Construction Research Congress 2012 © ASCE 2012 1920

Nitrogen Oxide Reduction and Nitrate Measurements on TiO2 Photocatalytic

Pervious Concrete Pavement

Marwa HASSAN1, Somayeh ASADI2, John T. KEVERN3, and Tyson

RUPNOW4

1
Louisiana State University, Department of Construction Management and Industrial
Engineering 128 PFT hall, Baton Rouge, LA, 70803; Email: marwa@lsu.edu
2
Louisiana State University, Department of Construction Management and Industrial
Engineering 3128 PFT hall, Baton Rouge, LA, 70803; Email: sasadi4@lsu.edu
3
University of Missouri-Kansas City, CE Department, assistant professor, 370H
Flarsheim Hall, 5100 Rockhill Rd. Kansas City, MO 64110-2499, email: kevernj@umkc.edu
4
Louisiana Transportation Research Center, Concrete Research Engineer, Louisiana
Transportation Research Center, 4101 Gourrier Ave., Baton Rouge, LA 70808, email:
tyson.rupnow@la.gov

ABSTRACT
Photocatalytic compounds such as titanium dioxide (TiO2) can be used to construct
pervious concrete pavements that can trap and degrade organic and inorganic particles in the air.
Photocatalytic pervious pavements transform harmful pollutants such as nitrogen oxides (NOx)
into nitrates salts when subjected to UV light from the sun purifying ambient air from vehicle
emissions. In spite of these benefits, an increase in nitrate levels may cause eutrophication. The
objective of this study is to evaluate the amount of nitrates released due to pervious
photocatalytic concrete and to assess potential eutrophication issues. To achieve this objective,
pervious concrete samples were tested in the laboratory for photocatalytic NOx reduction
efficiency according to JIS standard. The test was performed using an innovative lab setup and
conducted under different environmental and operational conditions including flow rate, UV
intensity, temperature, and relative humidity. After testing, samples were washed with deionized
water (DI) to collect the nitrates deposited on the surface. The concentration of nitrates collected
was measured using a colorimetric method known as cadmium reduction. Results showed that
photocatalytic pervious concrete is capable of purifying ambient air from NOx. Results also
showed that the concentrations of nitrate deposited on the surface are low and will not cause
eutrophication problems.

Keywords: Titanium dioxide, sustainable pervious concrete pavement construction,

photocatalyst, nitrogen oxides.

INTRODUCTION
Man-made ambient air pollution originates from poisonous gases emitted by traffic and
industrial activity. Traffic emissions include nitrogen oxide (NOx), which is identified as a
significant urban pollutant in major US cities. The US Environmental Protection Agency (EPA)
reported that the largest emissions of NOx originate from on-road motor vehicles (EPA 2010). In
Construction Research Congress 2012 © ASCE 2012 1921

fact, 35% of NOx, 60% of the carbon monoxide, and 25% of Volatile Organic Compounds
(VOCs) were attributed to vehicular emission in the US in 2005 (EPA 2010).
A solution to traffic air pollution is treatment of pollutants as close to the source as
possible (Beeldens 2008). Since automobile emissions come in contact with the road surface,
photocatalytic compounds such as TiO2 can be used to construct air purifying pavements by
integrating nano-TiO2 within the pavement surface. Photocatalytic highway pavements can trap
and decompose harmful pollutants including NOx, which is converted to water soluble nitrates
(Hassan et al. 2010). One concern of using photocatalytic pavement is that nitrate in water can
cause eutrophication. EPA estimates that eutrophication is the main cause of impaired surface
water quality (EPA 1999). Eutrophication is a process by which a body of water acquires high
concentration of nutrients leading to high growth rate of algae, which in time dies and
decomposes. The high nutrients in the water, as well as the decomposition of the algae, deplete
the body of water of its oxygen causing the death of other organisms.
The objective of this study is to quantify the amount of nitrates that are released due to
photocatalytic compound used in the preparation of pervious concrete and to assess its potential
effect on eutrophication. To achieve this objective, pervious concrete samples were tested in the
laboratory for photocatalytic NOx reduction efficiency according to Japanese Industrial Standard
(JIS) standards. Testing was conducted under different environmental and operational conditions
including flow rate, UV intensity, temperature, and relative humidity. To quantify the amount of
nitrates released due to photocatalytic activities, the colorimetric method of cadmium reduction
with a Shimadzu UV Spectrophotometer 1800 was adopted. Results were used to evaluate
potential eutrophication issues using the BEES model developed by EPA (2002).
EXPERIMENTAL PROGRAM

Laboratory Samples
Since nitrate salt is a direct product of photocatalytic activity, laboratory measurements
were conducted in this study to quantify the amount of nitrate deposited on the specimen surface.
Nitrate salts deposited on the pavement were measured for 21 samples with different design
parameters including three different void ratios (23, 27, and 31%) in combination with four
different depths of TiO2 (0.5, 1, 2, and 3 inches). The mixture proportions associated, with each
particular void content is shown in Table 1. The environmental efficiency of the prepared
pervious concrete in removing NOx pollutants from the air stream was evaluated at different
levels of pollutants’ flow rates, relative air humidity, temperature, and UV light intensities. Test
specimens were prepared in triplicates with dimensions of 10 in x 10 in x 3 in.
Laboratory Testing
The experimental setup used to collect the laboratory data was modified from the
Japanese Industrial Standard (JIS TR Z 0018 “Photocatalytic materials – air purification test
procedure”). The developed experimental setup consisted of a pollutant source, zero air source,
calibrator, humidifier, photoreactor, and chemiluminescent NOx analyzer as shown in Figure 1.
The setup simulates different environmental conditions by allowing for control of light intensity,
pollutant flow rate, temperature, and air humidity.
Construction Research Congress 2012 © ASCE 2012 1922

Table 1. Evaluated Pervious Mix Designs in the Experimental Program

Depth of TiO2 ( inch) Void Ratio (%) Replicates

3.0 23 3
3.0 27 3
3.0 31 3
0.5 23 3
1.0 23 3
2.0 23 3
Control Control 3

Figure 1. Illustration of The Experimental Laboratory Setup

Environmental Parametric Study

To evaluate the effects of different environmental conditions on photocatalytic efficiency
and the amount of associated nitrate, a partial factorial design was conducted for pollutant flow
rate, UV intensity, humidity, and temperature. Three levels were considered for each factor.
Nine combinations were tested with three replicates to account for variability. Table 2 presents
the factors varied in the analysis as well as the ranges considered.

Table 2. Levels of Factors for Parametric Study

Factors Level
Low Intermediate High
Relative Humidity 30 50 80
Pollutant Flow Rate (l/min) 3 5 9
Temperature (°C) 23 35 50
2
UV Intensity (W/m ) 0.9 2 3.7
Construction Research Congress 2012 © ASCE 2012 1923

Nitrate Laboratory Sampling

Since nitrate salt is a direct product of photocatalytic activity (see Equation 2), laboratory
measurements were conducted to quantify the amount of nitrate deposited on the pavement
surface. Nitrate salts deposited on the surface were measured for 21 samples with different mix
constituents. To measure the amount of deposited nitrate on the pavement surface, all the
samples were initially washed with distilled water based on the JIS standard to remove any
existing nitrates from the pavement surface. A nitrate baseline collection cycle was conducted
on all samples before the start of photocatalytic test. A flexi-glass container with dimensions (12
in x 12 in x 4 in) was fabricated and used to soak the samples. To collect the deposited nitrate,
3000 ml of Deionized (DI) water, purified by a Thermo Scientific Barnstead Nanopure ultrapure
purification system, was poured in the flexi-glass container. The samples were immersed in the
water and left for an hour to dissolve the nitrates. This procedure was repeated 3 times for each
sample. After first soaking, approximately 2700 ml of diluted solution was extracted. To get a
uniform concentration, the collected solution was stirred rigorously.
Nitrate Laboratory Determination
To quantify nitrate concentration in the collected water samples, the colorimetric method
cadmium reduction with a Shimadzu UV Spectrophotometer 1800 was adopted. In this method,
the cadmium metal is used to convert nitrite ions from nitrates into nitrites, which then reacts
with a reagent (chromotropic acid) to form a pink-colored solution. The intensity of color in the
solution is proportional to the concentration of nitrate in the sample. The color intensity is
measured by means of a UV VIS Spectrophotometer by measuring the amount of light absorbed
at a 508 nanometer wavelength (Osborn et al. 2012). The light absorption is then correlated to
nitrate concentration by means of a standard calibration curve.
In order to validate the experimental test in quantifying the nitrate level on the surface,
the amount of NOx removed by the test piece due to photocatalytic action was compared to the
nitrogen compound eluted from test piece. According to JIS standards, the nitrogen compound
eluted from the test piece was calculated as follows:
Qw= Qw1+ Qw2=Vw1 ([NO3] w1/62) + Vw2 ([NO3] w2/62) (3)
where ,
Qw= Nitrogen compound eluted from the test piece (µmol);
Vw= Volume of collected washing (ml);
NO3= Nitrate ion concentration eluent from the test piece (mg/l); and
W1 and W2= the first and second DI washes, respectively.

During the experiment, NOx introduced into the photocatalytic chamber will undergo four
transformations, adsorption by the photocatalytic pervious sample, conversion to nitrate,
conversion to nitrogen dioxide, and desorption by the test piece. The amount of NOx converted
into nitrates can be calculated using the following 5 steps as follows (JIS 2004):
Step 1. Calculate the amount of NOx removed by the adsorption action of the test piece but not
the photocatalytic action:

Q ads= [ ʃ ([NO]0 – [NO]) dt - ʃ ([NO2] dt] * f /22.4 (4)

Construction Research Congress 2012 © ASCE 2012 1924

where,
22.4 = a correction factor for standard temperature and pressure test conditions;
Q ads = the amount of NOx adsorbed by the test piece (µmol);
[NO]0 = supply concentration of nitrogen monoxide (vol ppm);
[NO] = nitrogen monoxide concentration at the reactor exit (vol ppm);
[NO2] = nitrogen dioxide concentration at the reactor exit (vol ppm);
t= time of the adsorption operation (min); and
f= air-flow rate converted into that at the standard state (0 °C, 10133 hPa) (l/min).

Step 2. Calculate the amount of NO removed by the test piece by photocatalytic action:
Q NO = (f/22.4) ʃ ([NO]0 – [NO]) dt (5)
where,
Q NO= the amount of the nitrogen monoxide removed by the test piece (µmol).

Step 3. Calculate the amount of NO2 formed by the test piece which formed secondarily by
photocatalytic action:
Q NO2 = (f/22.4) ʃ ([NO2] dt (6)
where,
Q NO2 = the amount of nitrogen dioxide formed by the test piece (µmol).

Step 4. Calculate the net amount of NOx desorbed by the test piece by the photocatalytic action:
Q des = (f/22.4) [ʃ [NO] dt + ʃ ([NO2] dt] (7)
where,
Q des= the amount of NOx desorbed from the test piece (µmol).

Step 5. Calculate the net amount of NOx converted into nitrates by photocatalytic action:
QNOx= Q ads+ Q NO- Q NO2- Q des (8)
where,
QNOx = the amount of NOx removed by the test piece (µmol).

Flow rate was corrected for Standard Temperature and Pressure (STP) conditions using
the combined gas law as follows:
SCF = ACF (P actual/P standard) (T standard/T actual) (9)
where,
SCF = the standard condition flow rate;
ACF = actual test condition flow rate,
P = the absolute pressure unit (kPa); and
T = the absolute temperature unit (K) - STP assumes T is 273 K and P is 101.3kPa.

EUTROPHICATION IMPACT ASSESSMENT

To estimate the possible impact of nitrate deposited on the surface due to photocatalytic
activity on eutrophication, the Building for Environmental and Economic Sustainability (BEES)
Construction Research Congress 2012 © ASCE 2012 1925

model was used (Lippiat 2007). This model provides a systematic methodology to select
sustainable construction alternatives that balance environmental and economic performances.
Since environmental factors such as eutrophication cannot be assessed using a regular monetary
scale, the BEES model computes a single index for each considered impact category in order to
quantify the effects of a product on the environment. Eutrophication potential is expressed in
grams of nitrogen produced per functional unit of a product. The eutrophication index is
calculated based on the following equation:
Eutrophication Index = ∑ mi x EPi (10)
i

where,
mi = mass (in grams) of harmful emission i produced per functional unit; and
EPi = conversion factor from one gram of harmful emission i to its equivalent of nitrogen.

For the purpose of this analysis, the eutrophication impact of photocatalytic pervious
concrete was compared to the eutrophication impact of regular concrete produced with regular
cement. For photocatalytic pervious concrete, two sources of eutrophication were considered:
(a) nitrate deposited on the surface, which would cause an increase in eutrophication potential
and (b) nitrogen oxide removed from the air atmosphere, which would cause a decrease on
eutrophication impact. Therefore, the analysis quantifies the net impact of the technology on
eutrophication. The functional unit was considered to be 1 square-feet of pavement and the
analysis was conducted for 50 years as recommended by BEES. During this 50-year
performance period, photocatalytic activity was assumed to occur for 9 hours per day. To
account for variability in environmental conditions including relative humidity, solar radiation,
and temperature, the analysis was conducted for three scenarios: worst-case (i.e., low NOx
removal efficiency), best-case (i.e., high NOx removal efficiency), and most-likely.
RESULTS AND ANALYSIS
Figure 2 presents the effect of void ratios and depths of TiO2 on NOx and NO
concentration for the pervious concrete samples tested at 30% humidity, UV intensity of 2
mW/cm2, and 3 l/min pollutant flow rate. As shown in this figure, NO and NOx removal
efficiency increased as the depth of the photocatalytic layer increased. Results show an average
NOx reduction efficiency of 35% for the 0.5 of TiO2 depth versus 74% reduction for the 3 in of
TiO2 depth samples. This can be explained by the fact that with pervious pavements, UV light
can infiltrate to greater TiO2 depth enhancing the photocatalytic efficiency of the sample. The
highest environmental performance was obtained from the sample with 3 in TiO2 depth and 31%
void ratio (Asadi et al. 2012).
Figure 3 presents the measured nitrate concentrations based on the cadmium reduction
method for different mix design of pervious concrete samples. Baseline concentrations were
subtracted from the concentrations quantified after the test by washing the sample with DI water
based on the JIS standard as described above. Error bars in the figure show ±1 standard
deviation. As shown in this figure, photocatalytic degradation of nitrogen oxide was validated
based on nitrate measurements and there is a direct relationship between nitrate concentration
and TiO2 thickness. Larger TiO2 depth results in more photocatalytic degradation of nitrogen
oxide and produces more nitrates on the surface.
Construction Research Congress 2012 © ASCE 2012 1926

350 80%
74% 73% NO

Percentage Reduction (%)

300 70% 70%
69% NOx
Concentration (ppb) 250 55%
NO Reduction 60%
51% 52%
46% 50%
200
37% 40%
150 33% 35%
30% 30%
100 20%
50 10%
0 0%
3 inch-31% 3 inch-27% 3 inch-23% 2 inch-27% 1 inch-27% 1/2 inch-27%
Depth -Void Ratio

Figure 2. Effects of the Depth of TiO2 and Void Ratio on NOx Reduction Efficiency

0.45
0.33 0.38
0.4 0.31
Nitrate Concentration (mg/l)

0.35 0.29
0.3 0.24 0.24
0.25
0.2
0.15
0.1
0.05
0
0.5 inch-27% 1 inch-27% 2 inch-27% 3 inch-23% 3 inch-27% 3 inch-31%

Pervious Concrete Sample

Figure 3. Nitrate Concentrations for Different Mix Design of Pervious Concrete Samples
after Six Hours of Photocatalytic Activity

Results of the cadmium reduction method were compared to the net amount of NOx
removed by the photocatalytic action. The net amount of NOx removed by the photocatalytic
action was calculated based on Equations (4) to (9). Figure 4 compares the net amount of NOx
removed by the test piece to the total of nitrogen compound eluted from the test piece for
different pervious concrete samples. Concentrations shown in this figure reflect the
concentrations after subtraction of the baseline concentrations measured after washing the
sample with DI water based on the JIS standard. As shown in this figure, there is a good
agreement between the results of both methods. From these results, it can be concluded that
measuring the nitrate ions accumulated on the surface is an accurate method to quantify NOx
reduction efficiency.
Construction Research Congress 2012 © ASCE 2012 1927

18 3.5
Net amount of NOx removed
Nitrate Concentration (μmol) 16 3
14 Nitrogen compound eluted
2.5
12 Error
10 2

Error (%)
8 1.5
6
1
4
2 0.5
0 0
0.5 inch- 1 inch-27% 2 inch-27% 3 inch-23% 3 inch-27% 3 inch-31%
27% Pervious Concrete Sample
Figure 4. Comparison Between the Net Amount of NOx Removed by the Test Piece
to the Total of Nitrogen Compound Eluted after Six Hours of Photocatalytic Activity

Environmental Parameters Test Results

The variation of NOx and NO removal efficiency with environmental conditions is shown
in Table 3. Results show the average NOX removal efficiency of three samples with 3 in of TiO2
depth and 31% void ratio test under different environmental conditions. As shown in this table,
Test Number 8 showed the highest average NO and NOx removal efficiency and Test Number 1
shows the lowest NO and NOx removal efficiency. The highest NOx reduction occurred at the
lowest relative humidity, highest UV intensity, lowest temperature, and lowest flow rate while
the lowest NOx reduction efficiency occurred at the highest relative humidity, lowest UV
intensity, highest temperature, and highest flow rate. In fact, Test Number 1, which was
conducted at high relative humidity, low UV intensity, and high pollutant flow rate, showed a
nitrate concentration of almost zero (1%), which means that photocatalytic action is almost
insignificant under these conditions.

Table 3. Variation of NOx Removal Efficiencies with Environmental Conditions

Test Factors
Test Pollutant Flow UV Temperature Humidity NO NOx
No. Rate Intensity (°C) (%) Reduction Reduction
(l/min) (mW/cm2) (%) (%)
1 9 0.8 50 80 0.7% 1%
2 9 2.0 23 50 14.3% 13.3%
3 9 3.7 35 30 37% 34%
4 5 0.8 50 30 22.8% 20.8%
5 5 2.0 35 80 3.5% 2.5%
6 5 3.7 23 50 48.6% 44.4%
7 3 0.8 35 50 17.5% 15.8%
8 3 2.0 23 30 77.9% 74.2%
9 3 3.7 50 80 10.3% 10%
Construction Research Congress 2012 © ASCE 2012 1928

Eutrophication Impact Assessment Result

Figure 5 shows the impact of photocatalytic pervious concrete on eutrophication potential
as determined by the BEES model. Results are expressed as a percentage of the eutrophication
impact of regular concrete produced with type I cement. Three different scenarios were
considered to assess the eutrophication impact of photocatalytic activities on the environment:
worst-case (i.e., low NOx removal rate at 10% efficiency), best-case (i.e., high NOx removal rate
at 74% efficiency), and most-likely (i.e., NOx removal rate at 34% efficiency). For the purpose
of this analysis, the positive effect of NOx removed from the air atmosphere due to photocatalytic
activities was subtracted from the negative effect of produced nitrate deposited on the surface.
As shown in this figure, photocatalytic pavement had an overall negative impact, which indicates
that this technology would reduce the overall eutrophication potential of concrete pavement
given its ability to reduce the concentration of nitrogen oxides in the atmosphere.

Best-Case Most-Likely Worst-Case

Eutrophication Impact of

0
Pervious Photocatalytic

-1
Pavement (%)

-2 -1.8
-3
-3.1
-4

-5

-6 -5.6

Figure 5. Eutrophication Impact of Pervious Photocatalytic Pavement

CONCLUSIONS
Based on the results of this study, the following conclusions were drawn:
• TiO2 was effective in removing NOx pollutants from the air stream with an efficiency
ranging from 37 to 67%. The maximum NOx removal efficiency was achieved at a 3 inch
depth of TiO2 with a 31% void ratio.
• Photocatalytic efficiency improved with the decrease in humidity, decrease in flow rate,
and the increase in UV light intensity.
• There was a good agreement between the total of nitrogen compound eluted and the net
amount of NOx removed under different mix design and environmental conditions.
• At high relative humidity, low UV intensity, high flow rate, and high temperature, the
measured nitrate concentration was almost zero, which means that photocatalytic activity
is almost insignificant under these environmental conditions.
• The concentrations of nitrate deposited on the surface are low and will not cause
eutrophication problems.
• The cost of the technology ranges from $1.19 /ft2 to $2.21 /ft2.
Construction Research Congress 2012 © ASCE 2012 1929

Based on the results presented in this study, further research is recommended to validate
the long-term efficiency of the technology in the field, including long-term environmental
performance durability.

ACKNOWLEDGEMENT
This study was funded through the Louisiana Transportation Research Center (LTRC).
Materials for this project were provided by Geiger Ready Mix, Essroc, Lafarge, and BASF.
Laboratory help at UMKC was provided by Greg Roberson.

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Construction Research Congress 2012 © ASCE 2012 1930

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