Measurement 200 (2022) 111453

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Measurement
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Photocatalysis as a method for reduction of ambient NOx in deep

underground mines
Aleksandra Banasiewicz a ,∗, Anna Janicka b , Anna Michalak a , Radosław Włostowski b
a
Faculty of Geoengineering, Mining and Geology, Wroclaw University of Science and Technology, Na Grobli 15, 50-421 Wroclaw, Poland
b
Faculty of Mechanical Engineering, Wroclaw University of Science and Technology, Łukasiewicza 5/7, 50-370 Wroclaw, Poland

ARTICLE INFO ABSTRACT

Keywords: Air pollution is a critical global issue. The introduction of further restrictions on the emission of harmful gases,
Nitrogen Oxides (NOx) such as carbon monoxide and nitrogen oxides (NOx), is posing a growing challenge to various industries. This
Gas hazards problem also affects the underground mining sector, where in most cases the entire fleets are powered by
Underground mine
diesel engines. It is therefore important, in order to improve the health and safety of underground miners,
Safety in mine
to develop appropriate methods to reduce exposures of underground miners to harmful gas and particulates.
This study investigated the effectiveness of photocatalysis as a method to reduce the concentration of nitrogen
oxides in underground copper mines in Poland. The study was based on laboratory measurements using an AVL
GAS PEMS gas analyzer. A number of experiments were carried out and the results obtained were subjected to
statistical analysis. By fitting appropriate curves – linear and sums of two exponents – an assessment was made
of the process carried out comparing the obtained coefficients. This study showed that methodology based on
photocatalysis has potential as a strategy for controlling exposures of underground miners to nitrogen dioxide.

1. Introduction Due to the negative impact of the above-mentioned substances,

The environmental conditions in deep underground mines are very
difficult, therefore intensive research, engineering, and technical work
are being carried out to improve them. The challenges associated
with controlling environmental conditions are increasing with ever-
increasing mine depths [1–6]. Dong et al. [7] and Zietek et al. [8]
report in their articles that combating the natural hazards present in
mines, such as climate hazards, gas hazards, fire hazards, and dust
hazards, is becoming increasingly difficult. In addition, the growing
awareness of people regarding their health and safety at work, as well
as the observable negative changes in the living environment caused
by industrial activity, are the basis for the development of sustainable
mining. The main action to contribute to its development is legal
changes concerning the introduction of increasing restrictions on the
emission of harmful gases into the atmosphere.
According to Banasiewicz [9] referring to the regulations of [10] the
most problematic and harmful gaseous substances are carbon monoxide
(CO), nitric oxide (NO), and nitrogen dioxide (NO2 ). NO, and NO2
are collectively referred to as NOx [11,12]. In addition to gaseous
substances, submicron particulates from diesel engines are a major
problem [13–15]
more stringent concentration limits in mine workings are being in-
troduced. The underground mining industry is facing difficulties in
reducing harmful gases. One of the main reasons is that relatively
large air streams of the mine atmosphere contain low levels of harmful
oxides. As the main sources of CO, NO, and NO2 in underground
mining are diesel machinery — it is on them that attention should be
focused [9].
Nitrogen oxide reduction methods can be divided into primary,
intake, and hybrid configurations. Primary methods include air staging,
low-emission burners, fuel staging, reduced air heating, and exhaust
gas recirculation. Secondary methods are mainly based on reducing
medium injection into gases in catalytic (SCR) or non-catalytic (SNCR)
selective reactions [16,17].
The research presented in this paper deals with the effectiveness
of NOx reduction using the photocatalysis process. This process, in
comparison with traditional — expensive methods of reducing harmful
gases, additionally does not require high temperatures for carrying out
the reaction [18].
The study was performed using titanium dioxide (TiO2 ) based pho-
tocatalytic coating. In order to achieve the target environmental con-
ditions (similar to real conditions in a deep underground mine on

∗ Corresponding author.
E-mail addresses: aleksandra.banasiewicz@pwr.edu.pl (A. Banasiewicz), anna.janicka@pwr.edu.pl (A. Janicka), anna.michalak@pwr.edu.pl (A. Michalak),
radoslaw.wlostowski@pwr.edu.pl (R. Włostowski).

https://doi.org/10.1016/j.measurement.2022.111453
Received 12 November 2021; Received in revised form 4 May 2022; Accepted 6 June 2022
Available online 14 June 2022
0263-2241/© 2022 Elsevier Ltd. All rights reserved.
A. Banasiewicz et al.
the example of copper ore mines of KGHM Polska Miedź S.A.), mea-
surements were carried out in a high and low-temperature chamber.
The temperature and humidity inside the test chamber were similar to
that observed in the mine Once the relevant environmental conditions
(temperature and humidity) had been obtained, the equivalent climatic
temperature (t𝑧𝑘 ) was checked — an indicator relating to Polish under-
ground mines that determine the possibility of working in underground
conditions due to high temperatures.
If it is not possible to reduce emissions of harmful substances into
the mine atmosphere, the only solution may be to replace the entire
machine park with current diesel engines with EURO Stage V or Tier 4
final engines or with electrically driven machines. Unfortunately, such
a solution takes time, its fast implementation is impossible and in many
companies may result in the closing part of the excavations or the whole
mine due to too high cost [8,9]. In the case of numerous operations,
however, the replacement of a significant part of diesel vehicles with
electric vehicles is practically inevitable in the next several years. The
economics of that process is still developing.
2. State of the art
Nowadays, the topic of air pollution is one of the most important
and loudest problems in the world. It is connected with almost every
branch of the economy. One of the most interesting chemical com-
pounds affecting the environment, atmosphere, and human health is
nitrogen oxides (NOx). According to Hesterberg and el. [19], the origin
of NOx compounds in the atmosphere is mainly related to anthro-
pogenic activities. Energy generation activities and, most importantly,
the ever-increasing number of vehicles with internal combustion or
diesel engines contribute to NOx air pollution [20,21].
Diesel-powered machines are the main contributors to mine air
pollution. The exhaust fumes from the operation of these machines
contain many chemical compounds – in solid, liquid, and gaseous states
– that are harmful to humans. The most important of these, according
to Debia [14], include carbon monoxide (CO), carbon dioxide (CO2 ),
nitric oxide (NO), nitrogen dioxide (NO2 ), sulfur dioxide (SO2 ), hy-
drocarbon compounds (CH𝑥 ), and diesel particulates. Following Rößler
approaches [22] it is nitrogen oxides that are considered most critical.
The author states in his publication that mainly two oxides of nitrogen,
NO and NO2 , are defined in diesel engine exhaust. Diesel engines that
are not equipped with SCR systems emit a mixture of nitrogen oxides
with NO making more than 90% and NO2 making up to 10% of that
mixture.
Both NO and NO2 are odorless gases, with nitric oxide additionally
being a colorless gas. Nitrogen dioxide, on the other hand, is a gas that
often takes on a brown coloration at high concentrations [21,23]. Nitro-
gen oxides are absorbed into the body through inhalation, ingestion, or
through the skin. The problems caused by groups of NOx compounds
are mainly eye irritation, respiratory irritation, lung disease, and up-
per respiratory tract disease [24–28]. Many studies conducted so far
conclude that NO2 is a more toxic gas than NO [29]. Following [30],
concentrations above 1.5 ppm already cause a significant increase in
respiratory distress. At a value of 5 ppm, a drop in human blood
pressure is observed. Human exposure to concentrations of NO2 in the
range of 25–75 ppm causes bronchitis or acute pneumonia. In addition
to its effects on the bronchi and lungs, NO2 also causes hemoglobin
to be converted to methemoglobin. Concentrations above 300 ppm
cause acute pulmonary edema and hypoxia, resulting in death. As
nitrogen oxides have such a strong and harmful effect on the human
organism, ensuring the safety of underground workers is of paramount
importance. It is therefore critical to select an appropriate method
for reducing NOx in underground workings. An appropriately selected
method will allow the mining of raw materials to continue without
endangering the health and lives of workers.
In addition to the negative impact on living organisms, nitrogen ox-
ides also have an impact on the environment. NO, and NO2 compounds,
2
Measurement 200 (2022) 111453
as confirmed by numerous publications, have a negative impact on the
atmosphere. The NO2 compound present in the troposphere under the
influence of photons (UV radiation) decomposes into NO and an oxygen
atom (O). The latter reacts with an oxygen molecule (O2 ) to form ozone
(O3 ) which is a greenhouse gas that negatively affects human health in
the low parts of the atmosphere. In turn, nitrogen oxide (NO) found in
the higher parts of the atmosphere — in the stratosphere, through its
propensity to react with ozone (O3 ) leads to the formation of NO2 and
O2 , which consequently results in the destruction of the ozone layer
and climate change on Earth [21,31–34].
The world has been introducing restrictions on the emission of
harmful substances into the atmosphere for some time. In the countries
of the European Union, restrictions on the emission of concentrations
of compounds such as carbon monoxide, nitrogen oxide, and nitrogen
dioxide were normalized by Directive 2017/164/EU in 2017. These
restrictions were introduced after the publication of the act in all
industrial sectors, except for the underground mining and tunnel con-
struction sector, for which a transition period ending on August 21,
2023, was set [35]. This period has been set to allow for technological,
technical, and organizational changes that will allow the plants to
continue operating Traditional methods of reducing these compounds
are risky, expensive, and require high reaction temperatures. Currently,
research is carried out all over the world to find proper methods
of NOx reduction or their complete elimination. The researches are
mainly devoted to techniques using photocatalysis processes such as
photocatalytic oxidation, decomposition, or photo-selective catalytic
reduction. The aforementioned methods allow for lowering the reaction
temperature while increasing the conversion efficiency of [36–39].
Oxides such as zinc oxide, platinum oxide, and molybdenum oxide
can be used alone or as an admixture in the photocatalysis process, and
the most commonly used one is titanium dioxide (TiO2 ). According to
Nguyen et al. and Nikokavour, et al. [39,40], TiO2 is most commonly
used as a catalytic coating in photocatalysis due to its wide availability,
low cost, and, most importantly, chemical stability and reliable cost. As
proved in many studies [39,41–43], TiO2 -based photocatalytic surface
strongly affects the photocatalytic NOx oxidation activity.
An underground mine is characterized by difficult environmental
conditions. Most methods of reducing harmful compounds from the
atmosphere can prove ineffective under deteriorating operating con-
ditions. An example is an original method, which assumes adjusting
the intensity of ventilation, i.e. increasing the air stream ventilating
the excavations when the normalized concentrations are exceeded. Due
to the scale of the increase in gas hazards, increasing the airflow rate
will cause the permissible values of air velocity in the excavation to
be exceeded. The world is now concentrating on improving existing
or developing new methods of reduction. Dilution by ventilation will
still be necessary and effective, but may not be sufficient to keep
concentrations below the new standards.
3. Experiment description
3.1. Test bench
The experimental work was done out using a low-temperature and
a high-temperature chamber, where the actual measuring station was
placed (Fig. 1(a)). The test stand consists of a hermetic measurement
chamber in which plates with a catalytic substance can be placed.
Above the plates, there is a connection plate for the light source (UV
LED) with the possibility of dividing the illuminated surface up to eight
sections. The distance between the plates and the light source can be
adjusted in steps of 5 mm in the range of 20–45 mm. The stand allows
testing of active surfaces up to 0.2 m2 . Depending on the research
needs, the effectiveness of coatings can be tested on single gases,
engine exhausts, or mixtures together with atmospheric air. During the
measurements, the concentrations of the criteria gases (NO and NO2 )
in the chamber were measured using an AVL GAS Portable Emission
A. Banasiewicz et al. Measurement 200 (2022) 111453

Fig. 1. Measurement station in the high and low temperature chamber.

Table 1
Gas analyzer parameters.
Range Unit Accuracy
NO 0 ÷ 500 ppm ± 0.2% FSa or ± 2% rel
NO2 0 ÷ 250 ppm ± 0.2% FSa or ± 2% rel
◦
Temperature −10 ÷ +45 C
Humidity ≤95%, non-condensing %
Max. exhaust pressure ± 50 mbar rel.
Weight Approx. 50 kg without accessories kg
Dimensions 19" x 8 HU x 670 (W x H x D) mm
a
FS (full scale).

Fig. 2. Measuring station scheme. 1. Cleaning module ; 2. Hermetically sealed chamber; 3. Gas cylinder with reference gas; 4. Flow meter for metering the amount of inlet gas;
5. Fan; 6. Flow meter to determine the speed of air flow through the stand; 7. AVL GAS PEMS gas analyzer.

Measurement System (PEMS) gas analyzer (Fig. 1(b)). The gas analyzer
used in this study uses the Non-Dispersive Ultra Violet Spectroscopy
(NDUV) method to measure the concentrations of the oxides of interest
(NO and NO2 ) [44–47]. The gas analyzer used in this study uses the
NDUV method to measure the concentrations of the oxides of interest
(NO and NO2 ). The specifications for the analyzer are shown in Table 1.
Fig. 1(a) shows the test bench consisting of a hermetically sealed
chamber (1), AVL Gas PEMS gas analyzer (2), reference gas cylinder
(3), shut-off valve (4), gas return line (5). The purification module
inside the hermetically sealed chamber is shown in Fig. 3. It should
be noted that the gases circulated in a closed-loop system.
After the reference gas was introduced into the chamber and the
measuring stand was started up - a continuous analysis of the air
composition was performed. The air samples collected by the analyzer
were then returned to a hermetically sealed chamber. A schematic of
the measuring station with the direction of the airflow and a description
of the individual components of the diagram (Fig. 2) is shown below.
The interior of the hermetically sealed chamber is shown in Fig. 3.
An octagonal cleaning module with a photocatalytic coating was placed
on the test stand (Fig. 3(a)). Additionally, an axial fan was mounted on
the module inlet, forcing air circulation inside the module. Fig. 3(b)
shows the interior of the purification module. The TiO2 -based pho-
tocatalytic coating was applied to the inner walls. Due to the pro-
posed reduction method (photocatalysis), the device was equipped with
luminous UV LEDs also visible in Fig. 3(b).
The focus was on measurements of NO and NO2 that make the
majority of NOx in the diesel exhaust [48–50]. The discrete vibrational
absorption bands and absorb radiation of NO and NO2 are in the
wavelength range from 200 to 500 nm. According to Maggos et al. [51],
UV light activates the coating consisting of TiO2 , and nitrogen oxides
are oxidized to nitrate. Chemical reactions take place in the AVL GAS
PEMS gas analyzer, which can be represented by a scheme of equations:
N2 + O2 → NO∗2 → NO + ℎ𝜈 (1)

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A. Banasiewicz et al. Measurement 200 (2022) 111453

Fig. 3. Cleaning module with TiO2 coating.

Table 2
Environmental parameters in the climate chamber.
2NO → N2 + O2 (2) Parameter Symbol Value Unit
◦
The radiation emitted by the UV radiation source is modulated using Temperature measured with a dry thermometer t𝑠 36.0 ±0.2 C
◦
Temperature measured with a wet thermometer t𝑤 29.1 ±0.2 C
a filter wheel and split into a measuring beam and a reference beam in Relative humidity 𝜙 60.0 ±0.3 %
a semitransparent beam splitter. In one measurement cycle, a total of Atmospheric pressure p 1010.0 ±0.4 hPa
four signals are recorded for two interference filter positions via the Air flow speed v 2.0 m/s
Equivalent climate temperature t𝑧𝑘 29.86 ◦C
measurement beam and the reference beam and calculated with the
formation of double quotients. This four-beam method forms the basis
for the high measuring stability attained in the NO measurement. It
makes the analyzer largely independent of any contamination in the bench. The volumetric flow rate through the analyzer was approxi-
measurement cuvette or aging of the radiation source. mately 3.5 L/min (according to the analyzer documentation). The flow
rate through the purification module was determined by a fan forcing
3.2. Measurement method air through the module The variable parameter was the pressure in the
chamber, which depended on the atmospheric pressure. The pressure
The first point before the actual start of the research was to stabilize given in the table is that of one measurement day.
the climate conditions in the low-temperature and high-temperature According to the ordinance of the [10], the equivalent climate
chamber, that is humidity and temperature conditions similar to those temperature (t𝑧𝑘 ) at the workstation in underground copper ore mining
prevailing in actual mine conditions (temperature about 36 ◦ C and plants must not exceed 32 ◦ C. For the set and measured values, t𝑧𝑘 was
humidity above 60%). According to Kotarba et al. [52], currently, calculated for the test stand.
in Polish ore mines, the air temperature in the deepest parts where
Before the measurement, the test stand hermeticity was tested by
mining is carried out is 35–45 ◦ C. Following the current regulations
creating pressure inside the measuring chamber (0.2 MPa), and observ-
contained in the [10] - if the air temperature measured with a dry
ing the pressure drop on the manometer, and checking all connections
thermometer exceeds 28 ◦ C (found in Polish copper ore mines), a
and seals with a leak detector. The next stage of the research was to
substitute climate temperature must be determined. If this temperature
perform a series of measurements for two operating conditions of the
is greater than 26 ◦ C but does not exceed 32 ◦ C - the underground
test stand. The first operating condition involved taking measurements
crew shall be allowed to work reduced hours (6 working hours). This
in an empty hermetically sealed chamber (without the purification
ambient temperature is mainly due to the high original temperature
module inside) to determine the spontaneous change in concentration
of the rocks — according to Soroko et al. [53], with values even
state. The second state of operation concerned the situation when in
above 45 ◦ C. In addition, heat is given off to the atmosphere by
a hermetically sealed chamber the purification module was placed
mining machinery (heated machine parts, exhaust gases). To calculate
in operation with the photocatalytic coating – based on TiO2 and
the equivalent climate temperature (t𝑧𝑘 ), temperature values measured
with a dry thermometer and a wet thermometer were measured using illuminated with UV light – applied on the inner walls. Each mea-
an Assmann psychrometer. The pressure inside the hermetically sealed surement lasted approximately one hour and each measurement was
chamber was close to atmospheric pressure. After the reference gas was repeated three times. Basic measurements were carried out in two steps,
injected into the chamber, the chamber valve was closed after about 5 s i.e. for a mixture of nitric oxide (NO) and nitrogen dioxide (NO2 )
to equalize the pressures. The pressure was measured using a sensor with air. In summary, the test methodology included measurement of
connected to a gas analyzer on the test bench. gas concentration for a mixture of nitrogen oxide (NO) and nitrogen
The environmental parameters are given in Table 2 apply to all test dioxide (NO2 ), as follows:
periods. Temperature and humidity values were set top-down in the
1. Step I - measurements of the NO2 gas mixture:
low and high-temperature chamber. Any changes in the parameters
were within the measurement error of the measuring instruments. The (a) Scenario A - operating condition without purification
same gas flow rate was enforced each time on the appropriate test module inside a hermetically sealed chamber,

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A. Banasiewicz et al. Measurement 200 (2022) 111453

Table 3 Table 4
The concentrations of the selected gases at the start of the tests and at the end of the Linear relationship coefficients and corresponding R-square parameters.
tests. Linear p1 p2 R-square
Concentration Gas concentration
NO2 without UV (1) p1*t + p2 −0.001477 17.58 0.9835
Start of the measurement End of the measurement NO2 without UV (2) p1*t + p2 −0.001559 17.73 0.9887
NO2 without UV (3) p1*t + p2 −0.00149 17.97 0.9945
ppm ppm % Vol. % Vol. ppm ppm % Vol. % Vol.
NO NO2 O2 CO2 NO NO2 O2 CO2
0.10 17.10 20.80 0.00 0.60 12.60 20.50 0.01
Step I - A 0.00 17.00 20.80 0.01 0.60 11.20 20.70 0.01 can be approximated by using nonlinear least-squares method with the
0.10 17.10 20.60 0.01 0.80 12.50 20.40 0.01
trust-region algorithm [54]. The concentration of NO2 decrease faster
0.40 17.10 20.90 0.01 5.20 2.20 20.70 0.01 than in the first case. The proposed model has the following form
Step I - B 0.50 17.00 20.40 0.01 5.90 2.80 20.10 0.01
0.90 17.10 20.10 0.01 6.70 1.90 20.00 0.01 𝑦𝑈 𝑉 _𝑁𝑂2 = 𝑎 ∗ 𝑒𝑏∗𝑡 + 𝑐 ∗ 𝑒𝑑∗𝑡 (4)
Step II - A 21.50 5.10 20.90 0.05 14.40 8.40 20.90 0.05
where 𝑎, 𝑏, 𝑐, 𝑑 are constant parameters, 𝑡 is the time and 𝑒 is the
Step II - B 22.80 3.60 20.70 0.05 17.10 4.00 20.60 0.05
exponential function.
The coefficient of determination (𝑅2 ) was used to determine the
goodness of fit of a model. It takes values between 0 and 1. The 𝑅2
(b) Scenario B - operating condition with purification module coefficient assess how good the regression model is. If 𝑅2 takes the
inside a hermetically sealed chamber. values close to 1, it means that the regression predictions fit to the data
very well.
2. Step II - measurements of the NO gas mixture:
4. Results
(a) Scenario A - operating condition without purification
module inside a hermetically sealed chamber,
4.1. Nitrogen dioxide reference gas - step i
(b) Scenario B - operating condition with purification module
inside the hermetically sealed chamber.
The first stage of the experiment concerned the measurement of
The chamber in which the measurements were conducted was filled nitrogen dioxide (NO2 ) values. For this purpose, the measuring station
with atmospheric air before the appropriate gas mixtures were injected described and shown in Fig. 2 above was used and the reference gas
into it. Table 3 shows the concentrations of the selected gases at the NO2 was introduced. The NO2 concentration values were measured
start of the tests and at the end of the tests. using the AVL GAS PEMS analyzer — separately for the operating
The respective gas concentrations were achieved by injecting a condition with the purification module (scenario B) and without the
mixture of synthetic gases into the measuring chamber until the con- module inside (scenario A). The values measured for one hour are
centration close to 17 ppm of NO2 was reached inside the measuring shown in the graph below (Fig. 4). The experiment was repeated
chamber. This value was top-down in order to be able to compare three times for each case. In addition, NO concentration values were
individual measurements. As gas mixtures were used for: measured during the experiment.
The graph clearly shows that there is a significant reduction in
• Nitrogen dioxide — mixtures of synthetic air and NO2 with a NO2 concentration when the purification module is in the middle of
concentration of 200 ppm, the hermetically sealed chamber. In each of the three cases, there is
• Nitric oxide — mixtures of nitrogen and NO with a concentration a decrease in the gas concentration from a value of about 17.0 ppm
of 200 ppm (due to the low stability of NO in air, synthetic air is to about 2.5 ppm per hour. In the operating state of the unit, when
not used as a fill gas). the hermetically sealed chamber is empty (without module), the NO2
content decreases slightly.
3.3. Data analysis For NO2 data without a module in a hermetically sealed chamber,
the decrease can be described by a linear relationship (coefficients in
In the next step, the authors analyze the obtained data series sets Table 4), a table fit R2 of 0.98 indicates that the proposed linear model
for the NO2 reference gas depending on the application or not of describes well the behavior occurring in the data.
the photocatalytic module. Based on their time behavior, linear and For NO2 data with the purification module in the middle of the
nonlinear models can be applied. hermetically sealed chamber, we can describe the slope by the sum of
2 exponents (coefficients in Table 5), a table fit R2 of 0.99 indicates
3.3.1. Linear model that the proposed linear model describes well the behavior occurring
in the data.
For NO2 reference gas without the photocatalytic module, the de-
The next graph below shows the concentration of nitric oxide (NO)
crease of NO2 concentration can be described by a linear relationship.
concentration during the interaction of the purification module with
The parameters of these linear relationships can be approximated by
the introduced NO2 gas and under operating conditions in an empty,
using the linear least-squares method. A simple linear model describing
hermetically sealed chamber (that is, without the purification module)
the time dependence of y𝑁𝑂2 has the following form
(see Fig. 5).
𝑦𝑁𝑂2 = 𝑝1 ∗ 𝑡 + 𝑝2 , (3) Data shows that when NO2 undergoes photocatalysis, as the NO2
content decreases, the NO content increases. This may suggest that NO2
where 𝑝1 is the parameter of the slope, 𝑝2 is the constant coefficient is partially reduced to NO. The apparent increase in NO concentration
and 𝑡 is the time. for the empty chamber indicates the spontaneous transformation of
NO2 inside the chamber. Successively, the graphs below show the sum
3.3.2. Non-linear model of NOx (NO + NO2 ) of each of the three measurements in the operating
For NO2 calibration gas with a TiO2 coated photocatalytic module condition of the device with the purification module installed in the
placed in a hermetically sealed chamber, the authors observe the non- chamber 6(a) and the chamber without the module 6(b).
linear relationship (the best fit was obtained using the sum of two ex- In the plot of 6(a) we can observe a decreasing content of NOx
ponential functions). The parameters of the model presented in Eq. (4) concentrations with measurement time for the two cases of operating

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A. Banasiewicz et al. Measurement 200 (2022) 111453

Fig. 4. Diagram of the time dependence of NO2 reduction as a function of the operating state.

Fig. 5. NO concentration reduction time dependence diagram in relation to the operating state.

Fig. 6. NOx concentration.

6
A. Banasiewicz et al.
Table 5
Sum of 2 exponential coefficients and corresponding R-square parameters.
Sum of two exponential
NO2 with UV (1) a*exp(b*t) + c*exp(d*t)
NO2 with UV (2) a*exp(b*t) + c*exp(d*t)
NO2 with UV (3) a*exp(b*t) + c*exp(d*t)
Fig. 7. Concentration diagram at different operating conditions for references gas NO.
conditions. It should be noted, however, that in the presence of the
purification module the decrease in the sum of NOx concentrations is
more pronounced, and after about 40 min even a slight increase can
be seen. This increase may be due to an increase in the concentration
of reactive oxygen species formed in the reduction reaction of NO2 to
NO, which probably oxidizes nitrogen to NO2 or NO. This phenomenon
will be verified in subsequent research work. For the sum of NOx in the
chamber without module 6, the decrease in concentrations is close to
linear with a tendency for the concentration gradient to decrease as a
function of time.
4.2. Nitric oxide reference gas - Step II
The second stage of the experiment concerned the measurement
of nitric oxide (NO) concentration values. During this stage, as in the
NO2 measurement, a reference gas was introduced into the chamber,
this time based on NO. The experiment was carried out for a single
measurement with the purification module and an operating condition
without the module inside a hermetically sealed chamber. An AVL GAS
PEMS gas analyzer was also used to measure the concentration values.
The NO and NO2 values measured for one hour are shown in the graph
below (see Fig. 7).
Analyzing the above graph, it can be seen that the purification
module with the photocatalytic coating based on TiO2 does not affect
the reduction of nitric oxide concentration. The curves of the concen-
tration values for both the operating condition with and without the
purification module in the center of the hermetically sealed chamber
are practically parallel to each other. This means that the nitrogen
oxide is not reduced by photocatalysis. Analyzing the curves of nitrogen
dioxide concentrations for the NO reference gas, it can be seen that with
the purification module on (photocatalysis process) their amount is
practically constant, which confirms the effectiveness of NO2 reduction.
5. Discussion and conclusions
In order to investigate the effect of the photocatalysis process on
NOx compounds under given conditions, tests were carried out on NO
Measurement 200 (2022) 111453
a b c d R-square
14.68 −0.0009442 2.124 −9.437e−06 0.9996
15.34 −0.0009357 1.994 2.729e−05 0.9994
13.89 −0.0009518 3.25 −6.509e−05 0.9996
and NO2 . The test results, their interpretation, and analysis allowed us
to draw the following conclusions:
1. The results presented in this article are based on the performance
of tests under laboratory conditions using synthetic gases. Per-
forming tests under laboratory conditions are necessary to assess
the validity of the experiment — an important step before per-
forming measurements under real mine conditions. The next step
will be to carry out pilot tests in an underground mine, based on
the concept of the experiment under laboratory conditions.
2. A photocatalysis process using a TiO2 -based catalytic coated
purification module effectively reduces NO2 concentration un-
der laboratory conditions simulated to mine conditions. Tests
were carried out to demonstrate the qualitative potential of the
photocatalysis process as a method of reducing NOx compounds.
The research has shown that a TiO2 -based catalytic coated pu-
rification module reduces nitrogen dioxide very well in the first
stage (Step I, scenario B). The reduction of this gas is probably
based on the breakdown of the compound into two separate
compounds — the free O molecule and the NO compound. We
can conclude this from the observed increase in the values of
nitric oxide concentrations with simultaneous reduction of NO2 .
Additionally, analyzing the results from the second stage (step I,
scenario A), where NO was the reference gas, it is noticeable that
at the operating condition with an empty chamber the content
of NO2 increases, while under the same conditions, but with the
participation of the photocatalysis process, the value of this gas
practically does not change.
3. Photocatalysis using a TiO2 -based catalytic coated purification
module does not reduce NO concentration under laboratory
conditions simulated to mine conditions. Tests carried out to
evaluate the effectiveness of the photocatalysis process as a
method of reducing NOx compounds showed that the NO com-
pound is not reduced in the photocatalysis process. The tests
carried out clearly indicated a similar behavior of the gas both
in the operating condition with an empty chamber (Step II,
scenario A) and with the purification module (Step II, scenario
7
A. Banasiewicz et al.
B) fitted. These results are also confirmed by the correlation
mentioned in conclusion 1 between the increase in nitric ox-
ide and the simultaneous reduction of nitrogen dioxide using
photocatalysis.
4. Due to the selectivity of the action on particular groups of com-
pounds, the effectiveness of the photocatalytic coating should
be verified for other wavelengths of the UV source. Further
studies should investigate the effect of other wavelengths of the
UV source on nitric oxide and nitrogen dioxide. It should be
checked whether the NO compound will undergo photocatalysis
at a different wavelength of UV radiation. Next, it is necessary
to analyze how a change in the wavelength of UV radiation will
affect the NO2 compound — an increase or decrease in the gas
reduction efficiency.
5. The selection of an appropriate NOx reduction method is es-
sential to ensure that mineral resources can continue to be
exploited in underground mines and, above all, to ensure the
safety of underground workers. As stated in Section 1, it is
the exhaust gases from diesel-powered machinery that generate
the most harmful chemicals. Research should therefore focus
primarily on the fleet of combustion machinery. Based on basic
research, photocatalysis appears to be a promising process for
reducing concentrations of harmful nitrogen oxides in mine air.
The research needs to be continued, especially with regard to
application in real conditions In further research work, studies
can be planned on the effectiveness of the proposed method pre-
sented in the manuscript to current SCR systems. These studies
will verify the cost-effectiveness of the method presented in the
manuscript.
6. The NOx reduction method proposed in this paper can form the
basis for further research into reducing the emissions of harmful
gases into mine workings from internal combustion engines.
CRediT authorship contribution statement
Aleksandra Banasiewicz: Conceptualization, Methodology, Valida-
tion, Investigation, Resources, Writing – original draft, Writing – review
& editing, Visualization. Anna Janicka: Conceptualization, Resources,
Writing – review & editing, Supervision. Anna Michalak: Valida-
tion, Resources, Visualization. Radosław Włostowski: Methodology,
Validation, Investigation, Resources.
Declaration of competing interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgment
R & D works are carried out in the GEO-3EM research complex
of the Wroclaw University of Technology, Na Grobli 13 street, Wro-
claw. This work is supported by European Institute of Innovation and
Technology (EIT), a body of the European Union, under the Horizon
Europe, the EU Framework Programme for Research and Innovation.
EIT RawMaterials GmbH under Framework Partnership Agreement
No. 21119 (VOT3D: Ventilation Optimizing Technology based on 3D-
scanning). All authors have read and agreed to the published version
of the manuscript.
8
Measurement 200 (2022) 111453
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