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Air Pollution and Climate Change

SEASONAL DISTRIBUTION OF GROUND-LEVEL OZONE AND


ITS PRECURSORS IN PLOIESTI, ROMANIA

Prof. Dr. Stefania IORDACHE1


Assoc. Prof Dr. Cornel IANACHE2
Lect. Dr. Laurenţiu PREDESCU1
Lect. Dr. Mirela PREDESCU1
Assoc. Prof Dr. Dumitru DUMITRU1
1
Valahia University of Targoviste, Romania
2
Petroleum Gas University of Ploiesti, Romania

ABSTRACT
Air pollution became a real public concern for countries all over the world. Increasing
anthropogenic emissions of nitrogen oxides (NO x) can cause a substantial increase in
ground-level ozone, which is a secondary air pollutant produced by photochemical
interaction of NO x and volatile organic compounds (VOCs), through a complex set of
reactions under the influence of solar radiation. Ploiesti is one of the main cities in
Romania, which is facing with anthropogenic atmospheric emissions that result
especially from its petrochemical industries, vehicular emissions or various combustion
processes (e.g. residential heating, power plants, fossil fuel). This study aimed to
investigate distribution characteristics of ground level ozone (O 3) in relationship with its
precursors (nitrogen dioxide (NO2), nitrogen monoxide (NO), and nitrogen oxides
(NOx)) using statistical analysis methods. Data analyzed consisted in hourly O 3 and NO x
measurements that were collected from January to September 2016 at an urban station
that belong to the Romanian National Network for Air Quality Monitoring (RNMCA).
It was also investigated seasonal variations of O3 and its precursors and their weekly
variations in order to observe the presence of the “ozone weekend effect”. The results
showed that the highest ozone concentration in Ploiesti was observed in summer period.
Seasonal variations of O3 concentrations have followed the order of summer > spring >
winter, while the pattern of seasonal variation for its precursors (NO, NO 2, and NO x)
was in opposite with that of ozone concentrations.
Keywords: ground-level ozone, NOx, time series analysis, urban site

1. INTRODUCTION
Ground-level ozone (O3) is an important air pollutant that has a negative impact on
human health and vegetation growth [1], [2]. Ozone is a secondary air pollutant that is
not directly emitted in the air; it is produced as result of the photochemical interaction
of nitrogen oxides (NO x) and volatile organic compounds (VOCs), by a complex set of
reactions under the influence of solar radiation [3]. Therefore, O3 concentrations depend
on the concentrations of its precursors and the intensity of solar radiation [4]. The
17th International Multidisciplinary Scientific GeoConference SGEM 2017

seasonal and diurnal variations of O3 and its precursors have been extensively studied
around the world [5], [6]. The local causes of O3 pollution at a specific site can be better
understood by analyze the influences that meteorological parameters exert on O 3 and its
precursors [7].
The present work investigated seasonal variations of O 3 concentrations in association
with its precursors (NO, NO2 and NO x) in Ploiesti city, Romania. This study was based
on time series analysis of O3 and NO x and has aimed to characterize temporal variations
of their concentrations recorded at an automated urban monitoring station in Ploiesti. It
was also investigated the weekday/weekend pattern of ozone and NO x in Ploiesti for a
better understanding of the mechanisms of reducing O 3 pollution threats.

2. MATERIALS AND METHODS

The time series of O3, NO, NO2, and NO x analyzed in this work, represents hourly
values recorded from January 2016 to September 2016 at an automated monitoring
station (PH-6, 44º56’17’’ N Lat; 26º02’42’’ E Long) in Ploiesti. The raw data of
pollutants concentrations were collected from http://www.calitateaer.ro, which is the
official site of Romanian National Network for Monitoring Air Quality (RNMCA). This
site is dedicated to inform the public in real time on air quality parameters, monitored
at more than 100 stations all over Romania.
Data obtained were statistically analyzed using SPSS software (SPSS Inc., Chicago, IL,
2011). Correlation analysis was done using Pearson correlations to establish the
relationship among different pollutants. Time series analysis was used to provide
diurnal pattern of pollutants.

3. RESULTS
Concentrations of O3 and its precursor’s gases (NO, NO2, and NO x,) were measured in
Ploiesti from January 2016 to September 2016 at PH-6 monitoring station. The average
concentrations of O3 , NO, NO 2, NO x, were 38.05 μg/m³, 10.24 μg/m³, 28.19 μg/m³, and
43.85 μg/m³, respectively. The hourly values ranged from 2.41 to 100.31 μg/m³ for O3,
0.35 to 129.25 μg/m³ for NO, 2.02 to 254.06 μg/m³ for NO2, and 4.76 to 471.68 μg/m³
for NOx, during the study period.
Table 1. Central tendency indicators of ozone and its precursors [μg/m³]

Ozone NO2 NO NO x
N 5421 5105 5101 5105
Mean 37.87 28.19 10.24 43.85
Std. Error of Mean 0.22 0.257 0.229 0.538
Median 35.95 22.93 6.34 33.24
Mode 35.66 25.60 5.41 33.89
Std. Deviation 16.25 18.37 16.39 38.50
Minimum 2.41 0.35 2.02 4.76
Maximum 100.31 129.25 254.06 471.68
Air Pollution and Climate Change

The average diurnal variations of NO x and O3 concentrations during the study period in
Ploiesti, on a weekly basis, are shown in fig. 1. It can be observed that the diurnal cycles
of O3 concentrations revealed a mid-day peak (2:00 p.m on weekdays and 4:00 p.m on
weekend), while NO x diurnal variations presented 2 daily peaks, one in the morning
(around 10:00 a.m.) and one in the evening (around 8:00 p.m on weekdays and 10:00
p.m. on weekend). This pattern observed in the temporal variability of O 3 and NO x was
presented in many other cities, worldwide [8],[9]. Even if the variations are sometimes
affected by local meteorological effects, the basic pattern always remains. It can be
observed that the O3 peak appears about 6 hours after the NO x peak. The decrease of
NOx concentration is in correlation with an increase in O3 level. This pattern is
consistent with data previously reported in literature for many cities [8],[9]. This
variation can be explained due to the photochemical reaction involved in formation of
O3 in the presence of its precursors.

90.0

80.0

70.0

60.0
Concentration [µg/mc]

Ozone weekdays
50.0
Ozone weekend
40.0 NOx weekdays
NOx weekend
30.0

20.0

10.0

0.0
0 2 4 6 8 10 12 14 16 18 20 22 24
Hours

Fig.1. Ozone and NO x weekdays/weekend pattern in Ploiesti from January to September


2016 at monitoring station PH-6 (raw data collected from www.calitateaer.ro)

Figure 1 indicates that NO x concentrations in ambient air were lower on weekends than
on weekdays in all time of day. In opposite with NO x, the highest O3 concentration
levels were recorded on weekend. A possible explanation of such weekly pattern could
be the fact that on weekend, in Ploiesti, the road traffic is lower than during weekdays
(because many companies do not operate in weekend)[10]. Consequently, the lower
traffic volumes produced less NO x, which resulted in less ozone destruction. Therefore,
the O3 levels were higher on weekend compared to weekdays. On weekend (fig.1), the
pattern for NO x and O3 was different, both in concentrations and in hourly interval of
peaks [10].
The seasonal variations in O3, NO, NO2, and NO x concentrations during the period of
study are represented graphically in figure 2. It can be observed that, for O3
concentrations, the lower values appeared in winter (colder periods), while in spring and
summer were observed higher values of diurnal cycle concentrations that were very
17th International Multidisciplinary Scientific GeoConference SGEM 2017

close in magnitude. The mean concentrations of O3 in different seasons follow the order
of summer > spring > winter (table 2). The diurnal variation of O3 was characterized by
high concentrations during daytime and low concentrations during late night and
morning. The minimum O3 concentration was observed during the morning hours (8.00
a.m. to 10.00 a.m). Data from our study showed some differences in hour of the day
when the maximum O3 concentrations appeared, depending on the season. In warm
season, the photochemical reactions are favored by the increase in solar radiation
intensity. In Ploiesti city, during this study, the maximum O3 concentration appeared
around at 1:00 p.m in summer, around at 2:00 p.m. in spring, and around at 4:00 – 5:00
p.m. in winter.
The seasonal variation pattern of the O 3 precursors (NO, NO2 , and NO x) were almost in
opposite with that of ozone (fig.2). The higher values were recorded in winter, while
the lower values were recorded in summer. This pattern corresponds with the results of
previous studies realized in other urban areas [11],[12]. One of the causes of this pattern
could be the increase in air pollutant emission in winter due to residential heating. In
figure 2 it can be observed a peak for NO x concentrations, which has a great magnitude
in the morning and might partly be attributed to the traffic, the “rush-hour” being the
hourly interval from 8:00 a.m to 10:00 a.m. The diurnal variations of NO, NO 2, and
NOx, concentrations showed peaks concentrations linked to traffic density, in every
season.

Table 2. Statistical summary of hourly averaged concentrations of O3, NO, NO2, NO x,


in different seasons over the period from January 2016 to September 2016 in Ploiesti.
Pollutant Statistical Season
Indicator Winter Spring Summer
O3 Mean 29.29 39.79 40.39
S.D 14.12 15.80 15.80
Median 27.96 36.70 39.24
Min 2.41 9.79 6.72
Max 78.19 100.31 85.45
NOx Mean 66.39 39.03 30.28
S.D 61.46 22.23 15.69
Median 45.66 33.77 26.69
Min 4.76 12.43 10.31
Max 471.68 280.86 154.43
NO Mean 18.02 6.72 7.76
S.D 29.30 6.33 3.37
Median 6.83 5.37 6.92
Min 2.58 2.02 2.21
Max 254.06 115.42 29.80
NO2 Mean 38.77 28.74 18.45
S.D 23.10 14.84 11.72
Median 34.56 25.22 15.70
Min 0.35 8.10 3.68
Max 129.25 103.89 109.77
Air Pollution and Climate Change

Ozone
Winter Spring Summer
70.0

Concentration [ µg/mc]
60.0
50.0
40.0
30.0
20.0
10.0
0.0
0 2 4 6 8 10 12 14 16 18 20 22 24
Hours

NOx
Winter Spring Summer
140.0
120.0
Concentration [ µg/mc]

100.0
80.0
60.0
40.0
20.0
0.0
0 2 4 6 8 10 12 14 16 18 20 22 24
Hours
NO2
Winter Spring Summer
60.0
Concentration [ µg/mc]

50.0

40.0

30.0

20.0

10.0

0.0
0 2 4 6 8 10 12 14 16 18 20 22 24
Hours

NO
Winter Spring Summer
50.0
45.0
Concentration [ µg/mc]

40.0
35.0
30.0
25.0
20.0
15.0
10.0
5.0
0.0
0 2 4 6 8 10 12 14 16 18 20 22 24
Hours
Fig.2. Seasonal variations of O3, NO, NO2 and NO x diurnal cycle observed in Ploiesti
from January to September 2016 (raw data collected from www.calitateaer.ro)
17th International Multidisciplinary Scientific GeoConference SGEM 2017

Table 3: Pearson’s Correlations of Ozone with precursor pollutants and meteorological


parameters in winter season

Solar Wind Wind


Ozone NOx Temp radiation RH direction speed
Ozone 1 -0.533** -0.099** 0.257** -0.301** 0.099** 0.281**
NOx 1 0.077** -0.047 0.044 -0.146** -0.237**
Temp 1 0.294** -0.108** 0.169** 0.094**
Solar radiation 1 -0.516** 0.268** 0.066*
RH 1 -0.212** -0.025
Wind direction 1 0.096**
Wind speed 1
**. Correlation is significant at the 0.01 level (2-tailed).
*. Correlation is significant at the 0.05 level (2-tailed).

Table 4: Pearson’s Correlations of Ozone with precursor pollutants and meteorological


parameters in summer season
Solar Wind
Ozone NOx Temp RH radiation direction Wind speed
Ozone 1 -0.182** 0.753** -0.797** 0.536** 0.003 0.393**
NOx 1 0.021 -0.040 -0.051* 0.077** -0.260**
Temp 1 -0.803** 0.577** -0.046 0.333**
RH 1 -0.581** -0.018 -0.300**
Solar radiation 1 -0.009 0.374**
Wind direction 1 -0.169**
Wind speed 1
**. Correlation is significant at the 0.01 level (2-tailed).
*. Correlation is significant at the 0.05 level (2-tailed).

The Pearson correlations between O3, NO x and meteorological parameters is shown in


table 3 (winter season) and table 4 (summer season). According to this analysis, a
medium negative correlation of O3 with NO x was observed in winter season (r =-0.533),
while in summer season correlation is poorer, but also negative (r = -0.182). This result
indicated that concentrations of precursor pollutants play an important role both in the
formation of ozone and also in its destruction. Except for relative humidity, the
correlation of ozone with the meteorological parameters considered for this study was
found to be positive. It can be observed that the metrological parameters and ozone are
more strongly correlated in summer season than in winter season.

4.CONCLUSIONS

The process of formation and destruction of ozone is a complex one and changes both
seasonally and diurnally. Ozone formation is influenced by its precursor pollutants
under favorable meteorological conditions. In Ploiesti city, the highest ozone
concentration was observed in summer season by comparison with spring and winter
season. The correlation of ozone with NO x was found to be negative in all seasons,
which is consistent with data reported in literature. In addition, the concentrations of
Air Pollution and Climate Change

NOx were found to be higher during the morning in the interval corresponding with the
“rush hours” of traffic, indicating the influence of vehicular activity around the
monitoring site. In the study area, the daily cycle of NO x concentration showed a diurnal
variation with 2 peaks: a morning peak (10:00 a.m.) and an evening peak between 8:00
p.m to 10:00 p.m. In addition, O3 and NO x showed a distinct pattern of weekly
variations. The O3 concentrations were slightly higher on weekends compared to
weekdays (the “ozone weekend effect”), in opposite with the pattern of the weekly
variations of NO x.
Seasonal variations of O3 concentrations have followed the order of summer > spring >
winter, while the pattern of seasonal variations for its precursors (NO, NO 2, and NO x)
was in opposite with that of ozone.

ACKNOWLEDGMENTS
The research leading to these results has received funding from European Economic
Area Financial Mechanism 2009-2014 under the project ROKIDAIR “Towards a better
protection of children against air pollution threats in the urban areas of Romania”
contract no. 20SEE/30.06.2014.

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17th International Multidisciplinary Scientific GeoConference SGEM 2017

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