTs used for our study contain 14.54% iron and 54.41% Science and Technology Research and Development Plan of China
SiO2. The main ferrous metal minerals are magnetite and pyrite. Railway Construction Group Co., Ltd., (No. 22-11b, 22-14b),
The content of silicate iron accounts for 11.82% of the total iron, Handan Science and Technology Research and Development
most of which are found in silicate minerals, including grunerite Program (21422111260). The funder was not involved in the
and hornblende. A small amount of iron exists in minerals such study design, collection, analysis, interpretation of data, the
as biotite, chlorite, and augite. writing of this article or the decision to submit it for publication.
2) IOTs have good grindability which is much better than that of
GBFS. After grinding for 120 min, the SSA of GBFS is
515 m2ˑkg−1 while that of IOTs powder reaches 1,041 m2ˑkg−1. Conflict of interest
From that time on, the SSA of IOTs basically remains stable even
if the grinding time is extended. Authors ZYu and LF were employed by China Railway
3) The ultrafine grinding of IOTs can generate a lot of particles Construction Group Co. Ltd, China.
with the size of less than 5 μm which can fill in the voids in the The remaining authors declare that the research was conducted
cement powder packed structure. After grinding for 140 min, in the absence of any commercial or financial relationships that
these particles account for 44.19% in the IOTs. The ultrafine could be construed as a potential conflict of interest.
grinding of IOTs can also generate submicron and
nanoparticles with good sphericity. Therefore, IOTs after
ultrafine grinding are expected to be applied to the cement- Publisher’s note
concrete industry, which is of great significance to improve the
material property. All claims expressed in this article are solely those of the authors and
4) According to the environmental risk assessment, the CCM do not necessarily represent those of their affiliated organizations, or
containing IOTs has low leaching toxicity. Its environmental those of the publisher, the editors and the reviewers. Any product that
risk coefficient is lower than the limit stipulated in Chinese may be evaluated in this article, or claim that may be made by its
National Standard GB5085.3-2007. Therefore, the CCM manufacturer, is not guaranteed or endorsed by the publisher.

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