Wang Et Al. 2022

Case Studies in Construction Materials 17 (2022) e01422
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Case Studies in Construction Materials

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Short communication
Utilization of fly ash as building material admixture: Basic

properties and heavy metal leaching
Chao-qiang Wang a, b, c, Ke Liu a, De-ming Huang a, Qiao Chen c, *, Min-jie Tu d,
Kai Wu e, Zhong-he Shui f, *
a
School of Material Science and Engineering, Chongqing Jiaotong University, Chongqing 400074, China
b
Chongqing Institute of Modern Construction Industry Development, Chongqing 400066, China
c
Chongqing Institute of Green Intelligent Technology, Chinese Academy of Sciences, Beibei, Chongqing 400714, China
d
CSCEC strait construction and development co.,ltd, Fuzhou 350015,China
e
Key Laboratory of Advanced Civil Engineering Materials (Tongji University), Ministry of Education, Shanghai 201804, China
f
State Key Laboratory of Silicate Materials for Architectures (Wuhan University of Technology), 430070, China
A R T I C L E I N F O A B S T R A C T
Keywords: The potential harm to the environment and human body caused by heavy metal elements such as
Fly ash Cd, Cr, Pb in fly ash cannot be ignored. In this study, microscopic analysis and heavy metal hazard
Heavy metal analysis were performed on fly ash samples from four regions in China. XRF, XRD, FTIR and SEM/
Leaching
EDS test results showed that the main components of fly ash are Si, Ca, Al, O and other elements,
Admixture
and the main mineral components are mullite, quartz and amorphous aluminosilicate. The results
Ecological risk assessment
showed that six heavy metal elements of As, Hg, Cd, Cr, Pb and Ni from the EDS test charts of
these four types of fly ash. Based on the detection of the six heavy metal contents in fly ash, the
results of the pollution evaluation of these four types of fly ash were consistent according to the
single factor index, potential ecological risk index, and index of geo-accumulation. This indicated
that Cd/Hg in FA 1, FA 2 and FA 3 has a high risk of environmental pollution. In the meantime, Cr
and As in fly ash need to be controlled, because the human health risk assessment showed that
they will bring carcinogenic risk to the human body through oral intake. The study on the
migration law of characteristic heavy metals by taking FA 4 as an example showed that the
leaching rate of Cr, Hg and Cd decreased with the increase of grinding particle size. Among the
three characteristic heavy metals, mercury had the highest leaching rate. From the XPS detection
results of FA 4, it was found that the valence states of these three heavy metals in FA 4 are Cr3+,
Cr6+, Cd2+, Hg2+ respectively. These harmful heavy metal ions gradually enter the deep soil and
groundwater through osmosis. Finally, based on the control model constructed in this study, the
contents of these three heavy metals in fly ash in different application scenarios were limited.
1. Introduction
Fly ash is a kind of solid waste discharged from coal-fired power generation in thermal power plants, and it is also a clay-like
pozzolanic material [1]. In China, the annual output of fly ash reaches 800–900 million tons. Except for the utilization of second
ary resources, the cumulative stockpile of fly ash in 2021 will be 3.1 billion tons [2]. A large amount of fly ash occupies land, pollutes
* Corresponding authors.
E-mail addresses: chenqiao@cigit.ac.cn (Q. Chen), 438516618@qq.com (Z.-h. Shui).
https://doi.org/10.1016/j.cscm.2022.e01422
Received 23 June 2022; Received in revised form 12 August 2022; Accepted 19 August 2022
Available online 22 August 2022
2214-5095/© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
C.-q. Wang et al. Case Studies in Construction Materials 17 (2022) e01422
water sources, and can cause huge damage to the environment. Fully understanding and utilizing fly ash is the key to promoting the
sustainable development of the power industry and related industries. In recent years, the comprehensive utilization of fly ash has
attracted more and more attention, which can not only reduce the land occupation, but also alleviate the pollution to the ecological
environment, and at the same time can create considerable economic benefits. Because fly ash has special physical and chemical
properties and is rich in various useful components, it is widely used in construction, chemical industry, agriculture and environmental
protection and other fields [3]. However, fly ash contains heavy metals to varying degrees. Due to the poor mobility of heavy metals
and inability to degrade, heavy metals accumulate in the ecosystem and increase toxicity, leading to the degradation of the ecosystem
and affecting human health through the food chain [4]. Over time, the pollution of heavy metals such as Pb, Cr, Cd, Hg, As and other
heavy metals to the soil was caused by excessive accumulation of heavy metals in fly ash and surrounding soil [5]. At present, fly ash is
the most widely used in the building materials industry. The first step of this study is to review other researchers’ research results on
the use of fly ash and the heavy metals in fly ash. In the second step, the basic properties of fly ash samples from four regions in China
were investigated experimentally, and the hazard evaluation of the characteristic heavy metals was carried out by means of multiple
methods. The third step is to select a fly ash to study the valence state, leaching law and migration characteristics of high-risk heavy
metals in it. Finally, according to the hazard evaluation results and for different fly ash usage scenarios, the risk content of its char
acteristic heavy metals is controlled.
2. Utilization of fly ash in building materials and it’s heavy metals
With the gradual deepening of related research, fly ash has become a widely used resource. At present, it is mainly used in industrial
fields such as building materials [6], chemical industry [7], sewage and flue gas treatment [8,9], etc. It is also used in agricultural fields
such as soil improvement [10] and fertilizer production [11]. In addition, the research on the high value-added utilization of fly ash has
gradually deepened, such as the extraction of hollow microbeads, magnetic beads, alumina from fly ash. Among all the resource
utilization methods of fly ash, it is the most widely used for building materials, and this method consumes a huge amount of it.
2.1. Application of fly ash in cement
Fly ash contains active substances with pozzolanic effect (such as CaO, SiO2 and Al2O3, etc.), so it can be used as a mixed material
and raw meal for the production of cement or as a concrete admixture instead of cement. When fly ash is mixed into cement, in addition
to the homogenization effect and lubrication effect brought by its own shape, the hydration products of fly ash can also fill the gaps in
the material, thereby increasing the strength and improving the impermeability [12]. The study of Fami et al. [13] showed that the
addition of lime and fly ash significantly reduced the permeability coefficient of cement-soil after standard curing for 28 days. The
specific performance is that the use of lime-activated fly ash can better fill the cement-soil through the hydration reaction process. The
pores in the fly ash cement soil make the structure of the fly ash more compact. Because the hydration reaction rate of fly ash is slower
than that of ordinary Portland cement, most fly ash cements have the disadvantage of low early strength. Zhang et al. [14] analyzed the
effect of fly ash incorporation on the cement hydration process by detecting the change of resistivity in the cement system. The results
showed that fly ash did not participate in the hydration reaction in the early stage of cement hydration, and was only used for filling
material, the fly ash particles dispersed in the cement slurry are hydrated to form hydrated gel after curing for 7–28 days. Zhao et al.
[15] found that the use of ultra-fine fly ash can overcome the shortcomings of low early strength of ordinary fly ash cement. In addition
to indirectly increasing the water-cement ratio, ultra-fine fly ash can reduce the aggregation of cement particles and make the dis
tribution of cement particles better. Fly ash provides a nucleation core for hydration product generation, which better promotes
cement hydration. The research results of Duan et al. [16] showed that after 3 days standard curing, the compressive strength of
ultrafine fly ash cement can reach 18–23 MPa, which is more than 240% of the strength of ordinary fly ash cement.
2.2. Application of fly ash in concrete
The addition of fly ash has a great influence on the fluidity, mechanics and anti-carbonation properties of concrete. Behl et al. [17]
found that when fly ash was added to fly ash concrete at a dosage of 20%, the acceptable crushing strength of concrete could be
satisfied within 7–28 days. At the same time, before determining the use of fly ash, the composition and quality of fly ash need to be
analyzed. Excessive fly ash addition will also reduce the compressive and flexural strength of concrete. Fuzail et al. [18] found that
with the increase of fly ash content, the compressive strength and flexural strength of fly ash concrete after standard curing for 28 days
showed a downward trend. When the dosage increased to 25 wt% (weight percentage), the compressive strength and flexural strength
of concrete under standard curing for 28 days decreased from 26.10 MPa and 2.56–22.60 MPa and 2.36 MPa, respectively. The reason
is that the hydration reaction of fly ash is slow at normal temperature, and the standard curing time of 28 days is not enough to make
the performance of fly ash concrete reach the best. Hansen and others [19] found that mixing fly ash and waste gypsum into concrete in
a certain proportion made concrete specimens obtain sufficient compressive strength. When the content of fly ash reaches 50%, the
90-day compressive strength of concrete can still meet the requirements.
2.3. Application of fly ash in bricks
Gel substances such as calcium silicate hydrate generated by fly ash hydration reaction can be used to bond aggregates to form a
certain mechanical strength. At present, methods such as sintering method and autoclaving method have been used to prepare fly ash-
2
based bricks. At present, there are more than 10 types of fly ash bricks, such as hollow bricks, wall panels and sound-absorbing bricks.
Among them, the production and consumption of sintered porous bricks and non-load-bearing hollow bricks are mostly [20]. Ordieres
et al. [21] made sintered bricks under 1100◦ calcination conditions with fly ash, coffee grounds and fermented clay as raw materials.
This brick has strong mechanical properties, but lacks durability due to the addition of organic substances such as coffee grounds. Leiva
et al. [22] evaluated the environmental safety of high-content fly ash sintered bricks including heavy metal leaching amount and
radioactivity can meet the requirements, but the sintering needs to be completed at 1000 ℃. Zhang and others [23] used vanadium ore
tailings, slaked lime and fly ash to prepare fly ash autoclaved bricks. The research results showed that in addition to providing hy
dration products, the hydrated aluminum silicate was produced by fly ash can react with sulfate in vanadium slag to form mayvandite,
thereby reducing or eliminating the erosive effect of sulfate on bricks. At the same time, fly ash itself can form higher strength through
geopolymer reaction. Wong et al. [24] used NaOH and Na2SiO3 to jointly stimulate the geopolymer reaction of fly ash, and doped 10 wt
% brick powder to further increase the strength. The final strength of fly ash geopolymer can reach 44.2 MPa, and this study can
provide a new idea for the application of high content of fly ash.
2.4. Study on heavy metals in fly ash
Due to the low price of fly ash and certain pozzolanic activity, the content of fly ash in various types of fly ash building materials is
10%− 20%, and it can even reach more than 50% through design and modification [25]. Fly ash contains a lot of heavy metal elements,
such as Hydrargyrum(Hg), Arsenic(As), Manganese(Mn), Copper(Cu), Cadmium(Cd), Nickel(Ni), Plumbum(Pb) and other heavy
metals. These toxic heavy metal elements are present in coal in various amounts and forms, depending on the different geological and
geochemical processes that occur during peat and coal formation. Compared with the parent state of coal, fly ash and the by-product of
coal combustion are rich in various toxic heavy metal elements, which is mainly attributed to the complex changes in coal particles
caused by heating and cooling during coal combustion. These changes include coke formation, agglomeration of molten inclusions,
and vaporization and condensation of volatile elements. Volatile elements such as arsenic, mercury, and chromium in the hot flue gas
may redeposit on the fly ash particles as the temperature decreases along the gas passages in the boiler. According to research reports,
the content of heavy metals in fly ash is usually above 50 mg/kg, which is generally about 4–10 times that of parent coal [26,27]. The
leaching of toxic elements in fly ash will have adverse effects on aquatic and terrestrial ecosystems. The leaching of potential toxic
substances into soil and groundwater will not only affect the growth of vegetation, but also change the composition of the growing
vegetation, resulting in the accumulation of toxic substances. Eventually enter the human body through the food chain. The con
centration of most of the leaching substances (such as pH, hardness, oxides, sulfides, heavy metals, suspended solids, etc.) in the
leaching solution greatly exceed the Chinese drinking water standards, and the heavy metal content is 10–100 times of the standard
content [28,29].
Fly ash contains Cr, Ni, Pb, As, Hg, Cd and other heavy metal elements that are harmful to human body, and there is leaching
behavior under the action of the external environment, which has potential harm to the environment and human body. However, there
is a lack of systematic evaluation and research on the harm degree of heavy metals in fly ash. At present, the relevant standards for fly
ash in China do not limit the content of harmful heavy metals in fly ash in different application scenarios. Therefore, in this study, fly
ash from four typical regions of China was selected and systematic study. Firstly, their strength activity indices were detected
respectively, and the basic properties of fly ash in four regions of China were analyzed by microscopic analysis instruments such as X-
Fig. 1. Fly ash sample.
3
Ray Fluorescence Spectrometer(XRF), X-Ray Diffraction Spectrometer(XRD), Fourier Transform Infrared Spectrometer(FTIR) and
Scanning Electron Microscope/Energy Dispersive Spectroscopy(SEM/EDS). After that, the content of six heavy metals, Cr, Ni, Pb, As,
Hg and Cd in the four fly ash samples, was detected by atomic fluorescence method. According to single factor index, potential
ecological risk index, index of geo-accumulation and human health risk assessment method, the hazards of heavy metals were eval
uated respectively, and the similarities, differences and applicability of these four methods were summarized and analyzed. Then, we
selected a kind of fly ash to carry out the simulated heap leaching experiment of characteristic heavy metals, and constructed the
mathematical model of heavy metal leaching. Their valence states were analyzed by X-ray Photoelectron Spectroscopy(XPS) test of
characteristic heavy metals, so as to further judge the hazard of characteristic heavy metals in fly ash. Finally, based on the current
Chinese national standards and the evaluation results of this study, the limit values of characteristic heavy metals of fly ash in different
application scenarios are proposed to ensure that the heavy metal content of fly ash is not harmful to human body and the
environment.
3. Materials and methods
3.1. Raw materials
In this study, the four types of fly ash were obtained from four regions in China, FA 1, FA 2, FA 3, and FA 4 from coal power plants in
the eastern, central, western and southwestern regions, respectively. The fly ash samples are shown in Fig. 1. The boilers used in the
power plant are circulating fluidized bed boilers of different types. The boiler informations corresponding to each type of fly ash are
shown in Table 1. The fuel of the boiler is coal produced locally. The sand used in the experiment is standard sand, and the cement is
Portland cement with a strength grade of 42.5 produced by a cement factory in Chongqing.
3.2. Experimental method
3.2.1. Determination of fly ash strength activity index

The test method for the strength of cement mortar was carried out in accordance with the "Method of testing cements: Determination of
strength" (GB/T 17671–1999), and the 28-day compressive strength of the test sample and the comparison sample were measured
respectively. The strength activity index of fly ash is determined by the ratio of the two. The calculation formula is (1). When H28 is
greater than 70%, it meets the relevant requirements of "Fly ash used for cement and concrete" (GB/T1596–2017). The fly ash strength
activity index H28 is calculated according to formula 1, and the calculation result is reserved to an integer.
R
H28 = × 100% (1)
R0
Where, H28—Intensity activity index, the unit is %. R—28-day compressive strength of the test sample after mixing with fly ash, the
unit is MPa. R0—28-day compressive strength of the comparative sample, the unit is MPa.
3.2.2. Loss on ignition test method

Loss on ignition analysis: According to the standard "Methods for chemical analysis of cement (GB/T 176–2017)" in the loss on
ignition detection method test: first weigh 1.0000 g of fly ash sample (accurate to 0.0001 g), then place the weighed fly ash in the
crucible. Set the muffle furnace temperature to 950 ± 25 ℃, burn for about 15–20 min, cool down to room temperature and weigh.
Repeat this process to constant weight. The formula for calculating the loss on ignition is formula 2.
ωLOI = (m2 − m3 )/(m2 − m1 ) × 100 (2)
Where: ωLOI , loss on ignition, %. m1, mass of crucible, g. m2, mass of crucible and sample, g. m3, mass of crucible and sample after
burning, g.
3.2.3. Instrument of microscopic analysis

The four kinds of fly ash were sampled and dried, and the element content of each fly ash was analyzed by X-ray fluorescence (XRF)
analysis method according to "Chemical Analysis of Cement" (GB176–87). The instrument model used is: XRF primus-2, Japan. The
mineral composition of fly ash was analyzed by X-ray diffraction (XRD), the model used was Bruker D8Advance, Germany. Fourier
transform infrared spectroscopy (FTIR) was used to analyze the types of functional groups on the surface of fly ash under infrared
Table 1
Boiler informations related to each type of fly ash.
Type Rated capacity (t/h) Nominal steam temperature (℃) Nominal steam pressure (MPa) Desulfurizer
FA 1 200WM CFB boiler 690 540 13.73 Limestone

FA 2 200WM CFB boiler 670 540 13.73 Dolomite
4
irradiation with a wavenumber of 400–4000 cm− 1. The model of FTIR is: Nicolet iS50, America. The particle size distribution of fly ash
was measured using a laser particle size analyzer (Mastersizer 2000, Malvern, UK). The model of X-ray Photoelectron Spectroscopy
(XPS) equipment is Thermo Scientific K-Alpha+ . The model of SEM/EDS is Zeiss Sigma300.
3.2.4. Determination of heavy metal content in fly ash

The content of arsenic in fly ash was determined by atomic fluorescence spectrometer AFS-930 ("Soil quality - Analysis of total
mercury, arsenic and lead contents- Atomic fluorescence Spectrometry-Part 2: Analysis of total arsenic in soils" GB/T 22105.2–2008). The
content of mercury in fly ash was determined by atomic fluorescence spectrometry using a double atomic fluorescence spectrometer
AFS-9700 ("Soil quality - Analysis of total mercury, arsenic and lead contents- Atomic fluorescence Spectrometry-Part 1: Analysis of total
mercury in soils "GB/T 22105.1–2008). Using atomic absorption spectrophotometer AA7000F, the content of lead and cadmium in fly
ash was determined by graphite furnace atomic absorption spectrophotometry ("Soil Quality-Determination of Lead, Cadmium-Graphite
Furnace Atomic Absorption Spectrophotometry"GB/T 17141–1997). Using atomic absorption spectrophotometer PAA900F, the content of
chromium and nickel in fly ash was determined by flame atomic absorption spectrophotometry ("Soil and Sediments-Determination of
Copper, Zinc, Lead, Nickel, Chromium-Flame Atomic Absorption Spectrophotometry"HJ 491–2019).
3.2.5. Heavy metal risk assessment methods
3.2.5.1. Single factor index. The single-factor pollution index evaluation method is the basis of other comprehensive soil pollution
evaluation methods. This method is to determine the single-item soil environmental quality parameter by evaluating the pollution
degree of a characteristic pollutant in the soil environment. The calculation formula is formula 3 [30].
Ci
Pi = (3)
Si
Where, Pi is the single factor index of a heavy metal element i in the test substance; Ci is the actual test value of heavy metal i (mg/kg);
Si is the reference value of heavy metal i (mg/kg). In this study, the prevention and control values of China’s national standard "Soil
Environmental Quality-Risk Control Standard for Soil Contamination of Agricultural Land (GB15618–2018)" were used as reference values.
The reference value of each heavy metal is shown in Table 2. If Pi ≥ 0.5, it indicates that the heavy metal has potential ecological
hazards and should be considered. Pi > 1 indicates that the soil is polluted, and the larger the value, the more serious the pollution.
3.2.5.2. Potential ecological risk index. The potential ecological risk index was proposed by the famous Swedish scientist Hakanson in
1980 [31]. The method is weighted by multiplying the ratio of the heavy metal to the reference value by the toxicity factor of the heavy
metal. It is a set of methods that can well reflect the potential impact of heavy metals on the ecological environment. The calculation
formula is formula 4.
∑ ∑[ ( i )]
Cs
RI = Ei Ti × (4)
Cis
Where, RI is the comprehensive potential ecological risk index of a certain fly ash. Ei is the potential ecological risk index of a single
heavy metal element, Cis is the measured value of heavy metal i in fly ash (mg/kg); Cin is the heavy metal i reference value(Table 2). The
prevention and control value of "Soil Environmental Quality-Risk Control Standard for Soil Contamination of Agricultural Land
(GB15618–2018)" was used as the reference value, and Ti was expressed as the toxicity response coefficient of heavy metal i. According
to Hakanson’s research results, TAs= 10, THg= 40, TPb= 5, TCd= 30, TCr= 2, TNi= 5.
3.2.5.3. Geoaccumulation index. The Geoaccumulation Index (Igeo) is often referred to as the Muller index, which was proposed by
German scientist Muller in 1969 [32]. Because the index of geoaccumulation can take into account the factors of background values
caused by natural geological processes, and can fully consider the impact of human activities on the pollution of heavy metals, it is now
widely used in the assessment of metals in the soil environment. Therefore, this study uses the index of geoaccumulation to evaluate
the environmental damage caused by the comprehensive utilization of fly ash. The calculation formula is formula 5.
[ ]
Cn
Igeo = log 2 (5)
K × Bn
Where, Cn represents the measured value of a certain heavy metal content in fly ash (mg/kg). K is the correction coefficient used to
consider the change of the background value that may be caused by the movement of the earth’s rocks (generally 1 or 1.5, this subject
takes 1.5), Bn represents the geochemical background value of n element in a certain area (mg/kg), which was taken from the soil
Table 2
Reference value of each heavy metal (mg/kg).
As Hg Pb Cd Cr Ni
Si 30.00 0.5 70.0 0.3 150 200
5
background value in China in this study, as shown in Table 3 [33].
3.2.5.4. Human health risk assessment. The heavy metals contained in fly ash will not only cause potential safety risks to the soil, but
also may cause carcinogenic risks to the human body. Using this method, the harm of fly ash heavy metals to human body can be
evaluated. This study draws on the Chinese national standard "Technical guidelines for risk assessment of soil contamination of land for
construction" (HJ 25.3–2019), the US Health Risk Assessment Method (US EPA), and previous research results [34–36]. Using the
American health risk assessment method, the non-carcinogenic human health risk assessment of As, Pb, Cd, Hg, Ni and Cr in fly ash was
carried out, and the carcinogenic human health risk assessment of As, Pb, Cd and Cr was carried out. This study mainly adopted three
different ingestion methods (oral ingestion, inhalation ingestion, and skin contact) to study the assessment of the health risks of heavy
metals in fly ash to human health. The calculation formulas are formula 6–12.
CαFAi × IRing × EF × ED
ADDing = × 10− 6
(6)
BW × AT
CαFAi × IRinh × EF × ED
ADDinh = × 10− 6
(7)
BW × AT × PEF
CαFAi × SA × AF × ABS × EF × ED
ADDder = × 10− 6
(8)
BW × AT
ADDi
HQ = (9)
RfDi
∑
n
ADDi
HI = (10)
i=1
RfDi
CR = ADDi × SFi (11)
∑
n
TCR = ADDi × SFi (12)
i=1
Where, ADDing, ADDinh and ADDder represent the average daily exposure dose by ingestion, inhalation, dermal contact, respectively
(mg⋅kg− 1⋅d− 1). CαFAi indicates the pollutant concentration of α heavy metal in fly ash (mg⋅kg− 1). ADDi represents the average daily
exposure dose for i intake modes (mg⋅kg− 1⋅d− 1). RfDi represents the non-carcinogenic reference dose of i heavy metal
(mg⋅kg− 1⋅d− 1)− 1. CSFi represents the cancer slope factor of i element (mg⋅kg− 1⋅d− 1)− 1. The hazard quotient (HQ) was used to estimate
the non-carcinogenic effects of heavy metals in EMM sintered bricks. Hazard Index (HI) equals the sum of the HQ for multiple heavy
metals or multiple exposure routes [37]. Referring to the US EPA standard, if HI < 1, it will not have a negative impact on human
health. The exposure estimation of carcinogens is expressed as CR. TCR represents the total cancer risk index of one or more heavy
metals. When CR/TCR > 10− 6, it is considered that there is no carcinogenic risk. When 10− 4 < CR/TCR < 10− 6, there is a certain risk
of harm, and CR/TCR > 10− 4 represents a very high cancer risk [38,39]. The recommended values for health risk assessment are
shown in Tables 4 and 5.
4. Results and analysis
4.1. Analysis of fly ash strength activity index
In the fly ash strength activity experiment, the experimental group with a fly ash content of 0 is set as the control group FA 0.
Table 6 shows the results of the four types fly ash strength activity tests. The calculation of the 28 days strength activity index of the
four kinds of fly ash showed that their strength activity index is not much different, and the order of H28 is FA 2 > FA 3 > FA 4 > FA 1.
Studies have shown that the strength index of fly ash is related to the content of active components (SiO2, Al2O3) in fly ash, and the
active components can react with Ca(OH)2 produced during the hydration of cement clinker respectively. The resulting hydration
products such as calcium silicate hydrate, calcium aluminate hydrate, etc., enable the mortar or concrete specimen to gain strength
[47].
Table 3
Elemental geochemical background values of fly ash sampling sites(mg/kg).
As Hg Pb Cd Cr Ni
FA 1 9.1 0.095 25.0 0.138 70.2 29.9

FA 2 11.4 0.034 19.6 0.074 63.8 26.7
FA 3 20.0 0.110 35.2 0.659 95.9 39.1
FA 4 10.4 0.061 30.9 0.079 79.0 32.6
6
Table 4
Value of health risk due to heavy metal exposure.
Parameter Definition Unit Value Reference
Adult Child
IRing Ingestion rate mg⋅d− 1 30 60 [40]

IRinh Inhalation rate m3⋅d− 1 7.63 20 [37]
EF Exposure frequency d⋅y− 1 180 180 [41]
ED Exposure duration y 24 6 [41]
BW Body weight kg 70 15 [41]
AT Averaging time d 25500 (Carcinogens) [42]
ED × 365(Non-carcinogens) [41]
PEF Particle emission factor m3⋅kg− 1 1.36E+ 0.9 1.36E+ 0.9 [37]
SA Skin surface area parameter cm2⋅d− 1 5700 2800 [41]
AF The adherence factor of soil to skin mg/cm2 0.07 0.2 [41]
ABS Dermal absorption fraction – 0.001 0.001 [41]
Table 5
Recommended values of RfDi and SFi for different heavy metals.
RfDi/ (mg⋅kg− 1⋅d− 1) SFi/ (mg⋅kg− 1⋅d− 1) Reference
RfDing RfDinh RfDder SFing SFinh SFder
Ni 2.00E-02 5.40E-03 2.06E-02 – – – [43]

Hg 3.00E-04 3.00E-04 8.60E-04 – – – [44]
As 3.00E-04 1.23E-04 3.00E-04 1.51E+ 00 1.51E+ 01 3.66E+ 00 [45]
Cr 3.00E-03 6.00E-05 2.86E-03 5.01E-01 4.20E+ 01 2.00E+ 01 [43,46]
Pb 3.50E-03 3.52E-03 5.25E-04 8.5E-03 8.5E-03 4.20E-02 [43]
Cd 1.00E-03 1.00E-06 1.00E-05 6.10E+ 00 6.3E+ 00 0.38E+ 00 [43,45]
Table 6
Fly ash strength activity test results.
R/MPa H28/%
FA 0 43.6 100
FA 1 30.8 70.6
FA 2 35.9 82.3
FA 3 33.7 77.3
FA 4 31.9 73.2
4.2. Analysis of loss on ignition of fly ash
Table 7 lists the results of the four fly ash loss on ignition tests. The calculation results showed that the loss on ignition of FA 1, FA 2,
FA 3 and FA 4 had reached the level I requirement in the Chinese national standard "Fly ash used for cement and concrete" (GB/T
1596–2017) - less than 5.0%. Loss on ignition is an indicator that reflects the amount of unburned residual carbon in fly ash, and it is
also one of the key components affecting the performance of fly ash cementitious materials. The study believes that residual carbon is
an inert component, and if the content is too high, the activity of fly ash will deteriorate. At the same time, too high carbon content will
increase the water demand of concrete and reduce the compactness. Carbon powder tends to concentrate on the surface of the concrete
during the curing and bleeding process of concrete, which will negatively affect the performance of the surface. However, the residual
carbon content in the four types of fly ash used in this study is significantly lower, and it will not greatly affect the water demand and
compactness of mortar and concrete during the application process.
4.3. Analysis of micro test results
4.3.1. Analysis of XRF test results

Four kinds of fly ash were sampled, and X-ray fluorescence spectrometer (XRF) was used to analyze the elemental composition of fly
ash. The test results are shown in Table 8.
Table 7
Calculation results of fly ash loss on ignition.
FA 1 FA 2 FA 3 FA 4
ωLOI 2.10% 2.61% 3.2% 4.2%
7
The chemical components of the four kinds of fly ash are SiO2, Al2O3, CaO, Fe2O3, etc., and are mainly composed of SiO2 and Al2O3.
The content of these two types of oxides in FA1 is the lowest, less than 50%. The two types of oxides in FA 2 account for 88.5%, of
which the content of Al2O3 accounts for 41.6%, which belongs to high-alumina fly ash. The content of SiO2 and Al2O3 in FA 3 and FA 4
reaches more than 70%. The main components of aluminosilicates are SiO2 and Al2O3. The higher the content of these components, the
higher the activity of fly ash [47]. According to the content of CaO in fly ash, fly ash can be divided into high calcium fly ash and low
calcium fly ash, that is, only FA 1 is high calcium fly ash among the four types of fly ash, and the rest are low calcium fly ash. According
to the analysis, the reason for the high content of CaO in fly ash is the influence of the desulfurizer or the minerals such as calcite in the
raw coal, and the reason for the high content of MgO in FA 1 is also due to the addition of the desulfurizer [48]. In addition, 4.92% of
FA 1 is Na2O and 6.42% is SO3, which is considered to be due to the presence of albite, inorganic sulfur and organic sulfur in the raw
coal. Judging from the Fe2O3 content in the fly ash, the Fe2O3 content of FA 1, FA 3 FA 4 is 12.1%, 10.2%, and 10.4%, respectively,
which are all iron-rich fly ash.
4.3.2. Analysis of XRD test results

According to Fig. 2, it can be seen that there are obvious mound peaks and dispersion peaks in each fly ash XRD pattern, which
proves that the four fly ash samples contain a large amount of amorphous glass phase. The main components of the four types of fly ash
are mullite and quartz. Most of the quartz is the melting residue of quartz in the process of coal combustion, and the crystal structure is
still in a low temperature state. Mullite is the product of in-situ decomposition and phase transition of clay minerals such as kaolinite
during coal combustion. Strong quartz, Al2O3 characteristic peaks and a small amount of CaO characteristic peaks can be detected in
the FA 1 spectrum, which is consistent with the previous XRF analysis results of FA 1, but the quartz characteristic peaks of the other
three fly ash are not. Significantly, this is because there is no obvious regularity between the quartz content and the SiO2 content of fly
ash. In addition, the content of mullite and glassy Al2O3 in fly ash are positively correlated with the total content of Al2O3. Therefore,
Al2O3 in the other three fly ash mainly exists in the form of mullite. It is worth noting that the four types of fly ash contain a small
amount of CaSO4 and CaCO3 characteristic peaks. The appearance of the CaCO3 characteristic peaks is caused by the addition of
limestone during the desulfurization process. The excess CaSO4 in the fly ash will prolong the setting time of the concrete and make the
volume stability of the concrete poor.
4.3.3. Analysis of FTIR test results

Fig. 3 shows the infrared spectra of the four types of fly ash. The overall trends of the infrared spectra of the four types of fly ash are
similar, and the distribution of each peak position is also relatively consistent. The fly ash samples have five characteristic peaks near
3450 cm− 1, 1635 cm− 1, 1150 cm− 1, 580 cm− 1 and 470 cm− 1. The characteristic peaks of FA 1, FA 2 and FA 3 are more obvious near
580 cm− 1. The characteristic peaks of the remaining peak positions are consistent with the four types of fly ash. The analysis shows that
the broad absorption peak near 3450 cm− 1 is caused by -OH vibration, and the absorption peak near 1635 cm− 1 is caused by -OH
vibration of fly ash and water. The two peaks are thought to be the stretching and deformation vibrations of -OH and H-O-H caused by
water molecules on the fly ash surface [49]. The absorption peak near 1150 cm− 1 is the Si-O stretching vibration of quartz [50]. The
vibrations around 470 cm− 1 and 580 cm− 1 are the asymmetric stretching and bending vibrations of the M-O (M is Si/Al/Fe/Ca) bond
[51]. Infrared analysis results show that the main chemical components of fly ash are mainly Si, Ca, Al, O and other elements, which
are consistent with XRF and XRD analysis results.
4.3.4. Analysis of fly ash particle size distribution test results

It is found from Fig. 4 that the particle sizes of the four types of fly ash are mainly concentrated between 1 and 100 µm. Among
them, FA1, FA3, and FA4 all showed obvious double peaks. The two peaks of FA1 are distributed around 0.6 µm and 5 µm, and the two
peaks of FA 3 and FA 4 are mainly concentrated at 0.6 µm and 50 µm. However, the particle size content of FA 1, FA 3, and FA 4 is less
at about 0.6 µm, and FA 2 presents a unimodal state with a wider distribution. The test results show that the d(0.5) of the four types of
fly ash are FA 4(26.835 µm) > FA 3(22.478 µm) > FA 2(19.711 µm) > FA 1(11.503 µm) in descending order. The d(0.9) of fly ash is in
descending order of FA 4(119.014 µm) > FA 3(84.990 µm) > FA 2(83.120 µm) > FA 1(72.877 µm), and FA 1 has fewer coarse par
ticles, on the contrary FA 4 has more coarse particles.
4.3.5. SEM/EDS analysis of fly ash

The above pictures in Fig. 5 show the SEM photos of the experimental fly ash FA 1, FA 2, FA 3, and FA 4. It can be seen from the
figures that the four kinds of fly ash are dominated by regular spherical particles, mostly aluminosilicate spheres and a small amount of
iron-rich spheres. The particle size is concentrated in 1–100 µm, which is the same as the particle size distribution test result. Most of
the spherical microbeads have smooth surfaces, and flake crystals are observed on the surface of FA 3 fly ash particles, and many round
Table 8
Results of fly ash XRF test (/%).
SiO2 Al2O3 CaO Fe2O3 Na2O SO3 MgO K2O
FA 1 34.3 15.4 16.3 12.1 4.92 6.42 8.14 1.28

FA 2 46.9 41.6 2.23 3.36 0.744 1.25 0.747 1.11
FA 3 43.3 27.2 7.48 10.2 2.22 1.84 2.53 2.04
FA 4 43.5 28.5 7.98 10.4 0.839 2.99 1.59 1.35
8
Fig. 2. XRD pattern of fly ash.
Fig. 3. FTIR spectrum of fly ash.
and smaller glass microbead aggregates are adsorbed. In the meantime, a small amount of irregular particles, mainly glass slag, can
also be seen. The formation of these spherical microbeads is due to the fact that the combustion temperature of the pulverized coal
furnace is as high as about 1400 ℃, and the ash is in a molten state in the combustion furnace [52]. When the temperature is suddenly
lowered in the flue, because of the action of surface tension, the edges and corners of the ash particles shrink into spherical shapes.
Four kinds of fly ash were scanned with EDS to obtain energy spectrum. It can be seen from Fig. 6 that the four types of fly ash
contain Si, Al, O, Ca and other elements. It is worth noting that a small amount of Cr is detected in these four types of fly ash, and the
mass fractions are 0.02%, 0.03%, 0.04%, and 0.10%, respectively. At the same time, FA 1, FA 2, and FA 3 all contain As, FA 2, FA 3, and
FA 4 contain 0.40%, 0.64%, and 0.73% of Hg, respectively, and 0.15% of Hg and 0.17% of Ni are detected in FA 1 and FA 4,
respectively. The EDS scanning results in Fig. 7 show that the four types of fly ash contain As, Cr, Cd, Hg, Ni and other heavy metal
elements that are harmful to human body to varying degrees. Therefore, this study further studies the harmfulness of these charac
teristic heavy metals.
The XRF, XRD, FTIR,SEM/EDS detection and analysis show that the four types of fly ash are mainly Si, Ca, Al, S, O and other
elements, but the content of each element varies due to different reasons such as the origin of raw coal. Except for FA 1, the content of
SiO2 in the other three kinds of fly ash is above 43%, because there is no obvious regularity between the content of quartz and the
9
Fig. 4. Particle size distribution of fly ash.
content of SiO2 in fly ash. Therefore, there are no significant quartz characteristic peaks in the XRD patterns of the four types of fly
ashes. But the infrared spectrum analysis shows that all four kinds of fly ash have strong Si-O stretching vibration absorption peaks of
quartz. The XRF test results show that the CaO content of FA 1 reached 16.3% due to the addition of desulfurizer, and the characteristic
peaks of CaO in the XRD pattern were also very significant, which belonged to high calcium fly ash. The XRF detection results and XRD
patterns of FA 2 prove that it contains a large amount of Al2O3, which belongs to high-alumina fly ash, and FA 3 and FA 4 belong to
iron-rich fly ash. Meanwhile, a small amount of CaSO4 is observed in the XRD patterns of the four types of fly ash, which is considered
to be formed by the reaction of CaO and SO2 during the desulfurization process. The M-O (M is Si/Al/Fe/Ca) bond vibration peaks
observed in the infrared spectra of the four types of fly ash indicate the existence of Si, Al, Fe, Ca related oxides. The particle size
distributions of the four types of fly ash are roughly the same, ranging from 1 to 100 µm. The SEM images of the fly ash samples show
that the four types of fly ash are mainly composed of spherical particles, and their particle sizes are mainly concentrated in the range of
1–100 µm, which is the same as the test results of particle size distribution. It is worth noting that in the EDS test patterns of these four
types of fly ash, we find the presence of heavy metal elements Cr, Cd, As, Pb, and Hg. Therefore, it is necessary to further evaluate the
heavy metal content, valence state and environmental hazards in fly ash.
4.4. Analysis of heavy metals
4.4.1. Detection of heavy metal content in original fly ash

In this study, the content of heavy metals (As, Hg, Pb, Cd, Cr, and Ni) in fly ash samples from power plants in four regions was
detected. The results are shown in Table 9, in which the standard value refers to the prevention and control value of the National
Standard "Soil Environmental Quality-Risk Control Standard for Soil Contamination of Agricultural Land "(GB15618–2018) as the standard
value. The Cd content in fly ash FA 1, FA 2 and FA 3 was 0.71 mg/kg, 0.72 mg/kg, 0.98 mg/kg respectively, and the Hg content in FA2
was 0.977 mg/kg, far exceeding the standard value. The contents of As, Hg, Pb, Cr, and Ni in FA 1 and FA3, As, Pb, Cr, Ni in FA 2, and
all six heavy metals in FA 4 do not exceed the soil pollution prevention and control values for agricultural land in China. Pb in FA 1,
heavy metals As and Cr in FA 3, and Cr content in FA 4 are all close to 50% of the standard value. The heavy metal leaching effect will
occur when the fly ash is accumulated in a large amount. Therefore, this study use multiple methods to analyze the six heavy metals
with potential ecological environment and human health hazards among the four types of fly ash.
4.4.2. Agricultural environmental safety assessment
4.4.2.1. Single factor index. The single factor index was used to evaluate the environmental safety of the six heavy metals As, Pb, Cd,
Hg, Ni and Cr in the four types of fly ash. The results are shown in Table 10. The evaluation results show that the Pi of the heavy metals
Hg and Pb in FA 1 are 0.784 and 0.594 (>0.5), respectively, the Pi of the heavy metal As in FA 3 is 0.500 (=0.500), and the heavy metal
Cr in FA 4 is 0.591 (>0.5). All of these heavy metals have potential environmental risks to agricultural soils. What is more noteworthy
is that the Pi of heavy metal Cd in FA 1, FA 2, and FA 3 are all much higher than 1, which are 2.367, 2.400, and 3.267, respectively.
There is a great risk of heavy metal pollution to agricultural land, which requires special attention. In addition, the Pi of Hg in FA 2 is
also higher than 1, and it is necessary to pay attention to the heavy metal Hg in the resource utilization of FA 2.
4.4.2.2. Potential ecological risk index. The potential ecological risk index divides the degree of ecological hazard into five levels, as
10
Fig. 5. SEM images of fly ash (FA 1: a, b; FA 2: c, d; FA 3: e, f; FA 4: g, h).
shown in Table 11. This method was used to assess the environmental risk of agricultural land for the heavy metals As, Pb, Cd, Hg, Ni
and Cr in the four types of fly ash. The calculation results are shown in Table 12. Firstly, for the three types of fly ash, FA 1, FA 2, and FA
3, the potential ecological risk index of heavy metal Cd is higher than 71. The ecological hazard degrees of Cd in FA 1 and FA 2 belong
to medium hazard, while the Cd ecological hazard of FA 3 belongs to strong hazard. In addition, the heavy metal Hg in FA 2 also has a
moderate degree of ecological damage to the environment. On the whole, the evaluation results of the single factor index and the
11
Fig. 6. The energy spectrum of four kinds of fly ash.
potential ecological risk index are similar, which verifies the accuracy of this analysis. By calculating the RI of each type of fly ash, the
RI of FA 1, FA 2, and FA 3 are all higher than 80, and the RI of FA 2 is as high as 153.06. The high RI of these three types of fly ash is
mainly affected by the heavy metals Cd and Hg, and the influence of the heavy metal As should also be noticed.
4.4.2.3. Geoaccumulation index method. According to the calculated geological accumulation index (Igeo), the results can be divided
into 7 grades as shown in Table 13. The environmental risk assessment of agricultural land is carried out on the heavy metals As, Pb,
Cd, Hg, Ni and Cr in four kinds of fly ash using the geological cumulative index method(Table 14). First of all, different from the
previous two analysis results, the geological accumulation index of heavy metal Cd in FA 3 is − 0.012 (<0), that is, the heavy metal Cd
in FA 3 does not pollute the environment. The reason is that the index of geo-accumulation considers the local soil background value.
The soil background value of heavy metal Cd in FA3 production area is not much different from the detection value of Cd in FA 3. No Cd
is detected in FA 4, so Cd in FA 3 and FA 4 is judged to be non-polluting to the environment. The Igeo of heavy metal Cd in the fly ash of
FA 1 and FA 2 were 1.778 and 2.697, respectively, and the pollution levels are 2 and 3, respectively. It is worth noting that the heavy
metal Hg pollution in the FA 1 and FA 2 can not be ignored. The pollution level of the Hg in the FA 2 is 5, which belongs to heavily-
extremely polluted. It can be seen that the fly ash has obvious enrichment phenomenon of Hg in the production process, and a large
amount of accumulation will cause serious harm to the soil environment and groundwater. Different from the previous two methods,
the evaluation of FA 4 by the index of geo-accumulation also find that the heavy metal Ni pollution level is 1, which has a potential
pollution risk to the soil. Therefore, it can be determined that for the fly ash in these four regions, the pollution levels of the six heavy
metals are Cd>Hg>Pb>As>Cr>Ni.
12
Fig. 7. Heavy metal energy spectrum (FA 1:a,b,c. FA 2:d,e,f. FA 3:g,h,i. FA 4:j,k,l).
4.4.3. Human health risk assessment

Non-carcinogenic risk analysis: After calculation, the non-carcinogenic risk indices of heavy metals in fly ash in the four regions
under different intake routes are shown in Table 15. Divided by adults and children, the non-carcinogenic comprehensive risk index of
each fly ash is less than 1. It can be seen that no matter for adults or children, the six heavy metals in the four types of fly ash have no
non-carcinogenic risks to human health. Specifically, under each intake route, the non-carcinogenic risk index of heavy metals in fly
ash to children is always an order of magnitude higher, indicating that heavy metals in fly ash are more harmful to children.
Carcinogenic risk analysis: The calculation results of the single heavy metal carcinogenic risk index (CR) under the three intake
routes are shown in Tables 16, 17 and 18, and the comprehensive carcinogenic risk index (TCR) of each fly ash is shown in Table 19. It
can be seen from Table 16 that the carcinogenic risk index of As and Cr in the four types of fly ash under the oral intake route is greater
than the risk prevention and control value (1 ×10− 6), which means that there is a carcinogenic risk. For children, the CRing of the Pb in
13
Table 9
Detection results of heavy metals in fly ash.
Elements Content (mg/kg) Standard (GB15618-2018)
FA 1 FA 2 FA 3 FA 4
As 6.34 4.59 15.0 12.3 30.00

Hg 0.392 0.977 0.110 0.064 0.50
Pb 41.6 17.0 ND 26.6 70.00
Cd 0.71 0.72 0.98 ND 0.30
Cr 16.8 6.2 60.8 88.6 150.00
Ni 12 3 10 53.0 200.00
Table 10
Calculation results of single factor pollution index.
Pi (FA 1) Pi (FA 2) Pi (FA 3) Pi (FA 4)
As 0.211 0.153 0.500 0.410

Hg 0.784 1.954 0.220 0.128
Pb 0.594 0.243 0.000 0.380
Cd 2.367 2.400 3.267 0.000
Cr 0.112 0.041 0.405 0.591
Ni 0.060 0.015 0.050 0.265
Table 11
Ecological hazard index and hazard degree.
Ei Ecological grade
＜40 Low risk

40–80 Moderate risk
80–160 Considerable risk
160–320 High risk
＞320 Extreme risk
Table 12
Calculation results of potential ecological risk index of heavy metal elements.
Elements Ei (FA 1) Ei (FA 2) Ei (FA 3) Ei (FA 4)
As 2.11 Low 1.53 Low 5.00 Low 4.10 Low

Hg 31.36 Low 78.16 Moderate 8.80 Low 5.12 Low
Pb 2.97 Low 1.21 Low 0.00 ND 1.90 Low
Cd 71.00 Moderate 72.00 Moderate 98.00 Considerable 0.00 ND
Cr 0.22 Low 0.08 Low 0.81 Low 1.18 Low
Ni 0.30 Low 0.07 Low 0.25 Low 1.32 Low
RI 107.97 153.06 112.867 13.625
Table 13
Geological accumulation index and pollution degree classification.
Igeo Class Implication
≤0 0 Unpolluted
0–1 1 Unpolluted-Moderately Polluted
1–2 2 Moderately-Polluted
2–3 3 Moderately-heavily Polluted
3–4 4 Heavily Polluted
4–5 5 Heavily-Extremely Polluted
＞5 6 Extremely Polluted
the four types of fly ash are higher than those in adults, which means that the Pb in the four types of fly ash has a greater carcinogenic
risk to children. Under the oral route, the carcinogenic risk index of Cr in FA 1 to children is 1.2 × 10− 4, and the carcinogenic risk index
of Cr in FA 3 to adults is 1.8 × 10− 4. The carcinogenic risk indices of Cr in FA 4 to adults and children were 1.6 × 10− 4 and
3.77 × 10− 4, respectively. At the same time, the carcinogenic risk index of Cr to human body under this intake route all exceeded
1 × 10− 5. Data analysis shows that Cr and As in fly ash under this intake route have a general carcinogenic risk to the human body, and
14
Table 14
Calculation results of geological accumulation index of heavy metal elements.
FA1 FA2 FA3 FA4
Igeo Class Igeo Class Igeo Class Igeo Class
As -1.106 0 -1.897 0 -1.000 0 -0.343 0

Hg 1.460 2 4.260 5 -0.585 0 -0.516 0
Pb 0.150 1 -0.790 0 ND 0 -0.801 0
Cd 1.778 2 2.697 3 -0.012 0 0.000 0
Cr -2.648 0 -3.948 0 -1.242 0 -0.420 0
Ni -1.902 0 -3.739 0 -2.552 0 0.116 1
Table 15
Non-carcinogenic risk index of heavy metals in fly ash by different intake routes.
FA 1 FA 2 FA 3 FA 4
Adult Children Adult Children Adult Children Adult Children
HIing 7.69E-02 1.79E-01 6.36E-02 1.53E-01 1.54E-01 2.16E-01 7.27E-02 1.70E-01

HIinh 1.24E-06 3.80E-06 6.10E-07 1.87E-06 3.46E-06 1.06E-05 4.71E-06 1.44E-05
HIder 1.72E-04 2.82E-04 1.19E-04 1.95E-04 1.64E-04 2.69E-04 1.21E-04 1.98E-04
Total 7.71E-02 1.80E-01 6.37E-02 1.53E-01 1.54E-01 2.16E-01 7.28E-02 1.70E-01
Table 16
Carcinogenic risk index of single heavy metal ingested orally.
Area FA 1 FA 2 FA 3 FA 4
As（CRing） 6.90E-06 1.61E-05 5.00E-06 1.17E-05 1.63E-05 3.81E-05 1.34E-05 3.13E-05

Pb（CRing） 1.27E-07 2.96E-07 5.18E-08 1.21E-07 0 0 8.11E-08 1.89E-07
Cd（CRing） 3.25E-07 7.58E-07 3.29E-07 7.68E-07 4.48E-07 1.05E-06 0 0
Cr（CRing） 5.12E-05 1.20E-04 1.89E-05 4.41E-05 1.85E-04 7.12E-05 1.62E-04 3.77E-04
Table 17
Carcinogenic risk index of single heavy metal ingested by inhalation.
As（CRinh） 1.30E-10 3.98E-10 9.41E-11 2.88E-10 3.08E-10 9.40E-10 2.52E-10 7.71E-10

Pb（CRinh） 4.80E-12 1.47E-11 1.96E-12 6.00E-12 0 0 3.07E-12 9.39E-12
Cd（CRinh） 5.88E-11 1.80E-10 5.96E-11 1.82E-10 8.12E-11 2.48E-10 0 0
Cr（CRinh） 1.14E-10 3.49E-10 4.21E-11 1.29E-10 4.13E-10 1.26E-09 6.01E-10 1.84E-09
Table 18
Carcinogenic risk index of single heavy metal through skin contact.
As（CRder） 2.24E-08 3.67E-08 1.62E-08 2.66E-08 5.30E-08 8.68E-08 4.35E-08 7.12E-08

Pb（CRder） 3.41E-10 5.59E-10 1.40E-10 2.28E-10 0 0 2.18E-10 3.58E-10
Cd（CRder） 2.61E-10 4.27E-10 2.64E-10 4.33E-10 3.60E-10 5.89E-10 0 0
Cr（CRder） 3.24E-08 5.31E-08 1.20E-08 1.96E-08 1.17E-07 1.92E-07 1.71E-07 2.80E-07
these two heavy metals in fly ash need to be controlled. It can be seen from Tables 17 and 18 that the carcinogenic risk index (CR) of
each heavy metal in the four types of fly ash through respiratory intake and skin contact intake is far less than 1 × 10− 6, which means
that these four types of fly ash do not pose a carcinogenic risk to humans under these two ingestion routes. Table 19 shows the
comprehensive carcinogenic risk index (TCR) of the four heavy metals As, Pb, Cr and Cd in each fly ash under different intake routes.
The calculation results show that the four types of fly ash have serious carcinogenic risks in the oral intake route, while skin contact and
inhalation intake will not cause carcinogenic risks to humans.
15
Table 19
Comprehensive carcinogenic risk index of fly ash heavy metals in different intake routes.
FA 1 FA 2 FA 3 FA 4
TCRing 5.86E-05 1.37E-04 2.43E-05 5.67E-05 2.02E-04 1.10E-04 1.75E-04 4.09E-04

TCRinh 3.08E-10 9.41E-10 1.98E-10 6.05E-10 8.01E-10 2.45E-09 8.57E-10 2.62E-09
TCRder 5.55E-08 9.08E-08 2.86E-08 4.68E-08 1.71E-07 2.80E-07 2.15E-07 3.52E-07
Total 5.86E-05 1.37E-04 2.43E-05 5.67E-05 2.02E-04 1.11E-04 1.75E-04 4.09E-04
4.4.4. Effect of fly ash particle size on leaching efficiency of characteristic heavy metals
Based on the results of a risk assessment of heavy metals in fly ash to soil and human health. Taking FA 4 as an example, the most
harmful Cd, Cr and Hg were selected to study the leaching and migration characteristics of heavy metals. In order to study the effect of
fly ash particle size on the leaching efficiency of characteristic heavy metals, the FA 4 was ground into three particle sizes of 26 µm,
12 µm and 5 µm. Three groups of 3 kg of fly ash were taken, and three groups of 3 kg of soil were taken at the same time, and the three
particle sizes of fly ash were naturally stacked on the randomly sampled soil to simulate the natural stacking of fly ash. The contents of
three characteristic heavy metals, Cr, Hg, and Cd, were tested again after 30 days of simulated storage treatment of fly ash with three
particle sizes. The weather for the thirty days was monitored simultaneously during the test. The experimental period was from April
12, 2022 to May 11, 2022. The weather record is shown in Fig. 8. The test results are shown in Tables 20 and 21.
According to the leaching rate data of fly ash characteristic heavy metal 30days in Table 21, it can be seen that the leaching rate of
Hg, Cr and Cd decreases with the increase of fly ash particle size. It shows that for fly ash FA 4, the larger the particle size of fly ash, the
smaller the leaching rate of three heavy metals Hg, Cr and Cd. The leaching rates of the three heavy metals are: Hg>Cr>Cd. That is to
say, Hg in fly ash is more easily leached under the same conditions.
4.4.5. Analysis of the valence state of characteristic heavy metals

The valence state analysis of the characteristic heavy metals in the selected fly ash requiring special control was carried out by
means of XPS to determine their harmful effects on the human body. The XPS detection results of FA4 are shown in Fig. 9. It can be seen
from the above figure a that in addition to Si, Al, O elements, FA 4 fly ash also contains some elements such as Ca, Hg, Cd, and Cr.
Therefore, in this study, XPS narrow spectrum scanning is performed on the three characteristic heavy metals Hg(2p), Cd(3d), and Cr
(2p) in FA 4 fly ash, and the Avantage software is used to perform peak fitting. The fitting results are shown in the figure. b, c, and d.
The XPS narrow spectrum of Cr2p3/2 is scanned for FA 4 and the peaks are fitted. The peak positions are at 579.06 and 576.22 eV,
representing Cr6+ and Cr3+, respectively. The XPS narrow spectrum of Cr2p1/2 is scanned and sub-peak fitting is performed. The peak
positions are at 588.22 and 585.38 eV, representing Cr6+ and Cr3+, respectively [53]. This proves that the valence states of heavy
metal Cr in the fly ash are mainly Cr6+ and Cr3+. The Hg4f in the fly ash is fitted with a peak, and the binding energy is 100.29 eV,
indicating that the Hg in the fly ash mainly exist in the form of Hg2+ [54]. Using Avantage software, the XPS high-resolution spectrum
of Cd3d in fly ash is fitted to obtain two peaks. The binding energies are 405.14 eV and 411.64 eV, respectively. The peak at 405.14 eV
is assigned to Cd3d5/2, and the peak at 411.64 eV is assigned to Cd3d3/2, indicating that the Cd element in fly ash mainly exists in the
form of Cd2+ [55]. The analysis results show that the elements Cr, Hg and Cd in the fly ash exist in the form of Cr6+, Cr3+, Hg2+ and
Cd2+ respectively. Cr6+, Hg2+, Cd2+ have serious carcinogenic risk to human body. Therefore, it is necessary to focus on controlling it.
4.4.6. Migration model of characteristic heavy metals in fly ash

The mobility of heavy metals was judged by studying the relationship between the release amount of characteristic heavy metals in
the soil-fly ash system and the stacking time. The object of this study was FA 4 fly ash with a thickness of 26 µm, and the leaching time
interval was selected as 30 days. A one-dimensional diffusion model based on Fick’s second law [56] was used to evaluate the
migration characteristics of the three heavy metals. The calculation formula is formula 13. Calculation results are shown in Table 22.
( )0.5
S D×t
Mtm = 2 × C0 × (13)
V π
Where: Mtm represents total release of heavy metals per unit mass of sample at time t (mg/kg). C0 represents the release amount of
heavy metals in the sample system (mg/kg). S represents the surface area of the sample device, the surface area of the three groups of
samples is taken as 0.16 m2. V means sample volume, the three groups of sample volumes are all taken as 0.004 m3. D represents
diffusion coefficient. According to the literature [56], DHg= 7.68 × 10− 10, DCr= 4.24 × 10− 14, DCd= 5.10 × 10–19 (m2/s). The t
represents leaching time (s).
According to the data in Table 22, it can be seen that the migration efficiency of the three heavy metals in the first 30 days is
significantly lower than that in the latter 30 days, because the heavy metals in the soil-fly ash system are mainly concentrated in the fly
ash. The migration route of heavy metals in the first 30 days is from fly ash to soil, so the total content of heavy metals change little. In
the last 30 days, due to changes in the physical and chemical properties of the soil and the impact of water flow caused by rainfall,
heavy metal elements migrate, so the total content of heavy metals in the system decrease significantly. According to the longitudinal
comparison of the data in Table 22, it can be seen that the mobility of Hg is stronger than that of Cd and Cr. When the fly ash is stacked
in the yard, the heavy metals in it are released by the external environment such as rainwater and gradually diffuse into the soil and
16
Fig. 8. 30-day weather records.
Table 20
Test results of characteristic heavy metal content in fly ash.
Hg0 Hg30 Cd0 Cd30 Cr0 Cr30
5.5 µm 0.4294 0.1625 0.0723 0.0459 5.1815 2.1324

12 µm 2.2391 1.2264 0.2515 0.1823 7.8373 5.0891
26 µm 1.6662 1.1523 0.5625 0.4356 23.2755 16.8756
Table 21
Calculation results of 30days leaching rate of characteristic heavy metals.
5.5 µm 12 µm 26 µm
Hg 62.16 45.23 30.84

Cd 36.51 27.51 22.56
Cr 58.85 35.07 27.50
groundwater(Fig. 10). Under long-term action, heavy metals in soil and groundwater will exceed the standard, which will endanger the
ecological environment and human health. Therefore, it is necessary to monitor and assess the environmental hazard of soil and
groundwater near the fly ash storage site. The results of this study can be applied in this field.
4.4.7. Risk control value of characteristic heavy metals in different application scenarios of fly ash
According to the results of single-factor index, potential ecological risk index and geoaccumulation index, Hg and Cd all have high
risks in these three evaluation methods. The results of human health risk assessment showed that Cr, Pb and As have carcinogenic risks,
and Cr had the highest carcinogenic risk. Therefore, in this study, Cr, Hg, and Cd were listed as characteristic heavy metal pollutants of
fly ash; Ni was not a potential risk in the three evaluation methods, so Ni was not used as a characteristic heavy metal in fly ash for
prevention and control. This study drew on the "Soil Environmental Quality-Risk Control Standard for Soil Contamination of Agricultural
Land (GB15618–2018)" and "Soil Environmental Quality Control Standard for Soil Contamination of Development Land (GB36600–2018)"
currently issued in China. The reference limits of heavy metals Cr, Hg and Cd in fly ash in different application scenarios are listed in
Table 23. When fly ash is applied to indoor plastering mortar and indoor concrete, it will come into direct contact with people.
Therefore, the most stringent human health risk assessment method is adopted to reduce the carcinogenic risk index of characteristic
heavy metals to below 1 × 10− 6. When fly ash is used on roads, the "Soil Environmental Quality-Risk Control Standard for Soil
17
Fig. 9. XPS detection of characteristic heavy metals of FA 4.
Table 22
Calculation results of release amount (mg/kg).
Initial content 30d 60d M0−
m
30
M30−
m
60
M0−
m
60
Hg 2.3724 1.7970 0.0216 1.16E+ 00 3.58E+ 00 6.69E+ 00

Cd 0.6192 0.5979 0.0652 3.19E-04 7.97E-03 1.17E-02
Cr 23.5818 18.8318 1.0633 2.46E-04 9.22E-04 1.65E-03
Contamination of Agricultural Land (GB15618–2018)" is used as a reference. Risk control was carried out using single factor index,
potential environmental risk index and index of geo-accumulation. Finally, among the three methods, the lowest limit value of
characteristic heavy metals is selected for risk control. Similarly, when fly ash is used in outdoor concrete, the "Soil Environmental
Quality Control Standard for Soil Contamination of Development Land (GB36600–2018)" is used as a reference. The single factor index, the
potential environmental risk index and the index of geo-accumulation are used for simultaneous risk control. Among the three
methods, the lowest limit value of characteristic heavy metals is selected for risk control. This study only limits the content of five
heavy metals in fly ash by scenario. The flow chart of limit value analysis is shown in Fig. 11, where C represents the output limit value,
and the rest of the symbols are the same as those in Section 3.2.5 in this study. The analysis results show that under the current Chinese
national standard conditions, when a large amount of fly ash is stored or utilized as a resource, it is necessary to focus on strengthening
the restriction of Cr, Hg, and Cd content, which have strong carcinogenic risks to the human body. It should be noted that the
18
Fig. 10. Schematic diagram of heavy metal leaching in fly ash storage yard.
Table 23
Reference limit values of characteristic heavy metals in fly ash(mg/kg).
Cr Hg Cd
Indoor plastering mortar and indoor concrete 0.14 0.25 0.3

Road 75 0.5 0.3
Outdoor concrete 75 4 10
characteristic heavy metals of fly ash are different due to different origins. When disposing of fly ash, the content of characteristic
heavy metals in the fly ash should be detected and treated in a harmless manner.
5. Conclusion
The fly ash from four regions in China was selected to study the basic properties and the risk assessment of heavy metals in it. At the
same time, the leaching laws and migration properties of three types of heavy metals with strong hazard were studied. Finally, the limit
values of heavy metal content in fly ash under different application scenarios are given. The specific conclusions are as follows.
Fig. 11. Reference model for characteristic heavy metal limit values.
19
1. The four kinds of fly ash strength activity indices were: FA 2 (82.3%) > FA 3 (77.3%) > FA 4 (73.2%) > FA 1 (70.6%). The content
of active components such as SiO2 and Al2O3 in fly ash led to the difference of its strength activity index. The characteristic peaks of
CaSO4 and CaO appearing in the XRD pattern were due to the addition of desulfurizers. The particle size distribution of the four
types of fly ash was concentrated between 1 and 100 µm. As, Hg, Cd, Cr, Pb and Ni were found in the EDS test pattern of fly ash.
2. Cd in FA 1, FA 2, FA 3 and Hg in FA 2 all exceeded the standard limit value of heavy metals in Chinese agricultural land soil. The
evaluation results of Cd, Pb, As, Cr, Hg and Ni in the four types of fly ash were relatively consistent by single factor index, potential
ecological risk index and index of geo-accumulation. That is, Cd and Hg in FA 1 and FA 2 had high pollution risks to the envi
ronment. The evaluation results of the index of geo-accumulation showed that the Cd in FA3 did not have a strong ecological hazard
because the Cd content in FA 3 was close to the local soil background value.
3. The results of human health risk assessment showed that Cd, Pb, As, Cr, Hg and Ni in fly ash have no non-carcinogenic risk. Under
the oral ingestion route, the carcinogenic risk index of Cr in these four kinds of fly ash was greater than 1 × 10− 4, that is, there was a
significant carcinogenic risk. The same heavy metal content was far more harmful to children’s health than adults. Based on the
results of soil pollution and human health risk assessment of heavy metals in fly ash, three heavy metals, Cr, Cd, and Hg, were
selected as the characteristic heavy metals with strong hazard.
4. FA 4 was selected to study the valence state and leaching and migration law of the heavy metals Cr, Cd and Hg, which were highly
hazardous. XPS analysis results showed that the valence states of the three heavy metals were Cr3+, Cr6+, Cd2+, and Hg2+,
respectively. The leaching rates of Cr, Hg and Cd decreased with the increase of grinding particle size. Experimental test data and
heavy metal migration simulation data showed that these harmful heavy metal ions migrate into deep soil and groundwater
through osmosis, and the mobility of Hg was stronger than that of Cr and Cd.
5. The risk control of Cr, Hg, and Cd was carried out according to the application scenarios of fly ash. Reference limit values for indoor
plastering mortar and indoor concrete: Cr < 0.14 mg/kg, Hg < 0.25 mg/kg, Cd < 0.3 mg/kg. Reference limit values for roads: Cr
< 75 mg/kg, Hg < 0.5 mg/kg, Cd < 0.3 mg/kg. Reference limit values for outdoor concrete: Cr < 75 mg/kg, Hg < 4 mg/kg, Cd
< 10 mg/kg.
CRediT authorship contribution statement
Chao-qiang Wang: Overall audit, experimental design, Data and relevant mechanism analysis, Writing – original draft. Ke Liu:
Assisting with research and experimentation, data and relevant mechanism analysis, revised and editing. De-ming Huang: Assisting
with experimental design, research, experiments and data analysis. Qiao Chen: Assisting with research and data analysis. Min-jie Tu:
Assisting with research and data analysis. Kai Wu: Assisting with experimental design, research and data analysis. Zhong-he Shui:
Assisting with research and data analysis.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
This work was financially supported by Science and technology research project of Chongqing Municipal Education Commission of
China (KJQN202100723), Opening Project of Key Laboratory of Solid Waste Treatment and Resource Recycle, Ministry of Education
(20kfck03), and Opening Project of Key Laboratory of Urban Pollutant Conversion, Chinese Academy of Sciences (KLUPC-KF-2020–2),
Key Laboratory of Advanced Civil Engineering Materials (Tongji University), Ministry of Education (202103), Chongqing Science and
Technology Commission (cstc2017jcyjAX0157), Western Scholar of Chinese Academy of Sciences Category A (E2296201). Opening
Project of State Key Laboratory of Silicate Materials for Architectures (Wuhan University of Technology) (SYSJJ2022–09), State Key
Laboratory of Silicate Materials for Architectures (Wuhan University of Technology) (SYSJJ2022–09).
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Case Studies in Construction Materials 17 (2022) e01422

Contents lists available at ScienceDirect

Case Studies in Construction Materials

Utilization of fly ash as building material admixture: Basic

2. Utilization of fly ash in building materials and it’s heavy metals

2.1. Application of fly ash in cement

2.2. Application of fly ash in concrete

2.3. Application of fly ash in bricks

2.4. Study on heavy metals in fly ash

Fig. 1. Fly ash sample.

3. Materials and methods

3.1. Raw materials

3.2. Experimental method

3.2.1. Determination of fly ash strength activity index

3.2.2. Loss on ignition test method

3.2.3. Instrument of microscopic analysis

FA 1 200WM CFB boiler 690 540 13.73 Limestone

3.2.4. Determination of heavy metal content in fly ash

3.2.5. Heavy metal risk assessment methods

Si 30.00 0.5 70.0 0.3 150 200

background value in China in this study, as shown in Table 3 [33].

CR = ADDi × SFi (11)

4. Results and analysis

4.1. Analysis of fly ash strength activity index

FA 1 9.1 0.095 25.0 0.138 70.2 29.9

IRing Ingestion rate mg⋅d− 1 30 60 [40]

RfDing RfDinh RfDder SFing SFinh SFder

Ni 2.00E-02 5.40E-03 2.06E-02 – – – [43]

4.2. Analysis of loss on ignition of fly ash

4.3. Analysis of micro test results

4.3.1. Analysis of XRF test results

ωLOI 2.10% 2.61% 3.2% 4.2%

4.3.2. Analysis of XRD test results

4.3.3. Analysis of FTIR test results

4.3.4. Analysis of fly ash particle size distribution test results

4.3.5. SEM/EDS analysis of fly ash

FA 1 34.3 15.4 16.3 12.1 4.92 6.42 8.14 1.28

Fig. 2. XRD pattern of fly ash.

Fig. 3. FTIR spectrum of fly ash.

Fig. 4. Particle size distribution of fly ash.

4.4. Analysis of heavy metals

4.4.1. Detection of heavy metal content in original fly ash

4.4.2. Agricultural environmental safety assessment

Fig. 5. SEM images of fly ash (FA 1: a, b; FA 2: c, d; FA 3: e, f; FA 4: g, h).

Fig. 6. The energy spectrum of four kinds of fly ash.

4.4.3. Human health risk assessment

As 6.34 4.59 15.0 12.3 30.00

As 0.211 0.153 0.500 0.410

＜40 Low risk

As 2.11 Low 1.53 Low 5.00 Low 4.10 Low

Igeo Class Igeo Class Igeo Class Igeo Class

As -1.106 0 -1.897 0 -1.000 0 -0.343 0

Adult Children Adult Children Adult Children Adult Children

HIing 7.69E-02 1.79E-01 6.36E-02 1.53E-01 1.54E-01 2.16E-01 7.27E-02 1.70E-01

Adult Children Adult Children Adult Children Adult Children

As（CRing） 6.90E-06 1.61E-05 5.00E-06 1.17E-05 1.63E-05 3.81E-05 1.34E-05 3.13E-05

Adult Children Adult Children Adult Children Adult Children

As（CRinh） 1.30E-10 3.98E-10 9.41E-11 2.88E-10 3.08E-10 9.40E-10 2.52E-10 7.71E-10

Adult Children Adult Children Adult Children Adult Children

As（CRder） 2.24E-08 3.67E-08 1.62E-08 2.66E-08 5.30E-08 8.68E-08 4.35E-08 7.12E-08

Adult Children Adult Children Adult Children Adult Children

TCRing 5.86E-05 1.37E-04 2.43E-05 5.67E-05 2.02E-04 1.10E-04 1.75E-04 4.09E-04

4.4.5. Analysis of the valence state of characteristic heavy metals