Archives of Environmental Contamination and Toxicology (2019) 77:197–213

https://doi.org/10.1007/s00244-019-00627-8

Average Hourly Concentrations of Air Contaminants in Selected Urban,

Town, and Rural Sites
Robert Cichowicz1   · Artur Stelęgowski1

Received: 23 December 2018 / Accepted: 1 April 2019 / Published online: 10 April 2019
© The Author(s) 2019

Abstract
The inhabitants of cities, towns, and villages are exposed to different levels of air pollution, which also vary throughout the
day. Information regarding episodes of poor and good air quality enables planning to mitigate the risks and maximize the
benefits of spending time outdoors. In this work, an analysis was made of the state of air quality 2012–2016, using data gath-
ered from automatic measuring stations located in five cities (> 50,000 inhabitants), five towns (5000–50,000 inhabitants),
and five villages (< 5000 inhabitants) in five neighboring provinces in central Poland, in Central Europe. The monitoring
stations were designated as “city background”, “town background”, and “rural background”. More than 3 million pieces of
data were collected from 15 monitoring stations. This allowed the average daily changes in the concentration of air pollut-
ants ­(NO2 and N­ Ox, ­O3, ­SO2, CO, P
­ M10, ­PM2.5, ­C6H6) to be determined, depending on the type of station and the size of the
settlement unit in both winter periods and summer periods. As a result, the most and least favorable hours in terms of levels
of air pollution were identified. This information could help to inform air quality management in modern cities, towns, and
villages and to improve the quality of life, particularly among those most susceptible to the negative effects of air pollution,
such as the elderly and children.
Graphical Abstract

Cities
Typical daily
variations

Towns
Monitoring
Stations

NO2, NOx, O3,SO2, CO,

PM10, PM2.5, C6H6

Villages
2012-2016

* Robert Cichowicz
robert.cichowicz@p.lodz.pl
1
Faculty of Civil Engineering, Architecture
and Environmental Engineering, Lodz University
of Technology, Lodz, Poland

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198 Archives of Environmental Contamination and Toxicology (2019) 77:197–213

State‑of‑the‑Art to the negative effects of air pollution, such as children, the

elderly, and people with asthma and respiratory illnesses
Worldwide air quality poses a risk both to human health (Künzli et al. 2000; WHO 2000, 2005). Such information
and the wider environment (Agudelo-Castañeda et  al. makes it possible for people to reduce their exposure to
2019; Ramírez et al. 2019; Oliveira et al. 2019). Studies air pollution, for example in response to recommendations
on air pollution focus not only on inhabited areas (Cicho- regarding the “most” and “least” favorable hours for stay-
wicz et al. 2017; Cichowicz 2018; Pérez et al. 2010) but ing outdoors. When there are high concentrations of air
also on agricultural and undeveloped areas, which are pollutants in the air, it is advisable to stay indoors. This is
used as background measurements (Hagenbjörk et  al. due to the inertia of the air in buildings, which can cause
2017; Putaud et al. 2004; Zheng et al. 2010). In many a “shift” and “lowering” of the daily maximum concentra-
countries, including in Europe, air quality assessments tions of several pollutants (Bouhambra et al. 2000; Hayes
use measurements performed by automatic measuring sta- 1991; Chaloulakou and Mavroidis 2002). The flow bal-
tions (Agudelo-Castaneda and Teixeira 2014; Malley et al. ance of air pollution inside a building depends not only
2018; Wielgosiński et al. 2018) and air quality modeling on outdoor air quality but also on the structure and air-
(Cichowicz and Stelegowski 2018a; Inness et al. 2013; tightness of the building, as well as indoor sources of pol-
Menut et al. 2012). Usually, the average annual, seasonal, lution (Cichowicz et al. 2016; Cichowicz and Stelęgowski
and monthly concentrations of air pollutants are analyzed 2018b; Colbeck et al. 2008; De Paoli et al. 2018). How-
(Cichowicz et  al. 2017; Guerreiro et  al. 2010; Malley ever, according to the literature, there may be shifts of
et al. 2018). Much less information is available regarding approximately 1 h and reductions of approximately 60%
daily fluctuations (Liu et al. 2014; Zhao et al. 2009). Daily for CO (Chaloulakou and Mavroidis 2002), of 90% for ­O3
variations in air pollution occur due to the high variabil- (Hayes 1991) and approximately 30% for benzene (Bou-
ity of sociophysical and chemical parameters during the hambra et al. 2000). When there are low concentrations of
day (Menut et al. 2012; Pérez et al. 2010). These changes pollutants outdoors, the situation is reversed. During such
depend largely on the day of the week (work days or week- periods, it is better to stay outside, where concentrations
ends) (Feng et al. 2014; Chaloulakou and Mavroidis 2002) can be half those in buildings (Chaloulakou and Mavroidis
and the season (Vouitsis et al. 2015). The average hourly 2002).
concentrations of air pollutants are usually analyzed only
for cities (Agudelo-Castaneda and Teixeira 2014; Vouitsis
et al. 2015) and in the vicinity of busy roads (Moreno et al.
2013; Pérez et al. 2010). There are few air-quality analy- Automatic Measuring Stations in Cities,
ses on other types of area, especially for settlement units Towns, and Villages
of different sizes, and those focus on average annual and
seasonal pollution levels (Hagenbjörk et al. 2017; Malley Hourly measurements of pollutant concentrations in the
et al. 2018; Putaud et al. 2004; Tecer and Tagil 2014) and ambient air are taken across a network of national air
only occasionally daily variations (Zheng et al. 2010). monitoring stations in Europe (Guerreiro et  al. 2010;
EEA 2016). These measurement stations are located in
the vicinity of point, areal, and linear emission sources
and provide data on the air quality in areas of, inter alia,
Outdoor and Indoor Air Pollution “urban traffic/kerbside” (UT), “urban background” (CB),
“suburban background” (SB), “rural background” (RB),
Concentrations of air pollutants depend on city density and and “natural background” (NB) pollution (Putaud et al.
on urban planning, and the level of industrialization also 2004).
has an impact (Landim et al. 2018; León-Mejía et al. 2018; There are various classifications of settlement units
Saikia et al. 2018). The daily activity patterns of people, in European Union countries. To unify this division, the
including time spent at home, working hours, and travel, Organization for Economic Cooperation and Development
are specific to particular areas and fluctuate during the day. with European Commission (OECD-EC) introduced the
The emission of air pollutants associated with such activi- definition of a city as an urbanized area with a popula-
ties, and the concentrations of pollutants in the ambient tion of more than 50,000 and population density above
air therefore vary (Cichowicz et al. 2017; Fenger 1999; 1500  inhabitants  km −2 (Dijkstra and Poelman 2012).
Nicolai et al. 2003). Although people spend only 10–20% According to the definition developed in the European Ter-
of their days outdoors, it is still important to provide infor- ritorial Observatory Network program (ESPON), towns
mation on air quality, especially for those most susceptible are urbanized areas with populations of 5000–50,000 and

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Archives of Environmental Contamination and Toxicology (2019) 77:197–213 199

population densities of 300–1500 inhabitants km−2 (Ser- summer. Most of Poland is located in the North European
villo et al. 2014). Plain, consisting of low plains. The north part of Poland
is a coastal lowland adjacent to Baltic Sea, and the south
part includes highlands and the Carpathian Mountains.
Daily Variations in Air Pollution The analyzed regions of Great Poland, Lodz, and Maso-
via are located in the lowlands (elevation up to 300 m).
Daily variations in air-pollution level depend, to a large The Lublin region includes mostly lowlands, highlands
extent, on both meteorological conditions (Pérez et al. (elevation up to 390 m), and Lower Silesia consists of
2010) and human activity. Human activity profiles are lowlands, highlands (up to 718 m), and mountains (up to
relatively stable in particular areas, resulting in distinc- 1603 m). The chosen areas are similar for weather con-
tive patterns air pollutant emissions (Gaffron 2012; Menut ditions. The annual average air temperature is 8 ± 1 °C,
et al. 2012). However, the concentrations of air pollutants precipitation is approximately 600 mm, with higher val-
in a given area are influenced by many factors, none of ues (up to 1300 mm) in the mountains (SP 2018). How-
which often is decisive. Depending on the location of the ever, the prevailing rainfall occurs in summer. The mean
measuring station, the levels of air pollution can be more monthly humidity usually range from 60 to 90%. The
or less closely associated with particular factors. This has dominant wind direction is west, and the average velocity
been confirmed by studies in which, for example, an analy- is 3 m s−1. The average insolation is 1600 h, and average
sis of the urban background pollution in the cities Canoas solar radiation is 1000 kWh/m2. In 2015, approximately
and Esteio in Brazil showed a correlation between ­O3 and 91% of energy was generated from nonrenewable sources
solar radiation intensity, and no correlation between P
­ M10 in Poland, primarily from hard coal and lignite (51%),
and air temperature (Agudelo-Castaneda and Teixeira crude oil (25%), and natural gas (15%) (IEA 2017). The
2014, 2017; Vouitsis et al. 2015). The Pearson correlation share of urban population in the total population of a
coefficient between ­O3 and radiation intensity was 0.558 region amounts to approximately 46% in Lublin voivode-
(average) and − 0.186 (low) for P ­ M10 and ambient temper- ship, 55% in Greater Poland, 64% in Lodz and Masovia,
ature (Agudelo-Castaneda and Teixeira 2014). However, at and 69% in Lower Silesia. The dominant air contamination
a short distance from the emission source, the relationship sources in the chosen areas are power industry, industrial
was much stronger. This was confirmed by analyses carried and nonindustrial combustion, and road transport. Those
out near a busy road in the city of Thessaloniki (Greece). economy sectors contribute to 97% of ­SO2, 80% of ­NOx,
The Pearson correlation coefficient between NO and CO and 70% of ­PM10 emissions in Poland (Dębski et al. 2015;
and road traffic intensity was significantly stronger: 0.91 SP 2017). The amount of total gaseous emissions form
and 0.94 respectively in summer, and 0.89 and 0.40 in win- point sources in 2017 was 12.0 × 106 Mg/year in Lower
ter (Vouitsis et al. 2015). The changes in NO concentration Silesia, 14.4 × 106 Mg/year for Greater Poland, 43.2 × 106
during winter and summer seem related mainly to changes Mg/year for Lodz, 29.1 × 106 Mg/year for Masovia, and
in road traffic intensity. Changes in CO concentration in 5.0 × 106 Mg/year for Lublin region. Dust emissions were
winter were possibly associated with other factors, such 1.9 × 103 Mg/year, 4.0 × 103 Mg/year, 2.3 × 103 Mg/year,
as emissions from fuel combustion for heating purposes. 2.7 × 10 3 Mg/year, and 1.7 × 10 3  Mg/year respectively
(https​: //bdl.stat.gov.pl). High point emissions in Lodz
region were mainly caused by power industry, especially
by large power plant “PGE GiEK” Belchatow. This power
Characteristics of the Tested Area plant has 5342 MWe electric power and uses brown coal
as a fuel (Cichowicz and Stelegowski 2018c). It is placed
Poland is located in a temperate transitional climate zone. 35 km from the analyzed location in Piotrków Trybunalski
There are low temperatures in winter, reaching approxi- city, 60 km Lodz city, and 100 km from Gajew village. In
mately − 14 °C (5th percentile) and on average ranging Greater Poland region, there is the “ZE PAK” (http://zepak​
from approximately − 3 to + 1  °C (http://old.imgw.pl/ .pl/en) power plant complex (2512 × MWe, fuel: brown
klima​t), depending on the region. As a result, there are coal), placed 10–30 km from the analyzed locations in
high levels of pollution from fuel combustion for heat- Konin city, 35 km from Piaski village, and 130 km from
ing purposes (nonindustrial combustion). In contrast, Poznan city. Also, each city and town in this analysis has
temperatures in summer are significantly higher, reach- its own, but smaller (< 500 MWe), power or combined heat
ing approximately + 28 °C (95th percentile), and on aver- and power plant, providing energy and/or heat for central
age ranging from approximately + 13 to + 19 °C (http:// part of its urbanized area.
old.imgw.pl/klima​t ), depending on the region. There- Due to the specific characteristics of emissions in dif-
fore, there are high levels of pollution from transport in ferent areas, it was decided to analyze the changes in the

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200 Archives of Environmental Contamination and Toxicology (2019) 77:197–213

a period of 5 years from January 2012 to December 2016.

The data were gathered from automatic air monitoring sta-
tions and were made available by the Voivodship Inspector-
ates for Environmental Protection (WIOŚ) and by the Main
Inspectorate for Environmental Protection (GIOŚ) in Poland
(http://powie​trze.gios.gov.pl/pjp/curre​nt). The monitoring
stations were categorized based on the character of the emis-
sions, as city background (CB), town background (TB), or
rural background (RB). Data from 15 monitoring stations
were selected for analysis: five stations located in cities (CB
stations), five in towns (TB stations), and five in villages (RB
stations). The CB and TB stations were located in the sur-
roundings of dense residential and service buildings, away
from large point air pollution sources. RB measuring sta-
tions were located in the agriculture areas.
Due to the prevailing western and south-western wind
directions in Poland, all the selected measuring stations
were on the “west–east” line, between 50 and 53°N lati-
tude and 15–24°E longitude. This area comprised five prov-
Fig. 1  Location of measuring stations in selected cities, towns, and inces in central Poland (Fig. 1). In the following analysis,
villages in Poland the locations are designated using symbols relating to the
size of the settlement units and their location in a particu-
lar voivodship: L—city, M—town, S—village; 1—Lower
average hourly concentrations of air pollutants at various Silesia voivodship, 2—Greater Poland voivodship, 3—Lodz
locations in Poland, depending on the size of the settlement voivodship, 4—Masovian voivodeship, 5—Lublin voivode-
unit. The analysis focused on the selected air pollutants, ship (Tables 1, 2, 3).
which are harmful to human health: the gaseous substances The measurements were made at automatic air monitor-
­NO2, ­NOx (NO + NO2), ­SO2, ­O3 and CO, as well as the dusts ing stations, according to the reference or equivalent meth-
­PM10 and ­PM2.5 and benzene (­ C6H6). The analysis covered ods (Table 4). However, due to technical/service breaks in

Table 1  Location of CB Symbol City name Population Density (inhabit- Station address City size
measurement stations in cities (inhabitants) ants km−2)

L1 Wrocław 639,000 2181 Korzeniowskiego St. XL

L2 Poznań 539,000 2057 Polanka St. XL
L3 Łódź 690,000 2354 Gdańska St. XL
L4 Warsaw 1,765,000 3412 Marszałkowska St. XXL
L5 Lublin 340,000 2310 Obywatelska St. L

Population status as of 31 Dec 2017. City size is defined according to the nomenclature of OECD-EC
classification, depending on the population of urban city center, as: L—large city, XL—extra-large city,
XXL—extra extra-large city

Table 2  Location of TB measurement stations in towns

Symbol Town name Population (inhab- Density (inhabit- Station address Town size
itants) ants km−2)

M1 Kłodzko 27,000 1098 Szkolna St. Medium SMST

M2 Konin 75,000 919 Wyszyńskiego St. Large SMST
M3 Piotrków Trybunalski 74,000 1114 Krakowskie Przedmieście St. Large SMST
M4 Piastów 23,000 3977 Pułaskiego St. Small SMST
M5 Biała Podlaska 57,000 1159 Orzechowa St. Large SMST

Population status as of 31 Dec 2017. City size is defined according to the OECD-EC classification

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Table 3  Location of RB measurement stations in villages Table 5  Number of measuring stations and the number of years that
met the criterion of completeness for results
Symbol Village name Population Latitude Longitude
(inhabit- Pollutant Stations × years
ants)
CB stations TB stations RB stations
S1 Osieczów 345 51°19′03.5″ N 15°25′54.2″ E
NO2 25 22 25
S2 Piaski 124 52°30′05.0″ N 17°46′24.5″ E
NOx 25 20 25
S3 Gajew 114 52°08′35.7″ N 19°41′49.0″ E
O3 14 23 25
S4 Belsk Duży 790 51°50′06.4″ N 20°47′29.6″ E
SO2 20 24 25
S5 Obrocz 525 50°35′26.9″ N 22°59′52.4″ E
CO 23 10 5
Population status as of 31 Dec 2009 PM10 18 15 7
PM2.5 12 2 n/a
benzene 12 n/a n/a
the operation of individual measuring stations, full data
could not be obtained for all gaseous substances and dusts.
Therefore, only the data from years with at least 75% com- respectively (Fig. 3). This means that the lowest concentra-
pleteness for a particular station were used in the analysis. tions occurred during SPs and the highest in winter, except
The average hourly concentrations were thus determined at locations L4 and M4 (stations in the Warsaw city and the
based on the number of years that met this criterion for a town of Piastów in the Mazovian Province). The shape of
given station (Table 5). the ­NO2 daily profile was always close to a bimodal distribu-
In Poland, the levels and nature of air pollutants vary tion, with two distinct minima and maxima. The daily maxi-
significantly between in winter periods (WPs) and summer mum concentration was higher in the evenings than in the
periods (SPs). Therefore, the measurements were divided morning. The lowest concentrations occurred in SPs in the
into two seasons. It was assumed that WP lasted from Octo- afternoon and, importantly, remained at a similar level for
ber 1 to March 31 and covered the entire heating season, 6–12 h. However, these periods of low N ­ O2 concentrations
whereas SP lasted from May 1 to August 31 and covered were much shorter, lasting 1–4 h. The shapes of the hourly
the vegetation period. profiles for the same type of settlement unit were similar.
The average hourly N ­ Ox concentrations in WPs ranged
from 20.27 to 142.77  μg  m −3 in cities, from 16.54 to
Results and Discussion 61.86 μg m−3 in towns, and from 10.74 to 18.33 μg m−3
in rural areas (Fig. 4). The concentrations were lower in
The analysis of average hourly pollutant concentrations in SPs and ranged from 12.56 to 110.57 μg m−3, from 8.11 to
the ambient air at stations CB, TB, and RB, in WP and SP in 45.79 μg m−3, and from 2.16 to 18.80 μg m−3, respectively
the years 2012–2016, revealed daily variations in air pollu- (Fig. 5). The shape of the N­ Ox daily profiles was close to a
tion levels. The periods during a “typical” day were identi- bimodal distribution, similar to the ­NO2 profiles. However,
fied when the daily maximum and daily minimum average in the case of N
­ Ox the morning and evening peaks had simi-
hourly concentrations of pollutants occurred. lar values. This was most likely caused by NO emissions
Mean hourly ­NO2 concentrations in WPs ranged from resulting from the morning rush hours. However, in summer
14.12 to 57.27 μg m−3 in cities, from 11.06 to 32.98 μg m−3 in the cities of Wrocław (L1) and Warsaw (L4), the morn-
in towns, and from 9.10 to 16.41  μg  m−3 in rural areas ing ­NOx peak concentrations were higher than those in the
(Fig. 2). In SPs, the mean hourly ­NO2 concentrations ranged evening, probably due to the heavier traffic congestion. The
from 8.29 to 60.10 μg m−3, from 4.47 to 36.33 μg m−3, and shapes of the ­NOx profiles were similar for particular types
from 1.75 to 4.47 μg m−3 for cities, towns, and rural areas, of settlement unit. The ­NOx level was also lower during SPs

Table 4  Methods of measuring Pollutant Measuring method

air pollution at measuring
stations NO, ­NO2 Chemiluminescence, according to EN 14211; precision ± 0.5%
SO2 Ultraviolet fluorescence, according to EN 14212; precision ± 1%
CO Infrared spectroscopy, according to EN 14626; precision ± 0.1 ppm
O3 Ultraviolet photometry, according to EN 14625; precision ± 1 ppb
PM10, ­PM2.5 Beta attenuation, according to EN 12341; precision ± 2 µg m−3
benzene Gas chromatography with flame-Ionization detection, according to
EN 16450:2017-05; precision ± 3.0%

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Fig. 2  Average hourly ­NO2 concentrations in winter periods

Fig. 3  Average hourly ­NO2 concentrations in summer periods

Fig. 4  Average hourly ­NOx concentrations in winter periods

than in WPs in the cities and towns. Similar results were pre- concentrations generally increased as the size of the settle-
viously reported (Schneider et al. 2016; Garcia et al. 2014; ment unit decreased. This confirms the results of previous
Martinello et al. 2014). scientific studies (Guerreiro et al. 2010; Hagenbjörk et al.
The average hourly O ­ 3 concentrations in WPs ranged 2017), which showed that the level of O ­ 3 decreases as the
from 20.02 to 41.23  μg  m −3 in cities, from 22.62 to NO concentration in the air rises. The NO level was usu-
48.73 μg m−3 in towns, and from 25.98 to 52.10 μg m−3 ally higher in those areas with heavier traffic. However, the
in rural areas (Fig.  6). The  concentrations were higher lowest ­O3 concentrations in SPs occurred in cities and were
in SPs, ranging from 29.98 to 92.27  μg  m−3 in cities, higher than the minimal values in towns and villages. Daily
from 21.61 to 94.67 μg m−3 in towns, and from 21.46 to fluctuations in O
­ 3 levels were the widest in rural areas. This
96.08 μg m−3 in rural areas (Fig. 7). Ground-level ozone contradicts research into ground-level ozone concentrations

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Fig. 5  Average hourly ­NOx concentrations in summer periods

Fig. 6  Average hourly ­O3 concentrations in winter periods

Fig. 7  Average hourly ­O3 concentrations in summer periods

in different types of area carried out by Zheng et al. (2010), The sudden drop in O ­ 3 concentration was more significant in
who reported smaller ozone changes in villages than in cit- the case of larger settlement units and occurred at 7:00–8:00
ies. The shapes of the ozone profiles were similar for par- (local time) in WPs and around 5:00 (local time) in SPs.
ticular types of settlement unit. The daily profiles for ­O3 This could be related to the decrease in the level of ozone,
concentrations were similar to a bimodal distribution in the which reacted with nitrogen oxide emitted during the morn-
case of towns and cities, and unimodal for the villages. The ing rush hours. The shape of the O ­ 3 diurnal profile in cities
maximum values occurred, irrespective of the season and during winter is puzzling, because the level of ozone at night
the size of the city/village, at around 14:00–15:00 local time.

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increased and at around 3:00 (local time) reached almost ¾ the profiles was more pronounced in SPs than in WPs, with
of the maximum daily value. a peak around 10:00 local time.
The average hourly ­S O 2 concentrations in WPs Of the 15 selected monitoring stations, 8 measured CO
ranged from 4.36 to 21.27 μg m−3 in cities, from 4.84 to concentrations in the ambient air. These were located mainly
23.29 μg m−3 in towns, and from 3.28 to 7.74 μg m−3 in in cities. Unfortunately, there were no CO measuring devices
rural areas (Fig. 8). The concentrations were much lower in installed at the other 7 stations, located in smaller settle-
SPs, ranging from 1.30 to 8.12 μg m−3 in cities, from 2.11 to ment units. The average hourly CO concentrations in WPs
5.65 μg ­m−3 in towns, and from 1.40 to 5.19 μg ­m−3 in rural ranged from 0.33 to 0.99 mg m−3 in cities, from 0.29 to
areas (Fig. 9). The level of S
­ O2 was generally the lowest in 1.03 mg m−3 in towns, and from 0.33 to 0.44 mg m−3 in
villages and higher in towns and cities. In the Greater Poland rural areas (Fig. 10). The concentrations were lower in SPs,
and Lublin regions, the concentrations of sulphur dioxide ranging from 0.17 to 0.61 mg m−3 in cities, from 0.17 to
in the cities of Poznań (L2) and Lublin (L5) were lower 0.51 mg ­m−3 in towns, and from 0.20 to 0.24 mg ­m−3 in rural
and comparable to those occurring in the towns of Piaski areas (Fig. 11). The CO level in the countryside changed
(S2) and Biały Słup (S5). The highest S ­ O2 level occurred only slightly during the day, in contrast to the fluctuations
in the Łódź region (Gajew/S3, Piotrków Trybunalski/M3, observed in towns and cities. The CO profiles were similar
and in Łódź/L3), where there is a very extensive network to a bimodal distribution and comparable to the ­NO2 daily
of power stations. Therefore, it was assumed that changes profiles. The highest peak in CO concentrations was in the
in ­SO2 concentrations were related to industrial power pro- evening, at 20:00–22:00 (local time), in both WP and SP.
duction in SPs and to emissions from the combustion of Of the 15 selected monitoring stations, 10 measured
fuels for heating individual buildings in WPs. The shapes of ­PM10 concentrations in the ambient air. These were mainly
the ­SO2 daily profiles were similar to unimodal (in SPs) or located in cities. Unfortunately, there were no P­ M10 meas-
bimodal (in WPs) distributions. The unimodal character of uring devices installed at the other 5 stations, located
in smaller settlement units. The average hourly P ­ M 10

Fig. 8  Average hourly ­SO2 concentrations in winter periods

Fig. 9  Average hourly ­SO2 concentrations in summer periods

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concentrations in WPs ranged from 28.76 to 62.54 μg m−3 ­P M 10 profiles at each location were characterized by a
in cities, from 31.00 to 75.87 μg m−3 in towns, and from bimodal distribution but with different shapes. The highest
25.07 to 43.16 μg m−3 in rural areas (Fig. 12). The con- ­PM10 concentrations during WPs occurred in the evening.
centrations in SPs ranged from 17.08 to 35.63 μg m−3 in This was in contrast to during SPs, when some locations
cities, from 16.09 to 34.00 μg m−3 in towns, and from (Wrocław/L1, Warsaw/L4, Konin/M2, and Gajew/S3) saw
15.90 to 28.78 μg m−3 in rural areas (Fig. 13). Therefore, their highest ­PM10 concentrations in the morning, around
during WPs the P ­ M10 levels in towns and cities were simi- 6:00–8:00 (local time). In others (Poznań/L2, Łódź/L3,
lar. In villages, they were approximately 50% lower. The Lublin/L5, Kłodzko/M1, Piotrków Trybunalski/M3, and

Fig. 10  Average hourly CO concentrations in winter periods

Fig. 11  Average hourly CO concentrations in summer periods

Fig. 12  Average hourly P
­ M10 concentrations in winter periods

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Fig. 13  Average hourly P
­ M10 concentrations in summer periods

Belsk Duży/S4), the highest peak occurred in the evening the condensation of water vapor and the coagulation of fine
at 21:00–22:00 (local time). dust particles (Pérez et al. 2010). However, in the study of
In the Polish air quality monitoring system, only CB air quality in Thessaloniki, Greece (Vouitsis et al. 2015),
stations measure ­PM2.5 and benzene concentrations in the the concentrations of particle number (PNC), P ­ M2.5, and
ambient air. The average hourly concentrations of ­PM2.5 in ­PM10, increased during the night (with peak at 23:00–24:00)
cities differed significantly depending on the season, rang- mostly in the winter period in traffic-affected sites, whereas
ing from 23.24 to 46.42 μg m−3 in WPs and from 8.40 to in city-background locations this was not clearly noticea-
18.18 μg m−3 in SPs (Fig. 14). The concentrations in SPs ble. On the other hand, in this analysis, ­PM2.5 concentration
were approximately three times smaller than during WPs decreased at night in winter, until around 3:00 local time.
and were lowest from 10:00 to 18:00 local time (depend- The differences in the shapes of the profiles and peak hours
ing on the location). The maximum values during WPs for ­PM10 and ­PM2.5 also were interesting. The diurnal vari-
occurred in the evening at approximately 21:00 (local time). ations in P
­ M10 concentration took various shapes in cities,
In SPs, the peak hours occurred between 6:00 and 24:00 whereas the concentrations of P ­ M2.5 followed very similar
local time. Interestingly, there were high concentrations of patterns. In addition, ­PM2.5 concentrations in the morn-
­PM2.5 throughout the night in SPs. Previous research on ing peak occurred 2 h earlier than the ­PM10 peak hours.
the composition of dust in urban areas of Barcelona, Spain In the study by Pérez et al. (2010), at weekdays the peaks
(Pérez et al. 2010) had also indicated the presence of large in PM1 and PM1–2.5 occurred at 6:00–9:00, whereas peak
amounts of organic matter, molecular carbon, and aero- in ­PM2.5–10 occurred at 10:00–15:00. At weekends, it was
sols in ­PM1–2.5 (approximately 48% of mass) and in ­PM1 around 2:00–8:00 and 11:00–12:00, respectively. However,
(around 85%) in urban ambient air. While in ­PM2.5–10 it con- in the case of traffic-affected site in the center of Madrid,
tributed only to 24%. This is puzzling, because sources of Spain, the peaks in P­ M2.5 and P
­ M10 were very close to each
anthropogenic emissions are inactive at night during sum- other (± 0.5 h) and occurred at 8:00–9:00 and 20:00–21:00
mer months. Therefore, it can be assumed that the increase (Moreno et al. 2013). Also, in urban areas, the average ­PM2.5
of ­PM2.5 concentrations at night might be associated with concentration are usually strongly correlated (­ R2 > 0.80) to

Fig. 14  Average hourly P­ M2.5

concentrations in cities

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Archives of Environmental Contamination and Toxicology (2019) 77:197–213 207

­PM10 and amounted to 60–90% of P ­ M10 concentrations the summer was three to four times lower than in winter.
(Gupta et al. 2006; Pérez et al. 2010). Nevertheless, obser- The highest concentrations always occurred in the evening,
vations of PM could indicate that differences in the vary- between 21:00 and 22:00 local time.
ing concentrations of course and finer particles in the urban The shapes of the average daily profiles of N ­ O2 and CO,
environment might be partially due to the different processes and ­NOx and ­PM10 were compared for different settlement
of their formation (Pérez et al. 2010). units (Figs. 16, 17, 18, 19). This was to verify the generally
As in the case of P
­ M2.5, the concentrations of benzene prevailing opinion that the N
­ O2 and N­ Ox concentrations usu-
­(C6H6) in cities changed and varied significantly depend- ally indicate road transport intensity, whereas the occurrence
ing on the season. The average hourly benzene concentra- of CO and P ­ M10 indicate emissions from road transport and
tions ranged from 0.48 to 1.42 μg m−3 in WPs and from area sources (so-called “low emission”). It was observed that
1.84 to 5.47 μg m−3 in SPs (Fig. 15). The benzene level in there was a co-occurrence of changes in the concentrations,

Fig. 15  Average hourly concen-

trations of benzene in cities

Fig. 16  Comparison of average hourly ­NO2 and CO profiles in WPs

Fig. 17  Comparison of average hourly ­NO2 and CO profiles in SPs

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208 Archives of Environmental Contamination and Toxicology (2019) 77:197–213

as well as of “peak hours” and “low hours,” in both WPs and Approximately 76% of ­PM2.5 emissions originates from
SPs. The high correspondence between the profile shapes fuel combustion in power generation, industrial, and non-
in SPs could indicate the impact of emissions from linear industrial combustion (Dębski et al. 2015). The presence
sources. However, it is more difficult to explain their consist- of benzene results from tobacco smoke and from burn-
ency in WPs, when there also were area emissions related to ing liquid fuels in car engines (WHO 2000). Also, in the
the heating of individual buildings. transport-affected sites, the carbonaceous compounds are
The shapes of the average hourly benzene and P ­ M2.5 pro- substantial (35–48%) components of ­PM2.5 (Gómez-Perales
files were compared for cities during WPs and SPs (Fig. 20). et al. 2004; Harrison et al. 2004, Pérez et al. 2010). In the
The presence of P ­ M2.5 in the ambient air is due mainly to analyzed locations, the changes in ­PM2.5 and benzene lev-
the burning of fossil fuels (50% of energy in Poland is gen- els had similar hourly profiles, indicating the co-occurrence
erated from hard coal and lignite, while crude oil provides of these air pollutants in urbanized areas. The co-existence
26% and natural gas 15% of the country’s energy needs). of PM and benzene (correlation coefficient of 0.69–0.97)

Fig. 18  Comparison of average hourly ­NOx and ­PM10 profiles in WPs

Fig. 19  Comparison of average hourly ­NOx and ­PM10 profiles in SPs

Fig. 20  Comparison of aver-
age hourly benzene and P
­ M2.5
profiles in cities

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Archives of Environmental Contamination and Toxicology (2019) 77:197–213 209

during the transport rush hours were previously reported at the following times: 7:00–8:00 and 21:00–22:00 in cit-
(Gupta et al. 2006). ies; 5:00–6:00 and 21:00–22:00 in towns; 6:00–9:00 and
There were significant shifts between the occurrence of 19:00–22:00 in villages. For a comparison, when consid-
the daily maximum and daily minimum in WPs and SPs ering PM and ­NO2 air contamination, in urban-traffic area
(Tables 6, 7, 8). The most favorable conditions, in terms in Madrid (Spain), the most favorable conditions occurred
of levels of air pollution, occurred in towns and cities in at around 4:00 and 15:00 local hour (Moreno et al. 2013).
the morning at 3:00–5:00 (local time) and in the afternoon In Barcelona (Spain), this was around 15:00 (Pérez et al.
at 12:00–15:00. In the villages, the best air quality occurred 2010), and in Thessaloniki (Greece) around 4:00–6:00 and
between 4:00 and 6:00 (local time). On  the other hand, 15:00–18:00 (Vouitsis et al. 2015). For comparison, in the
during WPs the least favorable conditions in terms of air cities of Canoas and Esteio, in Brazil, the most favorable air
quality occurred, regardless of location at 8:00–10:00 and quality conditions occurred at 4:00–6:00 and 14:00–17:00
19:00–21:00 (local hour). In SPs, air quality was poorest (Agudelo-Castaneda and Teixeira 2014).

Table 6  Daily maximum Peak hours Low hours

and daily minimum average
concentrations of air pollutants Winter period Summer period Winter period Summer period
in cities (CB stations)
Morning Evening Morning Evening Morning Evening Morning Evening

NO2 09:00 19:00 07:00 21:00 04:00 12:00 03:00 12:00

NOx 09:00 19:00 07:00 21:00 04:00 13:00 03:00 13:00
O3 03:00 14:00 n/a 15:00 08:00 20:00 06:00 n/a
SO2 12:00 19:00 10:00 n/a 05:00 16:00 04:00 n/a
CO 08:00 20:00 07:00 22:00 05:00 13:00 04:00 13:00
PM10 10:00 21:00 08:00 22:00 03:00 14:00 03:00 14:00
PM2.5 07:00 21:00 06:00 24:00 03:00 12:00 04:00 18:00
C6H6 09:00 21:00 07:00 22:00 05:00 14:00 05:00 15:00

Table 7  Daily maximum Peak hours Low hours

and daily minimum average
concentrations of air pollutants Winter period Summer period Winter period Summer period
in cities (TB stations)
Morning Evening Morning Evening Morning Evening Morning Evening

NO2 08:00 19:00 05:00 21:00 04:00 13:00 03:00 12:00

NOx 08:00 19:00 06:00 21:00 04:00 13:00 03:00 13:00
O3 02:00 14:00 n/a 15:00 08:00 20:00 05:00 n/a
SO2 10:00 20:00 10:00 n/a 05:00 14:00 04:00 n/a
CO 08:00 20:00 06:00 22:00 05:00 13:00 04:00 13:00
PM10 09:00 20:00 06:00 21:00 05:00 14:00 03:00 16:00

Table 8  Daily maximum Peak hours Low hours

and daily minimum average
concentrations of air pollutants Winter period Summer period Winter period Summer period
in villages (RB stations)
Morning Evening Morning Evening Morning Evening Morning Evening

NO2 08:00 19:00 n/a 22:00 05:00 13:00 n/a 13:00

NOx 09:00 19:00 07:00 21:00 04:00 13:00 03:00 13:00
O3 n/a 14:00 n/a 15:00 07:00 n/a 05:00 n/a
SO2 n/a 12:00 09:00 n/a 04:00 n/a 04:00 n/a
CO 08:00 22:00 06:00 22:00 06:00 14:00 03:00 14:00
PM10 09:00 20:00 06:00 19:00 06:00 13:00 03:00 15:00

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210 Archives of Environmental Contamination and Toxicology (2019) 77:197–213

According to the literature (Gaffron 2012; Menut et al. and villages. However, the “time shift” between emissions
2012; Moreno et al. 2013; Pérez et al. 2010; Vouitsis et al. and increases/decreases in air pollutant concentrations could
2015), daily variations in ­NO2 and ­PM10 concentrations be the result of meteorological factors, which may (or may
show a shift between peak hours during road transport rush not) result in dispersal processes and coagulation, as well as
hours (Table 9). In selected locations in Central Europe, in chemical and photochemical processes.
shifts of ± 3 h have been reported in the morning and of up
to + 5 h in the evening. In cities of South-Western Europe,
this shift reached up to + 4 h in both the morning and in Conclusions
the evening. In the city of Thessaloniki (Greece) in South-
Eastern Europe, there was a shift of ± 4 h in the morning The purpose of this investigation was to determine the
and 0–3 h in the evening. Therefore, the “most and least “most” and ‘”least favorable” hours during the day in terms
favorable” ambient air-quality conditions were not strictly of ambient air quality for different types of settlement unit
related/correlated to road traffic intensity in cities, towns, (cities, towns, and villages). The results could be used to

Table 9  Differences between Location, station type Peak hour/ Peak hour/ Source Description/period
the occurrence of maximum difference difference
average hourly N­ O2 and ­PM10 (h) (h)
concentrations and traffic rush
hours (described as “traffic” Central Europe
stations)
 Hamburg Traffic 08:00/- 17:00/- Gaffron (2012) Year
 Warsaw, CB NO2 – 22:00/+ 5 Menut et al. (2012) Model, summer
PM10 06:00/− 2 22:00/+ 5
 Poland, CB NO2 09:00/+ 1 19:00/+ 2 Own analysis Winter
PM10 10:00/+ 2 21:00/+ 4
NO2 07:00/− 1 21:00/+ 4 Summer
PM10 08:00/+ 0 22:00/+ 5
 Poland, TB NO2 08:00/+ 0 19:00/+ 2 Winter
PM10 09:00/+ 1 21:00/+ 4
NO2 05:00/− 3 21:00/+ 4 Summer
PM10 06:00/− 2 21:00/+ 4
 Poland, RB NO2 08:00/+ 2 19:00/+ 2 Winter
PM10 09:00/+ 1 20:00/+ 3
NO2 – 22:00/+ 5 Summer
PM10 06:00/− 2 19:00/+ 2
South-West Europe
 Barcelona Traffic 06:00/- 17:00/- Pérez et al. (2010) Summer, weekdays
 Barcelona,CB NO2 07/00/+ 1 21:00/+ 4 Summer, weekdays
PM1 06:00/+ 0 21:00/+ 4
PM1–2.5 09:00/+ 3 –
PM2.5–10 10:00/+ 4 14:00/− 3
 Madrid, UT NO2 08:00/+ 2 21:00/+ 4 Moreno et al. (2013) Winter
PM10 09:00/+ 3 20:00/+ 3
South-East Europe
 Thessaloniki Traffic 09:00/- 21:00/- Vouitsis et al. (2015) Winter
 Thessaloniki, CB PM10 13:00/+ 4 22:00/+ 1 Winter
PM10 11:00/+ 2 21:00/+ 0 Summer
 Thessaloniki, UT NO2 13:00/+ 4 21:00/+ 0 Winter
PM10 11:00/+ 2 24:00/+ 3
NO2 13:00/+ 4 21:00/+ 0 Summer
PM10 07:00/− 2 21:00/+ 0

Our study, based on Gaffron (2012), Menut et  al. (2012), Pérez et  al. (2010), Moreno et  al. (2013), and
Vouitsis et al. (2015)
UT air quality monitoring stations located near urban traffic

13
Archives of Environmental Contamination and Toxicology (2019) 77:197–213 211

help improve air quality management process in cities, air quality in the various settlement units differed by ± 2 h.
towns, and villages. The concentrations of air pollutants The best ambient air-quality conditions in cities, towns,
were found to change dynamically during the day. Each air and villages, with the exception of ozone and taking into
pollutant had a unusual, characteristic daily concentration account mainly concentrations of N ­ O2 and dust, occurred in
profile, resembling a unimodal or bimodal distribution. The the early mornings and in the afternoon. Therefore, the most
profiles changed significantly depending on the season. The favorable ambient air-quality conditions occurred between
concentrations of ­SO2, CO, ­PM10, ­PM2.5, and benzene were 3:00 and 5:00 and between 12:00 and 15:00 (local time).
significantly higher in winter periods than during summer. This information is particularly valuable for people to sched-
The time between “peak hours” of air pollutant concentra- ule outdoor activities, such as recreation or sport, as well
tion during the day also was shorter in the winter. as for structuring the working day (e.g., lunchtime, which
The level of air pollutants was generally higher in the usually takes place at 12:00–13:00) and time spent outside
analyzed cities than in the towns and villages. Although the buildings. As a result, for example, children and the elderly
level of air pollution depended largely on the size of the set- may be recommended to engage in outdoor activities before
tlement unit (city, town, or village), the daily profiles of the 18:00 in urban areas during summer, because later in the day
concentrations of air pollutants had relatively similar shapes. there is an increase in the concentrations of dust, N ­ O2, and
There were clear local maxima and minima during the day. CO. However, there is a higher concentration of ozone at this
The peak hours for air pollution usually did not coincide time. Thus, air quality should be assessed on a case-by-case
with the assumed traffic-intensity peaks (rush hours). This is basis, for each area/region, taking into account both the type
in contrast to claims made in the literature that air pollution of settlement unit, its geographical location, the climate, and
depends largely on road-traffic intensity (Agudelo-Castaneda the types of emission sources.
and Teixeira 2014; Menut et al. 2012; Moreno et al. 2013,
Pérez et al. 2010). Our analysis shows that there was a time Acknowledgements  The authors thank the Voivodship Inspectorates
for Environmental Protection (WIOŚ) in Poland and the Chief Inspec-
shift of ± 5 h between the peak hours of air pollution and torate for Environmental Protection (GIOŚ) in Poland for allowing the
the transport rush hours. However, this time shift depended use of measurement data obtained from air quality monitoring stations.
on the type of air pollutant, the season, and the size of the
settlement unit. Open Access  This article is distributed under the terms of the Crea-
Different approaches can be used to assess the daily tive Commons Attribution 4.0 International License (http://creat​iveco​
mmons​.org/licen​ses/by/4.0/), which permits unrestricted use, distribu-
changes in the concentration of pollution. It also is difficult tion, and reproduction in any medium, provided you give appropriate
to identify the most important air pollutants. The best and credit to the original author(s) and the source, provide a link to the
worst conditions in terms of ambient air quality should be Creative Commons license, and indicate if changes were made.
determined individually for each country/region, depend-
ing on the pollutants, the climate, and the characteristics
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