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<article xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:oasis="http://docs.oasis-open.org/ns/oasis-exchange/table" xml:lang="en" dtd-version="3.0">
  <front>
    <journal-meta><journal-id journal-id-type="publisher">SE</journal-id><journal-title-group>
    <journal-title>Solid Earth</journal-title>
    <abbrev-journal-title abbrev-type="publisher">SE</abbrev-journal-title><abbrev-journal-title abbrev-type="nlm-ta">Solid Earth</abbrev-journal-title>
  </journal-title-group><issn pub-type="epub">1869-9529</issn><publisher>
    <publisher-name>Copernicus Publications</publisher-name>
    <publisher-loc>Göttingen, Germany</publisher-loc>
  </publisher></journal-meta>
    <article-meta>
      <article-id pub-id-type="doi">10.5194/se-9-669-2018</article-id><title-group><article-title>Polycyclic aromatic hydrocarbon in urban soils of an Eastern European
megalopolis: distribution, source identification<?xmltex \hack{\break}?> and cancer risk evaluation</article-title><alt-title>Polycyclic aromatic hydrocarbon in urban soils of an Eastern European megalopolis</alt-title>
      </title-group><?xmltex \runningtitle{Polycyclic aromatic hydrocarbon in urban soils of an Eastern European megalopolis}?><?xmltex \runningauthor{G.~Shamilishvily et al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>Shamilishvily</surname><given-names>George</given-names></name>
          <email>george199207@gmail.com</email>
        <ext-link>https://orcid.org/0000-0002-2183-7630</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Abakumov</surname><given-names>Evgeny</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-5248-9018</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Gabov</surname><given-names>Dmitriy</given-names></name>
          
        </contrib>
        <aff id="aff1"><label>1</label><institution>St. Petersburg State University, Dept. of Applied Ecology, St. Petersburg, Russia</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>Institute of Biology, Komi Scientific Centre, Russian Academy of Sciences, Syktyvkar, Russia</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">George Shamilishvily (george199207@gmail.com)</corresp></author-notes><pub-date><day>23</day><month>May</month><year>2018</year></pub-date>
      
      <volume>9</volume>
      <issue>3</issue>
      <fpage>669</fpage><lpage>682</lpage>
      <history>
        <date date-type="received"><day>27</day><month>May</month><year>2017</year></date>
           <date date-type="rev-request"><day>16</day><month>August</month><year>2017</year></date>
           <date date-type="rev-recd"><day>17</day><month>March</month><year>2018</year></date>
           <date date-type="accepted"><day>16</day><month>April</month><year>2018</year></date>
      </history>
      <permissions>
        
        
      <license license-type="open-access"><license-p>This work is licensed under the Creative Commons Attribution 3.0 Unported License. To view a copy of this licence, visit <ext-link ext-link-type="uri" xlink:href="https://creativecommons.org/licenses/by/3.0/">https://creativecommons.org/licenses/by/3.0/</ext-link></license-p></license></permissions><self-uri xlink:href="https://se.copernicus.org/articles/.html">This article is available from https://se.copernicus.org/articles/.html</self-uri><self-uri xlink:href="https://se.copernicus.org/articles/.pdf">The full text article is available as a PDF file from https://se.copernicus.org/articles/.pdf</self-uri>
      <abstract>
    <p id="d1e106">This study explores qualitative and quantitative composition of
15 priority polycyclic aromatic hydrocarbons (PAHs) in urban soils of some parkland, residential and industrial
areas of the large industrial centre of
Saint Petersburg (Russian Federation) in Eastern Europe. The aim of the study was to test the
hypothesis on the PAH loading differences among urban territories with
different land use scenarios. Benzo(a)pyrene toxic equivalency factors (TEFs)
were used to calculate BaP<inline-formula><mml:math id="M1" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:math></inline-formula> in order to evaluate carcinogenic
risk of soil contamination with PAHs. Results of the study demonstrated that
soils within residential and industrial areas are characterized by common
loads of PAHs generally attributed to high traffic activity in the city.
Considerable levels of soil contamination with PAHs were noted. Total PAH
concentrations ranged from 0.33 to 8.10 mg kg<inline-formula><mml:math id="M2" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>. A larger portion of
high-molecular-weight PAHs along with determined molecular ratios suggest the
predominance of pyrogenic sources, mainly attributed to combustion of
gasoline, diesel and oil. Petrogenic sources of PAHs have a significant
portion and define the predominance of low-molecular-weight PAHs associated with petroleum, such as phenanthrene. Derived concentrations of seven
carcinogenic PAHs as well as calculated BaP<inline-formula><mml:math id="M3" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:math></inline-formula> were multiple times
higher than reported in a number of other studies. The obtained
BaP<inline-formula><mml:math id="M4" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:math></inline-formula> concentrations of the sum of 15 PAHs ranged from 0.05 to
1.39 mg kg<inline-formula><mml:math id="M5" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>. A vast majority of examined samples showed
concentrations above the safe value of 0.6 mg kg<inline-formula><mml:math id="M6" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> (CCME,
2010). However, estimated incremental lifetime risks posed to the population
through distinct routes of exposure were in an acceptable range. One-way
ANOVA results showed significant differences in total PAHs and the sum of
seven
carcinogenic PAH concentrations as well as in levels of FLU, PHE, FLT, PYR,
BaA, CHR, BbF, BaP and BPE among parkland, residential and industrial land
uses, suggesting the influence of the land use factor.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

<sec id="Ch1.S1" sec-type="intro">
  <title>Introduction</title>
      <p id="d1e180">There is a huge variety of toxic organic compounds, but in environment
control practices around the world evaluation of contaminated areas is often
based on priority listed pollutants. This list includes, for example,
polycyclic aromatic hydrocarbons (PAHs), which are ubiquitous organic
pollutants in the environment (Wilcke, 2000). PAHs are a large group of
aromatic organic compounds consisting of several hundred individual
homologues and isomers containing at least two condensed aromatic rings.
Their input to the environment has both natural and anthropogenic origins.
Natural sources include releases from vegetation fires, diagenetic processes
and volcanic exhalations (ATSDR, 1995; Wilcke, 2000). In turn, anthropogenic
PAHs occur from pyrolytic processes, especially incomplete combustion of
organics during industrial activities, domestic heating, waste incineration,
transportation and power generation (ATSDR, 1995; Wilcke, 2000). It is
believed that by far most PAHs are released into the environment by anthropogenic
combustion of wood and fossil fuels (Wilcke, 2000). Soil contamination with
PAHs is even noted in such remote places as Antarctica, basically near the
polar stations. However, the origin of PAHs in Antarctic soils is questioned,
considering that it could have both natural sources, for example,
decomposition<?pagebreak page670?> of organic matter, and anthropogenic sources, such as fuel
combustion, oil spills and long-range transport of solid atmospheric
particles containing PAH mixtures (Abakumov et al., 2014, 2015). Detection of
some individual PAHs is of the most environmental importance because of the
established carcinogenic, mutagenic and teratogenic effects on living
organisms and in humans particularly (Yu, 2002; Guo et al., 2013). There have been 16 PAHs listed as priority contaminants by both the US
Environmental Protection Agency (US EPA) and the European Union (EU). Among
them,
seven compounds, i.e., benzo(a)anthracene, chrysene, benzo(a)pyrene,
benzo(b)fluoranthene, benzo(k)fluoranthene, dibenz(a,h)anthracene and
indeno(1,2,3-cd)pyrene are considered to be probable human carcinogens (US EPA,
2002). In Canada, the USA and some European countries regulation of soil
contamination is based on developed soil quality criteria for selected PAHs
or their sum. Only a few countries have established comprehensive soil
guideline values for particular land use at least for the sum of
priority PAHs (<inline-formula><mml:math id="M7" display="inline"><mml:mi mathvariant="normal">Σ</mml:mi></mml:math></inline-formula>7–16). Generally, the existing soil critical values
provide only human health-risk-based approaches and do not consider
protection of other ecological receptors. In turn, the US EPA has developed
ecological soil screening levels (Eco-SSLs) for PAHs, which are derived
separately for four groups of ecological receptors: plants, soil
invertebrates, birds and animals. However, these screening levels are intended
to evaluate an unacceptable ecological risk to terrestrial receptors; they
are not designed to be used as clean-up levels. For this purpose the US EPA
adopted the human-health-based preliminary remediation goals for soil
using estimates of different routes of exposure. In contrast to this, the Russian
Federation has not yet developed soil guideline values, at least for the sum
of priority PAHs; normalization is provided only for soil contamination with
benzo(a)pyrene without distinction for particular land use. Furthermore,
no threshold values are provided for other POPs (polychlorinated biphenyls, chlororganic pesticides, benzene, toluene, ethylbenzene and xylenes). A summary of soil guideline
values for PAHs set in some countries is presented in Table S1 in the Supplement. Thus, studies on soil contamination with PAHs are of
the  utmost importance as they provide information that can be further used to
delineate special contaminated sites exhibiting a high risk of human exposure.
Thousands of reports about PAH concentrations, sources and health risk
assessments in urban and semiurban areas from all over the world were
published in recent years (Yunker et al., 2002; Liu et al., 2010; Wang et
al., 2013). Elevated levels of PAHs in urban soils were reported in Houston, USA
(Hwang et al., 2002); Beijing, China (Tang et al., 2005); Glasgow, UK;
Turin, Italy (Morillo et al., 2007); and Esbjerg, Denmark (Essumang et
al., 2011).</p>
      <p id="d1e190">St. Petersburg is the largest industrial and transport centre in the
north-western region of Russia and is of great interest from the viewpoint of
environmental concern. The ecological status of such a large centre reflects
the whole range of socioeconomic problems resulting in the decline of human
health under the influence of various chemical, physical and biological
factors. The ecological situation in the city is determined by the emissions
from more than a thousand industrial enterprises, a large railway junction,
a seaport and the large motor vehicle fleet – 1 670 794 cars and 207 975
trucks as of 2014 (Belousova et al., 2015). All this transport is served by a
huge number of petrol stations and transport companies: currently in St.
Petersburg there are 27 fuel operators and 397 petrol stations. Industrial
enterprises of the city include high-capacity, resource- and power-consuming
ecologically dangerous works. According to the data collected from the
automatic air monitoring system of the city in 2014, total emissions into the
air from both the stationary sources and vehicles has reached 513 200 t of chemicals in
2014, including 16 903 t of hydrocarbons (CH<inline-formula><mml:math id="M8" display="inline"><mml:msub><mml:mi/><mml:mi>x</mml:mi></mml:msub></mml:math></inline-formula>), 3000 t of black
carbon (BC) and 47 900 t of volatile organic compounds (VOCs) (Belousova et
al., 2015). The amount of emissions per capita is 135.9 kg yr<inline-formula><mml:math id="M9" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>, per
unit area – 434.5 t km<inline-formula><mml:math id="M10" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> (Belousova et al., 2015). At the same time,
91.9 % of emissions are attributed to transport activity. Industrial
and transport emissions along with inputs from petroleum products are the major source of soil contamination with PAHs
in urban areas. No systematic
survey of soil contamination with priority PAHs has been conducted yet in
St. Petersburg except for benzo(a)pyrene (Gorky and Petrova, 2012).
Considering this fact and environmental aspects of the territory described
above, St. Petersburg affords an excellent location to study geochemical
cycles of PAHs.</p>
      <p id="d1e226">Therefore, this study aims to test the hypothesis on the PAH load
differences among urban territories with different land use scenarios. The
results of this study would contribute to the knowledge about PAH
distribution in urban soils of the Eastern European region and may be used by
decision makers during land management.</p>
      <p id="d1e229">Objectives of the study were to (1) explore qualitative and quantitative
composition of 15 priority PAHs in urban soils in some parkland, residential
and industrial areas of St. Petersburg; (2) compare with existing data on the
PAH distribution in urban soils; (3) distinguish between PAH sources using
PAH molecular ratios; and (4) evaluate cancer risks (CRs) associated with soil
contamination with PAHs within selected areas.</p>
</sec>
<sec id="Ch1.S2">
  <title>Materials and methods</title>
<sec id="Ch1.S2.SS1">
  <title>Study site description</title>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T1" specific-use="star"><caption><p id="d1e246">Description of the study area.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="5">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1">Characteristics</oasis:entry>  
         <oasis:entry colname="col2">Units</oasis:entry>  
         <oasis:entry colname="col3">Primorsky</oasis:entry>  
         <oasis:entry colname="col4">Vasileostrovsky</oasis:entry>  
         <oasis:entry colname="col5">Kirovsky</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3">District</oasis:entry>  
         <oasis:entry colname="col4">District</oasis:entry>  
         <oasis:entry colname="col5">District</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M11" display="inline"><mml:mi>S</mml:mi></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2">km<inline-formula><mml:math id="M12" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">109.87</oasis:entry>  
         <oasis:entry colname="col4">17.1</oasis:entry>  
         <oasis:entry colname="col5">47.10</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Population</oasis:entry>  
         <oasis:entry colname="col2">–</oasis:entry>  
         <oasis:entry colname="col3">534 646</oasis:entry>  
         <oasis:entry colname="col4">211 048</oasis:entry>  
         <oasis:entry colname="col5">334 746</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Industries</oasis:entry>  
         <oasis:entry colname="col2">units</oasis:entry>  
         <oasis:entry colname="col3">250</oasis:entry>  
         <oasis:entry colname="col4">350</oasis:entry>  
         <oasis:entry colname="col5">70</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Number of potential contamination sources with petroleum products</oasis:entry>  
         <oasis:entry colname="col2">units</oasis:entry>  
         <oasis:entry colname="col3">14</oasis:entry>  
         <oasis:entry colname="col4">7</oasis:entry>  
         <oasis:entry colname="col5">10</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Density of potential contamination sources</oasis:entry>  
         <oasis:entry colname="col2">units per km<inline-formula><mml:math id="M13" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col3">0.13</oasis:entry>  
         <oasis:entry colname="col4">0.41</oasis:entry>  
         <oasis:entry colname="col5">0.21</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">CH<inline-formula><mml:math id="M14" display="inline"><mml:msub><mml:mi/><mml:mi>x</mml:mi></mml:msub></mml:math></inline-formula> emissions from stationary sources in 2014</oasis:entry>  
         <oasis:entry colname="col2">thousand tons</oasis:entry>  
         <oasis:entry colname="col3">0.556</oasis:entry>  
         <oasis:entry colname="col4">0.034</oasis:entry>  
         <oasis:entry colname="col5">0.708</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">VOC emissions from stationary sources in 2014</oasis:entry>  
         <oasis:entry colname="col2">thousand tons</oasis:entry>  
         <oasis:entry colname="col3">0.153</oasis:entry>  
         <oasis:entry colname="col4">0.099</oasis:entry>  
         <oasis:entry colname="col5">0.545</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">BC emissions from stationary sources in 2014</oasis:entry>  
         <oasis:entry colname="col2">thousand tons</oasis:entry>  
         <oasis:entry colname="col3">0.237</oasis:entry>  
         <oasis:entry colname="col4">0.037</oasis:entry>  
         <oasis:entry colname="col5">0.174</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <p id="d1e480">Choice of the study area, namely the Primorsky, Vasileostrovsky and Kirovsky
administrative districts of St. Petersburg, was made in the order of
increasing location density of potential stationary sources of contamination
with PAHs, population density and traffic activity. Detailed<?pagebreak page671?> characteristics
about each chosen area are given in Table 1. Certain recreational,
residential and industrial land use scenarios within each chosen district
were included in the study. Information on
the land use scenario of each chosen area was obtained using the online map
service “Regional Geoinformation System (RGIS)” developed with the support
of the committee for land resources and land management of St. Petersburg
(Fig. 1). Potential sources of PAH contamination affecting PAH levels in soil
here are high traffic activity (western highway and Primorsky prospect),
steel and chemical industries (Kirovsky engineering plant, Baltic Shipyard
plant, varnish factory Kronos SPb, and thermal power stations (North-West Thermal Power Plant).</p>
      <p id="d1e483">Climate is moderately continental and significantly affected by the Baltic Sea.
Annual amount of atmospheric precipitates varies from 565 to 635 mm. The
territory represents an almost flat plain with altitudes below 20 m above
the sea level (Neva lowland). Natural soil formation usually occurs on
ancient lake-marine littoral sands, sandy loams and loams (less) depleted in
calcium (Gagarina et al., 2008). Urban soils are formed on the bulk deposits
ranging from 0.9 to 4 m of thickness (Dashko et al., 2011). Soils are strongly disturbed by anthropogenic activities (buried,
sealed and/or contaminated), with small relatively intact islands in natural
and seminatural areas to the north, north-west and north-east of the city.
An example of natural soils in St. Petersburg are Albeluvisols, which are
widespread in suburb territories of the Leningradsky region. Soils of the
historical centre are presented by anthropogenic soil-like formations called <italic>urbanozems</italic> (Stroganova et al., 1992) or
<italic>urbiquazizems</italic> (Shishov et al., 2004)
in national soil classification systems and generally characterized by light grain
size and
modified soil profiles, with abundant inclusions of anthropogenic artefacts
in the form of debris, domestic wastes and remains of communications. They
also have a
neutral to alkaline pH; high humus, nitrogen and phosphorus content; humate
and fulvic-humate types of humus; and traces of chemical contamination
(Rusakov et al., 2005; Matinyan et al., 2005; Ufimtseva et al., 2011).
Investigated urban soils were classified as Technosols according to the World Reference
Base for Soil Resources (Michéli et al., 2006).</p>
</sec>
<sec id="Ch1.S2.SS2">
  <title>Sampling strategy and procedure</title>
      <p id="d1e498">Sampling was conducted in September 2013 at nine urban sites in dry and clear
weather conditions according to international standard protocol ISO 10381-1
(2002) and national sampling standard GOST 17.4.4.02-84 (1984). Soil samples
were taken from the 0 to 20 cm topsoil layer. A total of 135 grab soil samples were
collected diagonally from 25 m<inline-formula><mml:math id="M15" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula> sampling plots. Single samples were
combined into 27 composite samples of 0.7 kg each. Location of the
sampling sites was defined according to proximity to residential areas and
potential pollution sources (Fig. 1a, b, c).</p>
      <p id="d1e510">Sampling strategy responds to the study objectives and is aimed at providing
comprehensive characterization of the selected sites suspected to be
contaminated with PAHs.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1" specific-use="star"><caption><p id="d1e515">Location of the sampling sites.</p></caption>
          <?xmltex \igopts{width=497.923228pt}?><graphic xlink:href="https://se.copernicus.org/articles/9/669/2018/se-9-669-2018-f01.png"/>

        </fig>

      <p id="d1e524">Quantity of sampling sites ranged between two and five per each zone. The
description of sampling sites providing information on location, proximity
to potential sources of contamination, population density, road traffic and
dominating wind direction is given in Table S3 in the Supplement. All the
sampling plots were located near highways with different traffic rates with
a distance of no further than 200 m. Distance among sampling plots ranged
between 100 and 200 m. Total quantity of sampling plots was 34. The
sampling depth was common among all sites and matched a topsoil layer
of 0–20 cm. Depth of sampling is a function of exposure routes (e.g., soil
ingestion, dermal contact with soil and dust, inhalation of contaminated
dust, inhalation of volatile compounds). Five single initial samples of 0.05 kg each collected diagonally from 25 m<inline-formula><mml:math id="M16" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula> sampling plots were combined
into one grab sample of 0.1–0.2 kg, packed in a dark glass flask, marked,
transported to the laboratory and stored at <inline-formula><mml:math id="M17" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula>4 <inline-formula><mml:math id="M18" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C. A total of 135
grab soil samples were collected. Grab samples were combined into 27
composite samples of 0.7 kg each. The sampling scheme represents both the
purposive and judgment sampling techniques, delineating sample locations
that were assumed to be representative of the whole site and most contaminated.
Instruments for sample<?pagebreak page672?> derivation included a stainless steel scoop and
knife prewashed with acetone. The representativeness of collected samples
was provided through mixing and taking an average sample using a quartering
method.</p>
      <p id="d1e553">Collected samples were packed in labelled sterile plastic bags, kept in cool
conditions and transported to the laboratory. Once in the laboratory, soil
samples were dispersed on the sterile glass plates and air-dried at room
temperature for 5 days. Then they were cleaned of the organic and inorganic debris,
ground in a laboratory vibrating cup mill, sieved through a 0.25 mm caprone
sieve and finally stored in the dark glass containers prewashed with acetone
until analysis. This technique enables the prevention of cross-contamination as
well as losses of PAHs due to environmental factors (Berset et al., 1999).</p>
</sec>
<sec id="Ch1.S2.SS3">
  <title>HPLC, PAH source identification and risk evaluation</title>
      <p id="d1e562">A total of 15 PAHs were analysed, including naphthalene (NAP), acenaphthene (ANA),
fluorene (FLU), phenanthrene (PHE), anthracene (ANT), fluoranthene (FLT),
pyrene (PYR), benzo(a)anthracene (BaA), chrysene (CHR), benzo(b)fluoranthene
(BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP),
dibenz(ah)anthracene(DBA), benzo(g,h,i)perylene (BPE) and
indeno(1,2,3-cd)pyrene (IPY).</p>
      <p id="d1e565">PAH content in samples was determined on the basis of US EPA method 8310 (1996a), national standard method PND F 16.1:2:2.2:3.62-09 (2009), and
the method of Gabov (2007, 2008). Extraction of the PAHs was carried out at room temperature with
methylene chloride (high purity grade) and ultrasonic treatment via a Branson
5510 ultrasonic bath (USA, power 469 W, working frequency 42 kHz) following
the US EPA method 3550b (1996b). Solvent removal (evaporation) was carried
out with Kuderna–Danish concentrator (Supelco). PAH fractions were
purified by consecutive chromatography in columns filled with aluminum oxide
(Brockmann activity grade 2–3, Neva Reaktiv) and silica gel (Fluka) according
to the US EPA purification method 3660c (1996c). The purity was controlled by
the absence of peaks in the blank chromatogram. A standard mixture of 15
PAHs (Supelco) with the concentrations of each component in the range of
100–2000 <inline-formula><mml:math id="M19" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi></mml:mrow></mml:math></inline-formula> cm<inline-formula><mml:math id="M20" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> was used to prepare the standard PAH solutions.
Qualitative and quantitative determination of PAHs in soils was carried out
with reverse-phase high-performance liquid chromatography (HPLC) in gradient
mode with spectrofluorometric detection via the ”LYuMAHROM” chromatograph
(Lumex, Russia). Chromatography was performed at 30 <inline-formula><mml:math id="M21" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C on a
column Supelcosil™ LC-PAH n5 <inline-formula><mml:math id="M22" display="inline"><mml:mrow><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">m</mml:mi></mml:mrow></mml:math></inline-formula> (25 cm <inline-formula><mml:math id="M23" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 2.1 mm). The mobile phase was provided with an acetonitrile–water gradient. Samples of
10 <inline-formula><mml:math id="M24" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>L volume were injected using the injection<?pagebreak page673?> valve. Individual PAHs were
identified by the time of retention and comparison of fluorescence spectra
of the components coming from the column with spectra of the standard PAHs.
Quantitative analysis of PAHs was performed using an external standard method. For
the quality assurance purposes Standard Reference Materials<sup>®</sup> 1944 New York/New Jersey waterway sediment (National Institute of Standards
and Technologies (NIST), USA) containing a mixture of 15 PAHs was subjected
to the procedure described above. The error of measuring the PAHs
(benz[a]pyrene) in the soils was 35 % in the range of 5–40 ng g<inline-formula><mml:math id="M25" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> and 25 %
in the range of 40–2000 ng g<inline-formula><mml:math id="M26" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> with a confidence probability of <inline-formula><mml:math id="M27" display="inline"><mml:mrow><mml:mi>P</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.95</mml:mn></mml:mrow></mml:math></inline-formula>.</p>
      <p id="d1e663">PAH molecular markers and ratios were used to determine PAH sources (Yunker
et al., 2002; Hwang et al., 2003; Wang et. al 2015, 2017). The sum of
combustion PAHs (combPAH/15PAH) was used as the tracer of pyrogenic sources.
The combPAH/15PAH marker indicates the portion of the sum of combustion-specific
compounds in total PAH content, which are fluoranthene, pyrene, chrysene,
benzo(a)anthracene, benzo(k)fluoranthene, benzo(b)fluoranthene,
benzo(a)pyrene, benzo(g,h,i)perylene and indeno(1,2,3-cd)pyrene (Prahl and
Carpenter, 1983). Applied PAH molecular markers and ratios as well as their
ranges are given in Table S2 in the Supplement.</p>
      <p id="d1e666">Since BaP is the most studied PAH, the carcinogenic
potential of other PAHs is generally assessed referring it to that of BaP
(toxicity equivalence factors, TEFs; in a similar way to the toxic
equivalents (TEQs) used in the evaluation of the toxicity of dioxins and
furans. The benzo[a]pyrene potency equivalence approach is a major approach used
by the US EPA (1993, 1999), California EPA
(OEHHA, 1992), Netherlands (Verbruggen et al., 2001), UK (Duggan and
Strehlow, 1995) or provinces of British Columbia and Ontario, for example, for assessing
the human health risks of PAH-containing mixtures.</p>
      <p id="d1e670">Site-specific incremental lifetime CR was calculated in derived
soil samples taken from areas with different land uses by application of the
risk exposure model for chemicals of the Risk Assessment Information System
(RAIS). This calculation estimates a theoretical excess CR
expressed as the proportion of a population that may be affected by a
carcinogen during a lifetime of exposure. The CRs via
ingestion, dermal contact and inhalation of soil particles as well total
CR were estimated using the following Eqs. (1), (2) and (3) (US EPA, 2004):</p>
      <p id="d1e673"><disp-formula id="Ch1.E1" content-type="numbered"><mml:math id="M28" display="block"><mml:mrow><mml:msub><mml:mi mathvariant="normal">CR</mml:mi><mml:mi mathvariant="normal">ing</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">soil</mml:mi></mml:msub><mml:mo>×</mml:mo><mml:msub><mml:mi mathvariant="normal">IR</mml:mi><mml:mi mathvariant="normal">soil</mml:mi></mml:msub><mml:mo>×</mml:mo><mml:mi mathvariant="normal">EF</mml:mi><mml:mo>×</mml:mo><mml:mi mathvariant="normal">ED</mml:mi><mml:mo>×</mml:mo><mml:mi mathvariant="normal">CF</mml:mi></mml:mrow><mml:mrow><mml:mi mathvariant="normal">BW</mml:mi><mml:mo>×</mml:mo><mml:mi mathvariant="normal">AT</mml:mi></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>×</mml:mo><mml:msub><mml:mi mathvariant="normal">CSF</mml:mi><mml:mi mathvariant="normal">o</mml:mi></mml:msub><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
          where CR<inline-formula><mml:math id="M29" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">ing</mml:mi></mml:msub></mml:math></inline-formula> is the cancer risk (unitless) through ingestion of soil
particles. <inline-formula><mml:math id="M30" display="inline"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">soil</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> is the total BaP<inline-formula><mml:math id="M31" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:math></inline-formula> concentrations of soil PAHs;
IR<inline-formula><mml:math id="M32" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">soil</mml:mi></mml:msub></mml:math></inline-formula> is the soil ingestion rate (mg d<inline-formula><mml:math id="M33" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>; EF is the
exposure frequency (d yr<inline-formula><mml:math id="M34" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>); ED is the exposure duration
(years); CF is the conversion factor of 10<inline-formula><mml:math id="M35" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">6</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> mg kg<inline-formula><mml:math id="M36" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>; BW is
body weight (kg); AT is the average life span (d); CSF<inline-formula><mml:math id="M37" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">o</mml:mi></mml:msub></mml:math></inline-formula> is oral (ingestion)
cancer slope factor ((mg kg<inline-formula><mml:math id="M38" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M39" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:msup><mml:mo>)</mml:mo><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>;
CSF<inline-formula><mml:math id="M40" display="inline"><mml:mrow><mml:msub><mml:mi/><mml:mi mathvariant="normal">o</mml:mi></mml:msub><mml:mo>=</mml:mo></mml:mrow></mml:math></inline-formula> 7.3 (mg kg<inline-formula><mml:math id="M41" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M42" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:msup><mml:mo>)</mml:mo><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>, for BaP
(US EPA, 2004).</p>
      <p id="d1e911"><disp-formula specific-use="align" content-type="numbered"><mml:math id="M43" display="block"><mml:mtable displaystyle="true"><mml:mtr><mml:mtd><mml:mrow><mml:mstyle class="stylechange" displaystyle="true"/><mml:msub><mml:mi mathvariant="normal">CR</mml:mi><mml:mi mathvariant="normal">derm</mml:mi></mml:msub></mml:mrow></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">soil</mml:mi></mml:msub><mml:mo>×</mml:mo><mml:mi mathvariant="normal">SA</mml:mi><mml:mo>×</mml:mo><mml:msub><mml:mi mathvariant="normal">AF</mml:mi><mml:mi mathvariant="normal">soil</mml:mi></mml:msub><mml:mo>×</mml:mo><mml:mi mathvariant="normal">ABS</mml:mi><mml:mo>×</mml:mo><mml:mi mathvariant="normal">EF</mml:mi><mml:mo>×</mml:mo><mml:mi mathvariant="normal">ED</mml:mi><mml:mo>×</mml:mo><mml:mi mathvariant="normal">CF</mml:mi></mml:mrow><mml:mrow><mml:mi mathvariant="normal">BW</mml:mi><mml:mo>×</mml:mo><mml:mi mathvariant="normal">AT</mml:mi></mml:mrow></mml:mfrac></mml:mstyle></mml:mrow></mml:mtd></mml:mtr><mml:mlabeledtr id="Ch1.E2"><mml:mtd/><mml:mtd><mml:mstyle displaystyle="true" class="stylechange"/></mml:mtd><mml:mtd><mml:mrow><mml:mstyle displaystyle="true" class="stylechange"/><mml:mo>×</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi mathvariant="normal">CSF</mml:mi><mml:mi mathvariant="normal">o</mml:mi></mml:msub></mml:mrow><mml:mi mathvariant="normal">GIABS</mml:mi></mml:mfrac></mml:mstyle><mml:mo>,</mml:mo></mml:mrow></mml:mtd></mml:mlabeledtr></mml:mtable></mml:math></disp-formula>

            where CR<inline-formula><mml:math id="M44" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">derm</mml:mi></mml:msub></mml:math></inline-formula> is the cancer risk (unitless) for the dermal contact
pathway,
SA is the exposed surface area of the skin (cm<inline-formula><mml:math id="M45" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">2</mml:mn></mml:msup></mml:math></inline-formula>), AF<inline-formula><mml:math id="M46" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">soil</mml:mi></mml:msub></mml:math></inline-formula> is the dermal
adherence factor (mg cm<inline-formula><mml:math id="M47" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>), ABS is the absorption factor
(unitless) and GIABS is the fraction of contaminant absorbed in the gastrointestinal
tract (unitless).</p>
      <p id="d1e1036"><disp-formula id="Ch1.E3" content-type="numbered"><mml:math id="M48" display="block"><mml:mrow><mml:msub><mml:mi mathvariant="normal">CR</mml:mi><mml:mi mathvariant="normal">inh</mml:mi></mml:msub><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mrow><mml:msub><mml:mi>C</mml:mi><mml:mi mathvariant="normal">soil</mml:mi></mml:msub><mml:mo>×</mml:mo><mml:msub><mml:mi mathvariant="normal">IR</mml:mi><mml:mi mathvariant="normal">air</mml:mi></mml:msub><mml:mo>×</mml:mo><mml:mi mathvariant="normal">EF</mml:mi><mml:mo>×</mml:mo><mml:mi mathvariant="normal">ED</mml:mi></mml:mrow><mml:mrow><mml:mi mathvariant="normal">PEF</mml:mi><mml:mo>×</mml:mo><mml:mi mathvariant="normal">BW</mml:mi><mml:mo>×</mml:mo><mml:mi mathvariant="normal">AT</mml:mi></mml:mrow></mml:mfrac></mml:mstyle><mml:mo>×</mml:mo><mml:msub><mml:mi mathvariant="normal">CSF</mml:mi><mml:mi mathvariant="normal">i</mml:mi></mml:msub><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
          where CR<inline-formula><mml:math id="M49" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">inh</mml:mi></mml:msub></mml:math></inline-formula> is the cancer risk (unitless) for the inhalation
pathway. IR<inline-formula><mml:math id="M50" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">air</mml:mi></mml:msub></mml:math></inline-formula> is the inhalation rate (m<inline-formula><mml:math id="M51" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M52" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>,
CSF<inline-formula><mml:math id="M53" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">i</mml:mi></mml:msub></mml:math></inline-formula> is the inhalation cancer slope factor
((mg kg<inline-formula><mml:math id="M54" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> d<inline-formula><mml:math id="M55" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:msup><mml:mo>)</mml:mo><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula> and CSF<inline-formula><mml:math id="M56" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">i</mml:mi></mml:msub></mml:math></inline-formula> is obtained from the
inhalation unit risk (IUR, (<inline-formula><mml:math id="M57" display="inline"><mml:mi mathvariant="normal">µ</mml:mi></mml:math></inline-formula>g m<inline-formula><mml:math id="M58" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup><mml:msup><mml:mo>)</mml:mo><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) of BaP according to
the recommended method by the US EPA (2013). PEF is the soil particle
emission factor (m<inline-formula><mml:math id="M59" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">3</mml:mn></mml:msup></mml:math></inline-formula> kg<inline-formula><mml:math id="M60" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>. The total incremental lifetime
carcinogenic risk (TILCR) was calculated by summing the CRs for children and
adults. Evaluation of CRs in industrial areas was provided only for adults
(composite workers) as the dominating group of population. Due to differences
in activities, physiology (body weight, skin surface, lung volume) and
habits, adults and children are exposed to PAHs through different routes and
on different scales. For example, children are less vulnerable to dermal
contact with dust and ash particles containing PAHs due to the smaller skin
surface, which leads to smaller CRs (Wang et al., 2015). This paper provides
results of CR evaluation only for the sum of adults and children without
separation for individual groups.</p>
</sec>
<sec id="Ch1.S2.SS4">
  <title>Soil property analysis and statistical treatment</title>
      <p id="d1e1249">Total organic carbon (TOC) was determined using a Leco CHN628 elemental
analyser (USA, combustion temperature 1030 <inline-formula><mml:math id="M61" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula>C, oxygen boost time
28 s). Inorganic carbonates were removed before analysis by in
situ acidification of the ground samples with 1 M hydrochloric acid in order to avoid
uncertainty in TOC determination. Clay content was determined with a Shimadzu SALD-2201 laser
diffractometer (Japan). All measurements were carried out in
triplicate. All measurements were converted to an absolutely dry sample.</p>
      <p id="d1e1261">Statistical treatment of the data was carried out with STATISTICA 10.0
software. One-way ANOVA was applied in order to test statistical
significance of differences among obtained data. The essence of the method
is based on estimation of the significance of the average differences among
three or<?pagebreak page674?> more independent groups of data combined by one feature (factor).
The null hypothesis of the average equality is tested during the analysis,
suggesting the provisions on the equality or inequality of variances. In
case of rejection of the null hypothesis, basic analysis is not applicable. If
the variances are equal, the <inline-formula><mml:math id="M62" display="inline"><mml:mi>f</mml:mi></mml:math></inline-formula>-test Fisher criterion is used for evaluation of
intergroup and intergroup variability. If <inline-formula><mml:math id="M63" display="inline"><mml:mi>f</mml:mi></mml:math></inline-formula> statistics exceed the critical
value, the null hypothesis is rejected considering inequality of averages.
A post hoc test (Fisher's least significant difference) was used to provide detailed evaluation of
average differences among analysed groups of data. A feature of the
post hoc test is application of intra-group mean squares for the assessment
of any pair averages. Differences were considered to be significant at the
95 % confidence level. All calculations were carried out via STATISTICA
10.0 software. PAH concentrations were analysed at least in triplicate.
Calculated mean concentrations were provided with standard deviations (<inline-formula><mml:math id="M64" display="inline"><mml:mrow><mml:mi>a</mml:mi><mml:mo>±</mml:mo><mml:mi>b</mml:mi></mml:mrow></mml:math></inline-formula>).</p>
</sec>
</sec>
<sec id="Ch1.S3">
  <title>Results and discussion</title>
<sec id="Ch1.S3.SS1">
  <title>PAH concentrations in studied soils</title>
      <p id="d1e1302">Data on analysed properties of the studied soils are presented in Table 2.
Measured TOC concentrations in studied samples ranged between 3.82 and
6.41 % with a median value of 4.80 %. Numerous studies suggested that
soil organic matter (SOM) content plays an important role in retention of
PAH in soil (Chung and Alexander, 2002). In simple terms, the higher SOM
concentrations are, then the higher the amount of PAH that can be absorbed (Wilcke,
2000). Entering the soil from the atmosphere, PAHs are preferentially sorbed
to aggregate surfaces (Wilcke, 1996). The close association of PAHs with SOM
results in differentiation of organic contaminant pools among particle size
fractions (Guggenberger et al., 1996). A significant increase in PAH
concentrations in finer fractions is shown in a number of studies (Wilcke,
1996). Clay content in studied soils ranges between 1.87 and 8.50 %.
Correlation coefficients were calculated in the present study in order to
reveal the
relationship between levels of PAH in soil and analysed soil parameters. A
strong positive correlation was found between the sum of 15 PAH in soil and clay
content (<inline-formula><mml:math id="M65" display="inline"><mml:mrow><mml:mi>r</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.91</mml:mn></mml:mrow></mml:math></inline-formula>; <inline-formula><mml:math id="M66" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">27</mml:mn></mml:mrow></mml:math></inline-formula>; <inline-formula><mml:math id="M67" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.95</mml:mn></mml:mrow></mml:math></inline-formula>); however, no correlation of total
PAH and TOC concentrations in soil was detected.</p>
      <p id="d1e1341">The levels of 15 individual PAH compounds analysed in soils are shown in
Table 3. The sum of 15 PAHs and the sum of seven compounds included in the group
of probable human carcinogens (<inline-formula><mml:math id="M68" display="inline"><mml:mi>B</mml:mi></mml:math></inline-formula>2) by the US EPA (1993) are additionally given. Total PAH concentrations in studied soils were found to range
from traces to 8.06 mg kg<inline-formula><mml:math id="M69" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> (sum of 15 priority PAHs, hereafter
referred to as 15 PAH). The vast majority of samples were characterized by
concentrations of more than 1 mg kg<inline-formula><mml:math id="M70" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>, which is set as a guide level
for total PAH content in soil by a number of countries. The highest 15 PAH
levels were observed in soil samples collected from residential and
industrial sites, reaching an average of 4.19 and 4.01 mg kg<inline-formula><mml:math id="M71" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>,
respectively, with a maximal value of 8.06 mg kg<inline-formula><mml:math id="M72" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> for an industrial site
in Kirovsky district (hereafter – K.D.) Concentrations found in parkland
areas were substantially lower than those of residential and industrial areas, with
an average value of 1.08 mg kg<inline-formula><mml:math id="M73" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>.</p>
      <p id="d1e1412">Distribution of the sum of the seven carcinogenic PAHs (7 PAH) in soils of
the studied urban sites is generally characterized by the same pattern as the
total PAH content in soils. The highest 7 PAH levels were measured in soil
samples taken from residential sites (1.94 mg kg<inline-formula><mml:math id="M74" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>, with an absolute
value of 3.47 mg kg<inline-formula><mml:math id="M75" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> in Technosol of a K.D. residential area. The
7 PAH levels in parkland areas corresponds to the distribution of
15 PAH. All sampling sites were located in a proximity of less than 250 m
to the highways (Korablestroiteley street, Stachek prospect, Optikov
prospect, university embankment, Bolshoi prospect in Vasilievsky Ostrov and
others) showing heavy traffic. The portion of 7 PAH to the 15 PAH in all
tested samples ranged between 41 and 46 %, which evidently shows that the
soils may represent a considerable health risk for humans.</p>
      <p id="d1e1442">The sum of PAHs is mostly dominated by heavy-molecular-weight PAHs with four
to five rings. The portion of four-ringed PAH compounds in the soils of residential and
industrial sites accounts for 50 % of the sum, decreasing to 34 % in
parkland soils. Five-ringed PAHs including such compounds as BaP, BbF, BkF and
DBA contribute up to 31 % of the sum of PAH, insignificantly varying
among studied areas. The rest is accounted for by the six-ringed
(10–14 %) and low-molecular-weight PAHs with two or three rings in structure
(11–17 %).</p>
      <p id="d1e1446">The pie chart illustrating composition of PAH mixtures in soils is depicted
in Fig. 2. The obvious equality in PAH distribution patterns in all studied
sites clearly indicates the common source of PAHs. Pyrene and fluoranthene
(four-ring PAHs) are the most abundant compounds in the examined samples, and
account for 16–18 % of 15 PAH. The following predominant compounds are
five-ring PAHs benzo(b)fluoranthene (10–11 %) and benzo(a)pyrene
(8–11 %). The rest is represented by lighter-weight PAHs (two- to
three-ring PAHs) and is generally dominated by phenanthrene (6–9 %).
Domination of four- and five-ring PAHs, mainly PYR, FLT, BbF and BaP, in
studied soils is indicative of elevated diesel fuel consumption activity in
the area. Estimated diesel consumption in St. Petersburg reaches 38 % of
the total fuel use for transportation (Belousova et al., 2015). As is known,
the emission rate of heavyweight PAH fraction during diesel combustion is several
times higher than that during gasoline combustion (Marr et al., 1999).</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T2" specific-use="star"><caption><p id="d1e1452">Physicochemical properties of the studied soils.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="8">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="left"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:colspec colnum="7" colname="col7" align="right"/>
     <oasis:colspec colnum="8" colname="col8" align="right"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1">District</oasis:entry>  
         <oasis:entry colname="col2">Land use</oasis:entry>  
         <oasis:entry colname="col3">Soil name</oasis:entry>  
         <oasis:entry colname="col4">Munsell colour</oasis:entry>  
         <oasis:entry rowsep="1" colname="col5">TOC</oasis:entry>  
         <oasis:entry rowsep="1" colname="col6"><inline-formula><mml:math id="M76" display="inline"><mml:mrow><mml:msub><mml:mi>N</mml:mi><mml:mi mathvariant="normal">tot</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>  
         <oasis:entry rowsep="1" colname="col7">Clay</oasis:entry>  
         <oasis:entry colname="col8">pH</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3">(WRB)</oasis:entry>  
         <oasis:entry colname="col4">chart index</oasis:entry>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6">%</oasis:entry>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">Parkland</oasis:entry>  
         <oasis:entry colname="col3">Mollic <?xmltex \hack{\hfill\break}?>Technosol</oasis:entry>  
         <oasis:entry colname="col4">2.5 YR <?xmltex \hack{\hfill\break}?>4/1</oasis:entry>  
         <oasis:entry colname="col5">4.10 <inline-formula><mml:math id="M77" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.01</oasis:entry>  
         <oasis:entry colname="col6">0.35 <inline-formula><mml:math id="M78" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.06</oasis:entry>  
         <oasis:entry colname="col7">5.83 <inline-formula><mml:math id="M79" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.21</oasis:entry>  
         <oasis:entry colname="col8">6.52</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Primorsky</oasis:entry>  
         <oasis:entry colname="col2">Residential</oasis:entry>  
         <oasis:entry colname="col3">Urbic <?xmltex \hack{\hfill\break}?>Technosol</oasis:entry>  
         <oasis:entry colname="col4">2.5 YR <?xmltex \hack{\hfill\break}?>4/1</oasis:entry>  
         <oasis:entry colname="col5">3.82 <inline-formula><mml:math id="M80" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.03</oasis:entry>  
         <oasis:entry colname="col6">0.41 <inline-formula><mml:math id="M81" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.08</oasis:entry>  
         <oasis:entry colname="col7">7.43 <inline-formula><mml:math id="M82" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.06</oasis:entry>  
         <oasis:entry colname="col8">7.34</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">Industrial</oasis:entry>  
         <oasis:entry colname="col3">Urbic <?xmltex \hack{\hfill\break}?>Technosol</oasis:entry>  
         <oasis:entry colname="col4">10 YR <?xmltex \hack{\hfill\break}?>4/1</oasis:entry>  
         <oasis:entry colname="col5">5.49 <inline-formula><mml:math id="M83" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.02</oasis:entry>  
         <oasis:entry colname="col6">0.23 <inline-formula><mml:math id="M84" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.04</oasis:entry>  
         <oasis:entry colname="col7">8.50 <inline-formula><mml:math id="M85" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.10</oasis:entry>  
         <oasis:entry colname="col8">7.15</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">Parkland</oasis:entry>  
         <oasis:entry colname="col3">Mollic <?xmltex \hack{\hfill\break}?>Technosol</oasis:entry>  
         <oasis:entry colname="col4">2.5 YR <?xmltex \hack{\hfill\break}?>4/1</oasis:entry>  
         <oasis:entry colname="col5">5.39 <inline-formula><mml:math id="M86" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.01</oasis:entry>  
         <oasis:entry colname="col6">0.28 <inline-formula><mml:math id="M87" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.07</oasis:entry>  
         <oasis:entry colname="col7">7.3 <inline-formula><mml:math id="M88" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.20</oasis:entry>  
         <oasis:entry colname="col8">7.04</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Vasileostrovsky</oasis:entry>  
         <oasis:entry colname="col2">Residential</oasis:entry>  
         <oasis:entry colname="col3">Urbic <?xmltex \hack{\hfill\break}?>Technosol</oasis:entry>  
         <oasis:entry colname="col4">2.5 YR <?xmltex \hack{\hfill\break}?>4/1</oasis:entry>  
         <oasis:entry colname="col5">6.41 <inline-formula><mml:math id="M89" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.02</oasis:entry>  
         <oasis:entry colname="col6">0.33 <inline-formula><mml:math id="M90" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.05</oasis:entry>  
         <oasis:entry colname="col7">1.87 <inline-formula><mml:math id="M91" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.12</oasis:entry>  
         <oasis:entry colname="col8">7.45</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">Industrial</oasis:entry>  
         <oasis:entry colname="col3">Urbic <?xmltex \hack{\hfill\break}?>Technosol</oasis:entry>  
         <oasis:entry colname="col4">5 YR <?xmltex \hack{\hfill\break}?>7/1</oasis:entry>  
         <oasis:entry colname="col5">5.28 <inline-formula><mml:math id="M92" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.02</oasis:entry>  
         <oasis:entry colname="col6">0.29 <inline-formula><mml:math id="M93" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.06</oasis:entry>  
         <oasis:entry colname="col7">3.27 <inline-formula><mml:math id="M94" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.15</oasis:entry>  
         <oasis:entry colname="col8">7.76</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">Parkland</oasis:entry>  
         <oasis:entry colname="col3">Mollic <?xmltex \hack{\hfill\break}?>Technosol</oasis:entry>  
         <oasis:entry colname="col4">2.5 YR <?xmltex \hack{\hfill\break}?>4/1</oasis:entry>  
         <oasis:entry colname="col5">4.19 <inline-formula><mml:math id="M95" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.03</oasis:entry>  
         <oasis:entry colname="col6">0.32 <inline-formula><mml:math id="M96" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.09</oasis:entry>  
         <oasis:entry colname="col7">7.5 <inline-formula><mml:math id="M97" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.10</oasis:entry>  
         <oasis:entry colname="col8">6.84</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Kirovsky</oasis:entry>  
         <oasis:entry colname="col2">Residential</oasis:entry>  
         <oasis:entry colname="col3">Urbic <?xmltex \hack{\hfill\break}?>Technosol</oasis:entry>  
         <oasis:entry colname="col4">5 YR <?xmltex \hack{\hfill\break}?>7/1</oasis:entry>  
         <oasis:entry colname="col5">4.80 <inline-formula><mml:math id="M98" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.03</oasis:entry>  
         <oasis:entry colname="col6">0.30 <inline-formula><mml:math id="M99" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.05</oasis:entry>  
         <oasis:entry colname="col7">3.27 <inline-formula><mml:math id="M100" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.15</oasis:entry>  
         <oasis:entry colname="col8">7.12</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">Industrial</oasis:entry>  
         <oasis:entry colname="col3">Urbic <?xmltex \hack{\hfill\break}?>Technosol</oasis:entry>  
         <oasis:entry colname="col4">5 YR <?xmltex \hack{\hfill\break}?>7/1</oasis:entry>  
         <oasis:entry colname="col5">3.09 <inline-formula><mml:math id="M101" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.02</oasis:entry>  
         <oasis:entry colname="col6">0.27 <inline-formula><mml:math id="M102" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.04</oasis:entry>  
         <oasis:entry colname="col7">7.67 <inline-formula><mml:math id="M103" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.06</oasis:entry>  
         <oasis:entry colname="col8">7.05</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T3" specific-use="star"><caption><p id="d1e2018">Mean PAH concentrations in soils of St. Petersburg (mg kg<inline-formula><mml:math id="M104" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="11">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="right"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right" colsep="1"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:colspec colnum="7" colname="col7" align="right" colsep="1"/>
     <oasis:colspec colnum="8" colname="col8" align="right"/>
     <oasis:colspec colnum="9" colname="col9" align="right"/>
     <oasis:colspec colnum="10" colname="col10" align="right"/>
     <oasis:colspec colnum="11" colname="col11" align="right"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1">Compound</oasis:entry>  
         <oasis:entry rowsep="1" namest="col2" nameend="col4" align="center">Parkland (<inline-formula><mml:math id="M106" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">9</mml:mn></mml:mrow></mml:math></inline-formula>) </oasis:entry>  
         <oasis:entry rowsep="1" namest="col5" nameend="col7" align="center">Residential (<inline-formula><mml:math id="M107" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">9</mml:mn></mml:mrow></mml:math></inline-formula>) </oasis:entry>  
         <oasis:entry rowsep="1" namest="col8" nameend="col10" align="center">Industrial (<inline-formula><mml:math id="M108" display="inline"><mml:mrow><mml:mi>n</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">9</mml:mn></mml:mrow></mml:math></inline-formula>) </oasis:entry>  
         <oasis:entry colname="col11"><inline-formula><mml:math id="M109" display="inline"><mml:mi>P</mml:mi></mml:math></inline-formula> One-way</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">Mean <inline-formula><mml:math id="M110" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> SD</oasis:entry>  
         <oasis:entry colname="col3">Max</oasis:entry>  
         <oasis:entry colname="col4">Min</oasis:entry>  
         <oasis:entry colname="col5">Mean <inline-formula><mml:math id="M111" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> SD</oasis:entry>  
         <oasis:entry colname="col6">Max</oasis:entry>  
         <oasis:entry colname="col7">Min</oasis:entry>  
         <oasis:entry colname="col8">Mean <inline-formula><mml:math id="M112" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> SD</oasis:entry>  
         <oasis:entry colname="col9">Max</oasis:entry>  
         <oasis:entry colname="col10">Min</oasis:entry>  
         <oasis:entry colname="col11">ANOVA</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7"/>  
         <oasis:entry colname="col8"/>  
         <oasis:entry colname="col9"/>  
         <oasis:entry colname="col10"/>  
         <oasis:entry colname="col11">(<inline-formula><mml:math id="M113" display="inline"><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mo>=</mml:mo><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula>)</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">NAP</oasis:entry>  
         <oasis:entry colname="col2">0.06 <inline-formula><mml:math id="M114" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.08</oasis:entry>  
         <oasis:entry colname="col3">0.28</oasis:entry>  
         <oasis:entry colname="col4">0.03</oasis:entry>  
         <oasis:entry colname="col5">0.05 <inline-formula><mml:math id="M115" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.02</oasis:entry>  
         <oasis:entry colname="col6">0.07</oasis:entry>  
         <oasis:entry colname="col7">0.00</oasis:entry>  
         <oasis:entry colname="col8">0.09 <inline-formula><mml:math id="M116" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.07</oasis:entry>  
         <oasis:entry colname="col9">0.21</oasis:entry>  
         <oasis:entry colname="col10">0.00</oasis:entry>  
         <oasis:entry colname="col11">0.42</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">ANA</oasis:entry>  
         <oasis:entry colname="col2">0.02 <inline-formula><mml:math id="M117" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.06</oasis:entry>  
         <oasis:entry colname="col3">0.18</oasis:entry>  
         <oasis:entry colname="col4">0.00</oasis:entry>  
         <oasis:entry colname="col5">0.00</oasis:entry>  
         <oasis:entry colname="col6">0.01</oasis:entry>  
         <oasis:entry colname="col7">0.00</oasis:entry>  
         <oasis:entry colname="col8">0.01</oasis:entry>  
         <oasis:entry colname="col9">0.03</oasis:entry>  
         <oasis:entry colname="col10">0.00</oasis:entry>  
         <oasis:entry colname="col11">–</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">FLU</oasis:entry>  
         <oasis:entry colname="col2">0.10 <inline-formula><mml:math id="M118" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.06</oasis:entry>  
         <oasis:entry colname="col3">0.23</oasis:entry>  
         <oasis:entry colname="col4">0.05</oasis:entry>  
         <oasis:entry colname="col5">0.17 <inline-formula><mml:math id="M119" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.11</oasis:entry>  
         <oasis:entry colname="col6">0.40</oasis:entry>  
         <oasis:entry colname="col7">0.03</oasis:entry>  
         <oasis:entry colname="col8">0.17 <inline-formula><mml:math id="M120" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.11</oasis:entry>  
         <oasis:entry colname="col9">0.31</oasis:entry>  
         <oasis:entry colname="col10">0.06</oasis:entry>  
         <oasis:entry colname="col11">0.04</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">PHE</oasis:entry>  
         <oasis:entry colname="col2">0.16 <inline-formula><mml:math id="M121" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.13</oasis:entry>  
         <oasis:entry colname="col3">0.45</oasis:entry>  
         <oasis:entry colname="col4">0.05</oasis:entry>  
         <oasis:entry colname="col5">0.26 <inline-formula><mml:math id="M122" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.17</oasis:entry>  
         <oasis:entry colname="col6">0.47</oasis:entry>  
         <oasis:entry colname="col7">0.03</oasis:entry>  
         <oasis:entry colname="col8">0.36 <inline-formula><mml:math id="M123" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.22</oasis:entry>  
         <oasis:entry colname="col9">0.65</oasis:entry>  
         <oasis:entry colname="col10">0.07</oasis:entry>  
         <oasis:entry colname="col11">0.04</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">ANT</oasis:entry>  
         <oasis:entry colname="col2">0.06 <inline-formula><mml:math id="M124" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.11</oasis:entry>  
         <oasis:entry colname="col3">0.37</oasis:entry>  
         <oasis:entry colname="col4">0.01</oasis:entry>  
         <oasis:entry colname="col5">0.04 <inline-formula><mml:math id="M125" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.04</oasis:entry>  
         <oasis:entry colname="col6">0.11</oasis:entry>  
         <oasis:entry colname="col7">0.00</oasis:entry>  
         <oasis:entry colname="col8">0.05 <inline-formula><mml:math id="M126" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.03</oasis:entry>  
         <oasis:entry colname="col9">0.09</oasis:entry>  
         <oasis:entry colname="col10">0.01</oasis:entry>  
         <oasis:entry colname="col11">0.87</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">FLT</oasis:entry>  
         <oasis:entry colname="col2">0.18 <inline-formula><mml:math id="M127" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.07</oasis:entry>  
         <oasis:entry colname="col3">0.35</oasis:entry>  
         <oasis:entry colname="col4">0.09</oasis:entry>  
         <oasis:entry colname="col5">0.69 <inline-formula><mml:math id="M128" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.52</oasis:entry>  
         <oasis:entry colname="col6">1.49</oasis:entry>  
         <oasis:entry colname="col7">0.04</oasis:entry>  
         <oasis:entry colname="col8">0.72 <inline-formula><mml:math id="M129" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.48</oasis:entry>  
         <oasis:entry colname="col9">1.50</oasis:entry>  
         <oasis:entry colname="col10">0.11</oasis:entry>  
         <oasis:entry colname="col11">0.02</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">PYR</oasis:entry>  
         <oasis:entry colname="col2">0.18 <inline-formula><mml:math id="M130" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.08</oasis:entry>  
         <oasis:entry colname="col3">0.35</oasis:entry>  
         <oasis:entry colname="col4">0.09</oasis:entry>  
         <oasis:entry colname="col5">0.74 <inline-formula><mml:math id="M131" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.55</oasis:entry>  
         <oasis:entry colname="col6">1.67</oasis:entry>  
         <oasis:entry colname="col7">0.04</oasis:entry>  
         <oasis:entry colname="col8">0.70 <inline-formula><mml:math id="M132" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.46</oasis:entry>  
         <oasis:entry colname="col9">1.50</oasis:entry>  
         <oasis:entry colname="col10">0.16</oasis:entry>  
         <oasis:entry colname="col11">0.02</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">BaA</oasis:entry>  
         <oasis:entry colname="col2">0.19 <inline-formula><mml:math id="M133" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.17</oasis:entry>  
         <oasis:entry colname="col3">0.53</oasis:entry>  
         <oasis:entry colname="col4">0.04</oasis:entry>  
         <oasis:entry colname="col5">0.35 <inline-formula><mml:math id="M134" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.26</oasis:entry>  
         <oasis:entry colname="col6">0.64</oasis:entry>  
         <oasis:entry colname="col7">0.02</oasis:entry>  
         <oasis:entry colname="col8">0.30 <inline-formula><mml:math id="M135" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.20</oasis:entry>  
         <oasis:entry colname="col9">0.67</oasis:entry>  
         <oasis:entry colname="col10">0.07</oasis:entry>  
         <oasis:entry colname="col11">0.05</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">CHR</oasis:entry>  
         <oasis:entry colname="col2">0.15 <inline-formula><mml:math id="M136" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.14</oasis:entry>  
         <oasis:entry colname="col3">0.44</oasis:entry>  
         <oasis:entry colname="col4">0.01</oasis:entry>  
         <oasis:entry colname="col5">0.31 <inline-formula><mml:math id="M137" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.24</oasis:entry>  
         <oasis:entry colname="col6">0.69</oasis:entry>  
         <oasis:entry colname="col7">0.02</oasis:entry>  
         <oasis:entry colname="col8">0.28 <inline-formula><mml:math id="M138" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.18</oasis:entry>  
         <oasis:entry colname="col9">0.54</oasis:entry>  
         <oasis:entry colname="col10">0.07</oasis:entry>  
         <oasis:entry colname="col11">0.05</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">BbF</oasis:entry>  
         <oasis:entry colname="col2">0.23 <inline-formula><mml:math id="M139" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.21</oasis:entry>  
         <oasis:entry colname="col3">0.69</oasis:entry>  
         <oasis:entry colname="col4">0.05</oasis:entry>  
         <oasis:entry colname="col5">0.46 <inline-formula><mml:math id="M140" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.30</oasis:entry>  
         <oasis:entry colname="col6">0.84</oasis:entry>  
         <oasis:entry colname="col7">0.02</oasis:entry>  
         <oasis:entry colname="col8">0.41 <inline-formula><mml:math id="M141" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.30</oasis:entry>  
         <oasis:entry colname="col9">1.00</oasis:entry>  
         <oasis:entry colname="col10">0.10</oasis:entry>  
         <oasis:entry colname="col11">0.04</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">BkF</oasis:entry>  
         <oasis:entry colname="col2">0.15 <inline-formula><mml:math id="M142" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.17</oasis:entry>  
         <oasis:entry colname="col3">0.56</oasis:entry>  
         <oasis:entry colname="col4">0.02</oasis:entry>  
         <oasis:entry colname="col5">0.19 <inline-formula><mml:math id="M143" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.14</oasis:entry>  
         <oasis:entry colname="col6">0.36</oasis:entry>  
         <oasis:entry colname="col7">0.01</oasis:entry>  
         <oasis:entry colname="col8">0.16 <inline-formula><mml:math id="M144" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.11</oasis:entry>  
         <oasis:entry colname="col9">0.33</oasis:entry>  
         <oasis:entry colname="col10">0.04</oasis:entry>  
         <oasis:entry colname="col11">0.82</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">BaP</oasis:entry>  
         <oasis:entry colname="col2">0.22 <inline-formula><mml:math id="M145" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.22</oasis:entry>  
         <oasis:entry colname="col3">0.70</oasis:entry>  
         <oasis:entry colname="col4">0.04</oasis:entry>  
         <oasis:entry colname="col5">0.43 <inline-formula><mml:math id="M146" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.32</oasis:entry>  
         <oasis:entry colname="col6">0.87</oasis:entry>  
         <oasis:entry colname="col7">0.02</oasis:entry>  
         <oasis:entry colname="col8">0.34 <inline-formula><mml:math id="M147" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.23</oasis:entry>  
         <oasis:entry colname="col9">0.73</oasis:entry>  
         <oasis:entry colname="col10">0.07</oasis:entry>  
         <oasis:entry colname="col11">0.04</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">DBA</oasis:entry>  
         <oasis:entry colname="col2">0.03 <inline-formula><mml:math id="M148" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.06</oasis:entry>  
         <oasis:entry colname="col3">0.18</oasis:entry>  
         <oasis:entry colname="col4">0.00</oasis:entry>  
         <oasis:entry colname="col5">0.02 <inline-formula><mml:math id="M149" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.01</oasis:entry>  
         <oasis:entry colname="col6">0.04</oasis:entry>  
         <oasis:entry colname="col7">0.00</oasis:entry>  
         <oasis:entry colname="col8">0.02 <inline-formula><mml:math id="M150" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.03</oasis:entry>  
         <oasis:entry colname="col9">0.08</oasis:entry>  
         <oasis:entry colname="col10">0.00</oasis:entry>  
         <oasis:entry colname="col11">0.93</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">BPE</oasis:entry>  
         <oasis:entry colname="col2">0.17 <inline-formula><mml:math id="M151" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.14</oasis:entry>  
         <oasis:entry colname="col3">0.46</oasis:entry>  
         <oasis:entry colname="col4">0.04</oasis:entry>  
         <oasis:entry colname="col5">0.29 <inline-formula><mml:math id="M152" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.21</oasis:entry>  
         <oasis:entry colname="col6">0.52</oasis:entry>  
         <oasis:entry colname="col7">0.01</oasis:entry>  
         <oasis:entry colname="col8">0.27 <inline-formula><mml:math id="M153" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.20</oasis:entry>  
         <oasis:entry colname="col9">0.69</oasis:entry>  
         <oasis:entry colname="col10">0.06</oasis:entry>  
         <oasis:entry colname="col11">0.05</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">IPY</oasis:entry>  
         <oasis:entry colname="col2">0.12 <inline-formula><mml:math id="M154" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.15</oasis:entry>  
         <oasis:entry colname="col3">0.49</oasis:entry>  
         <oasis:entry colname="col4">0.00</oasis:entry>  
         <oasis:entry colname="col5">0.17 <inline-formula><mml:math id="M155" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.17</oasis:entry>  
         <oasis:entry colname="col6">0.45</oasis:entry>  
         <oasis:entry colname="col7">0.01</oasis:entry>  
         <oasis:entry colname="col8">0.15 <inline-formula><mml:math id="M156" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 0.13</oasis:entry>  
         <oasis:entry colname="col9">0.38</oasis:entry>  
         <oasis:entry colname="col10">0.00</oasis:entry>  
         <oasis:entry colname="col11">0.76</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M157" display="inline"><mml:mo>∑</mml:mo></mml:math></inline-formula>15 PAH</oasis:entry>  
         <oasis:entry colname="col2">2.02 <inline-formula><mml:math id="M158" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.50</oasis:entry>  
         <oasis:entry colname="col3">4.78</oasis:entry>  
         <oasis:entry colname="col4">0.58</oasis:entry>  
         <oasis:entry colname="col5">4.17 <inline-formula><mml:math id="M159" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2.91</oasis:entry>  
         <oasis:entry colname="col6">8.10</oasis:entry>  
         <oasis:entry colname="col7">0.33</oasis:entry>  
         <oasis:entry colname="col8">4.02 <inline-formula><mml:math id="M160" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 2.61</oasis:entry>  
         <oasis:entry colname="col9">8.06</oasis:entry>  
         <oasis:entry colname="col10">0.86</oasis:entry>  
         <oasis:entry colname="col11">0.04</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M161" display="inline"><mml:mo>∑</mml:mo></mml:math></inline-formula>7 PAH<inline-formula><mml:math id="M162" display="inline"><mml:msup><mml:mi/><mml:mo>*</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2">1.08 <inline-formula><mml:math id="M163" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.04</oasis:entry>  
         <oasis:entry colname="col3">3.18</oasis:entry>  
         <oasis:entry colname="col4">0.21</oasis:entry>  
         <oasis:entry colname="col5">1.94 <inline-formula><mml:math id="M164" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.36</oasis:entry>  
         <oasis:entry colname="col6">3.47</oasis:entry>  
         <oasis:entry colname="col7">0.10</oasis:entry>  
         <oasis:entry colname="col8">1.66 <inline-formula><mml:math id="M165" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.13</oasis:entry>  
         <oasis:entry colname="col9">3.20</oasis:entry>  
         <oasis:entry colname="col10">0.36</oasis:entry>  
         <oasis:entry colname="col11">0.05</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table><table-wrap-foot><p id="d1e2036">
NAP – naphthalene; ANA – acenaphthene; FLU – fluorene; PHE –
phenanthrene; ANT – anthracene; FLT – fluoranthene; PYR – pyrene; BaA –
benzo(a)anthracene; CHR – chrysene; BbF – benzo(b)fluoranthene; BkF –
benzo(k)fluoranthene; BaP – benzo(a)pyrene; DBA – dibenz(ah)anthracene; BPE
– benzo(g,h,i)perylene; IPY – indeno(1,2,3-cd) pyrene.<?xmltex \hack{\newline}?>
<inline-formula><mml:math id="M105" display="inline"><mml:msup><mml:mi/><mml:mo>*</mml:mo></mml:msup></mml:math></inline-formula> Carcinogenic PAHs: chrysene, benzo(a)anthracene,
benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)
pyrene and dibenz(ah)anthracene.</p></table-wrap-foot></table-wrap>

      <p id="d1e3235">The data obtained are nearly consistent with data from Lodygin et al. (2008)
exploring PAH levels (sum of 11 PAHs) in soils of Vasil'yevskiy
Island in St. Petersburg). The main anthropogenic impact on soils of
residential areas of the<?pagebreak page675?> island was exerted by light polyarens, including
two- to four-ring substances (as stated by the author), the portion of which
in the total content of PAHs was more than 50 %. Maximum concentrations
of PAHs were detected in soils along highways with intense traffic and
considerable emissions of combustion gases. The reported total PAH content
ranged from 0.197 to 8.20 mg kg<inline-formula><mml:math id="M166" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> between different land utilization
types. The described distribution patterns of individual PAHs are similar to
those of this study: the most abundant are four- to five-ring PAHs,
particularly pyrene (17 %), fluoranthene (17 %), benzo(g,h,i)perylene
(13 %), benzo(b)fluoranthene (12 %) and benzo(a)pyrene (12 %).
Several samples were noticed to exhibit higher contents of heavy polyarens of
natural origin, as both of the samples were represented by fresh organic
material (peat), which is used as amendment in soils of residential areas and
roadsides. Thus the findings of the above-mentioned study suggest that
spatial distribution of PAHs is mainly dictated by the closeness to highways
and by the artificial input of peat material in the urban soils.</p>
      <p id="d1e3250">There is still a lack of information about PAH concentrations in the soils of
St. Petersburg; thus the data on the pollutant distribution in water
sediments obtained from<?pagebreak page676?> environmental monitoring systems may be applied in
discussion for evaluation of the PAH loads. Comparative PAH levels were
detected in bottom sediments in different parts of Neva Bay (Gulf of
Finland) and along the Niva River waterway. Reported total PAH
concentrations ranged between 0.01 and 14.5 mg kg<inline-formula><mml:math id="M167" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> (HELCOM,
2014). Benzo(a)pyrene was detected in 96 % of sediment samples taken, with
an average concentration of 0.09 mg kg<inline-formula><mml:math id="M168" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2"><caption><p id="d1e3280">Composition of PAH mixtures in studied soil.</p></caption>
          <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://se.copernicus.org/articles/9/669/2018/se-9-669-2018-f02.png"/>

        </fig>

      <p id="d1e3289">Total PAH concentrations in soils of urban and industrial sites from a
number of investigations set in other countries are summarized in Table 4.
In general terms, the predominance of three- to five-ring PAHs is noted, which is
mainly attributed to the influence of anthropogenic activities on the
studied territories.</p>
</sec>
<sec id="Ch1.S3.SS2">
  <title>Determination of the PAH sources and statistics</title>
      <p id="d1e3298">While a domination of high-molecular-weight PAH fraction indicates a
combustion origin (pyrogenic), enrichment of low-molecular-weight PAHs is
common in fresh fuels (petrogenic) (Budzinski et al., 1997). Special
molecular markers and ratios, proposed by Yunker et al. (2002), and a total
combustion PAH index, reported by Hwang et al. (2003), were applied for PAH
source apportionment. Obtained meanings of applied PAH molecular ratios are
listed in Table 5. Applied markers allow us to distinguish between pyrogenic
and petrogenic as well as traffic and non-traffic sources of PAHs, namely
ANT <inline-formula><mml:math id="M169" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> (ANT <inline-formula><mml:math id="M170" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> PHE), FLT <inline-formula><mml:math id="M171" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> (FLT <inline-formula><mml:math id="M172" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> PYR), BaA <inline-formula><mml:math id="M173" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> (BaA <inline-formula><mml:math id="M174" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> CHR), IPY <inline-formula><mml:math id="M175" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> (IPY <inline-formula><mml:math id="M176" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> BPE),
CombPAH <inline-formula><mml:math id="M177" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> 15PAH and BaP <inline-formula><mml:math id="M178" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> BPE. Calculated ratios for samples taken from
residential and industrial areas exhibited numbers that point to a domination of
pyrogenically formed PAHs. The cross plots of the PAH ratios are depicted in
Fig. 3</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T4" specific-use="star"><caption><p id="d1e3375">Reported total concentrations of PAHs in urban soils (mg kg<inline-formula><mml:math id="M179" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> dry weight) from a number of studies.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="5">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="left"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="left"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1">Location</oasis:entry>  
         <oasis:entry colname="col2">Study area</oasis:entry>  
         <oasis:entry colname="col3">Concentrations</oasis:entry>  
         <oasis:entry colname="col4"><inline-formula><mml:math id="M180" display="inline"><mml:mo>∑</mml:mo></mml:math></inline-formula>PAH</oasis:entry>  
         <oasis:entry colname="col5">Reference</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3"><?xmltex \hack{\hfill\break}?>(mg kg<inline-formula><mml:math id="M181" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> d.w.)</oasis:entry>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">Houston, TX, USA</oasis:entry>  
         <oasis:entry colname="col2">Urban/suburban</oasis:entry>  
         <oasis:entry colname="col3">0.2–2.2</oasis:entry>  
         <oasis:entry colname="col4">23</oasis:entry>  
         <oasis:entry colname="col5">Hwang et al. (2002)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Mexico City, Mexico</oasis:entry>  
         <oasis:entry colname="col2">Urban/industrial</oasis:entry>  
         <oasis:entry colname="col3">0.20–1.10</oasis:entry>  
         <oasis:entry colname="col4">17</oasis:entry>  
         <oasis:entry colname="col5">Hwang et al. (2003)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Beijing, China</oasis:entry>  
         <oasis:entry colname="col2">Urban</oasis:entry>  
         <oasis:entry colname="col3">0.22–27.82</oasis:entry>  
         <oasis:entry colname="col4">16</oasis:entry>  
         <oasis:entry colname="col5">Tang et al. (2005)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">New Orleans, USA</oasis:entry>  
         <oasis:entry colname="col2">Urban</oasis:entry>  
         <oasis:entry colname="col3">3.73 (median)</oasis:entry>  
         <oasis:entry colname="col4">16</oasis:entry>  
         <oasis:entry colname="col5">Mielke et al. (2001)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Tarragona County,</oasis:entry>  
         <oasis:entry colname="col2">Urban/residential/</oasis:entry>  
         <oasis:entry colname="col3">0.11–1.00</oasis:entry>  
         <oasis:entry colname="col4">16</oasis:entry>  
         <oasis:entry colname="col5">Nadal et al. (2004)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Catalonia, Spain</oasis:entry>  
         <oasis:entry colname="col2">industrial</oasis:entry>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Swiss soil monitoring</oasis:entry>  
         <oasis:entry colname="col2">Urban parkland/</oasis:entry>  
         <oasis:entry colname="col3">0.05–0.62</oasis:entry>  
         <oasis:entry colname="col4">16</oasis:entry>  
         <oasis:entry colname="col5">Bucheli et al. (2004)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">system (NABO), Switzerland</oasis:entry>  
         <oasis:entry colname="col2">semiurban</oasis:entry>  
         <oasis:entry colname="col3"/>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Tallinn, Estonia</oasis:entry>  
         <oasis:entry colname="col2">Urban</oasis:entry>  
         <oasis:entry colname="col3">2.20 <inline-formula><mml:math id="M182" display="inline"><mml:mo>±</mml:mo></mml:math></inline-formula> 1.40</oasis:entry>  
         <oasis:entry colname="col4">12</oasis:entry>  
         <oasis:entry colname="col5">Trapido (1999)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Linz, Austria</oasis:entry>  
         <oasis:entry colname="col2">Industrial</oasis:entry>  
         <oasis:entry colname="col3">1.45 (median)</oasis:entry>  
         <oasis:entry colname="col4">18</oasis:entry>  
         <oasis:entry colname="col5">Weiss et al. (1994)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Tokushima, Japan</oasis:entry>  
         <oasis:entry colname="col2">Urban</oasis:entry>  
         <oasis:entry colname="col3">0.61</oasis:entry>  
         <oasis:entry colname="col4">13</oasis:entry>  
         <oasis:entry colname="col5">Yang et al. (2002)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Shanghai, China</oasis:entry>  
         <oasis:entry colname="col2">Main urban</oasis:entry>  
         <oasis:entry colname="col3">0.13–8.65/0.08–7.22</oasis:entry>  
         <oasis:entry colname="col4">26 <inline-formula><mml:math id="M183" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> 16</oasis:entry>  
         <oasis:entry colname="col5">Wang et al. (2013)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">El-Tebbin, Egypt</oasis:entry>  
         <oasis:entry colname="col2">Urban/industrial</oasis:entry>  
         <oasis:entry colname="col3">0.05–5.56</oasis:entry>  
         <oasis:entry colname="col4">16</oasis:entry>  
         <oasis:entry colname="col5">Havelcová et al. (2014)</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Phoenix, Arizona, USA</oasis:entry>  
         <oasis:entry colname="col2">Urban (highways)</oasis:entry>  
         <oasis:entry colname="col3">0.06–10.12</oasis:entry>  
         <oasis:entry colname="col4">20</oasis:entry>  
         <oasis:entry colname="col5">Marusenko et al. (2011)</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T5" specific-use="star"><caption><p id="d1e3728">PAH ratios in studied soils.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="7">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="right"/>
     <oasis:colspec colnum="3" colname="col3" align="left"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="left"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:colspec colnum="7" colname="col7" align="left"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1">Ratio</oasis:entry>  
         <oasis:entry colname="col2">Parkland</oasis:entry>  
         <oasis:entry colname="col3">Indicated source</oasis:entry>  
         <oasis:entry colname="col4">Residential</oasis:entry>  
         <oasis:entry colname="col5">Indicated source</oasis:entry>  
         <oasis:entry colname="col6">Industrial</oasis:entry>  
         <oasis:entry colname="col7">Indicated source</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3">(origin)</oasis:entry>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5">(origin)</oasis:entry>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">(origin)</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">ANT <inline-formula><mml:math id="M184" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> (ANT <inline-formula><mml:math id="M185" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> PHE)</oasis:entry>  
         <oasis:entry colname="col2">0.19</oasis:entry>  
         <oasis:entry colname="col3">Pyrogenic</oasis:entry>  
         <oasis:entry colname="col4">0.09</oasis:entry>  
         <oasis:entry colname="col5">Petrogenic</oasis:entry>  
         <oasis:entry colname="col6">0.12</oasis:entry>  
         <oasis:entry colname="col7">Pyrogenic</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">FLT <inline-formula><mml:math id="M186" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> (FLT <inline-formula><mml:math id="M187" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> PYR)</oasis:entry>  
         <oasis:entry colname="col2">0.51</oasis:entry>  
         <oasis:entry colname="col3">Grass; coal and</oasis:entry>  
         <oasis:entry colname="col4">0.49</oasis:entry>  
         <oasis:entry colname="col5">Gasoline, diesel and</oasis:entry>  
         <oasis:entry colname="col6">0.50</oasis:entry>  
         <oasis:entry colname="col7">Gasoline, diesel and</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3">wood combustion</oasis:entry>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5">crude oil combustion</oasis:entry>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">crude oil combustion</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">BaA <inline-formula><mml:math id="M188" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> (BaA <inline-formula><mml:math id="M189" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> CHR)</oasis:entry>  
         <oasis:entry colname="col2">0.58</oasis:entry>  
         <oasis:entry colname="col3">Grass; coal and</oasis:entry>  
         <oasis:entry colname="col4">0.52</oasis:entry>  
         <oasis:entry colname="col5">Grass; coal and</oasis:entry>  
         <oasis:entry colname="col6">0.51</oasis:entry>  
         <oasis:entry colname="col7">Grass; coal and</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3">wood combustion</oasis:entry>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5">wood combustion</oasis:entry>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">wood combustion</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">IPY <inline-formula><mml:math id="M190" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> (IPY <inline-formula><mml:math id="M191" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> BPE)</oasis:entry>  
         <oasis:entry colname="col2">0.30</oasis:entry>  
         <oasis:entry colname="col3">Liquid fossil</oasis:entry>  
         <oasis:entry colname="col4">0.40</oasis:entry>  
         <oasis:entry colname="col5">Liquid fossil</oasis:entry>  
         <oasis:entry colname="col6">0.34</oasis:entry>  
         <oasis:entry colname="col7">Liquid fossil</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3">fuel combustion</oasis:entry>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5">fuel combustion</oasis:entry>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">fuel combustion</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">BaP <inline-formula><mml:math id="M192" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> BPE</oasis:entry>  
         <oasis:entry colname="col2">1.20</oasis:entry>  
         <oasis:entry colname="col3">Traffic sources</oasis:entry>  
         <oasis:entry colname="col4">1.64</oasis:entry>  
         <oasis:entry colname="col5">Traffic sources</oasis:entry>  
         <oasis:entry colname="col6">1.31</oasis:entry>  
         <oasis:entry colname="col7">Traffic sources</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">CombPAH <inline-formula><mml:math id="M193" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> <inline-formula><mml:math id="M194" display="inline"><mml:mo>∑</mml:mo></mml:math></inline-formula>PAH</oasis:entry>  
         <oasis:entry colname="col2">0.79</oasis:entry>  
         <oasis:entry colname="col3">Combustion-</oasis:entry>  
         <oasis:entry colname="col4">0.80</oasis:entry>  
         <oasis:entry colname="col5">Combustion-</oasis:entry>  
         <oasis:entry colname="col6">0.81</oasis:entry>  
         <oasis:entry colname="col7">Combustion-</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3">dominated source</oasis:entry>  
         <oasis:entry colname="col4"/>  
         <oasis:entry colname="col5">dominated source</oasis:entry>  
         <oasis:entry colname="col6"/>  
         <oasis:entry colname="col7">dominated source</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <?xmltex \floatpos{t}?><fig id="Ch1.F3"><caption><p id="d1e4118">PAH source apportionment.</p></caption>
          <?xmltex \igopts{width=241.848425pt}?><graphic xlink:href="https://se.copernicus.org/articles/9/669/2018/se-9-669-2018-f03.jpg"/>

        </fig>

      <?pagebreak page677?><p id="d1e4127">Several markers are indicative of certain combustion sources of PAHs,
pointing to gasoline, diesel, crude oil or grass, coal and wood combustion
origins, namely FLT <inline-formula><mml:math id="M195" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> (FLT <inline-formula><mml:math id="M196" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> PYR), BaA <inline-formula><mml:math id="M197" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> (BaA <inline-formula><mml:math id="M198" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> CHR),
IPY <inline-formula><mml:math id="M199" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> (IPY <inline-formula><mml:math id="M200" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> BPE) and BaP <inline-formula><mml:math id="M201" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> BPE. The calculated
FLT <inline-formula><mml:math id="M202" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> (FLT <inline-formula><mml:math id="M203" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> PYR) (0.49–0.51), IPY <inline-formula><mml:math id="M204" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> (IPY <inline-formula><mml:math id="M205" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> BPE) (0.30–40)
and BaP <inline-formula><mml:math id="M206" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> BPE (1.20–1.64) values point to a domination of gasoline,
diesel and oil combustion. However, obtained values of
FLT <inline-formula><mml:math id="M207" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> (FLT <inline-formula><mml:math id="M208" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> PYR) and BaA <inline-formula><mml:math id="M209" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> (BaA <inline-formula><mml:math id="M210" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> CHR) ratios suggested that
coal and wood combustion have a certain role in PAH origination as well. It
is important to note that the shift of heavy- and low-molecular-weight PAH
ratios towards the heavy ones cannot be explained by only the anthropogenic
factor, the degradation of lighter PAHs due to environmental factors such as
photolysis under direct sun rays in the topsoil layers or thermal
degradation; biological uptake and biodegradation may play a significant role
as well (Wild and Jones, 1995; Johnsen, 2005; Choi et al., 2010). These processes are
predetermined by physical and chemical properties of the lighter fraction
PAHs such as low molecular weight, high vapour pressure and high volatility
rate (Mackay and Hickie, 2000). Volatilization proved to play the most
significant role in the global degradation of the two- and three-ringed PAHs
especially. Park et al. (1990) reported that approximately 30 % loss of
naphthalene accounts for volatilization, while for the remaining compounds
this process was insignificant. Heavy-weight PAHs, i.e., four- to six-ring
compounds, have low solubility in water, low volatility, and a strong
affinity to particulates (BC and SOM, fine fractions) and are less accessible
for biological uptake and degradation and thus are more persistent in the
environment (Johnsen, 2005; Haritash, 2009). It has been proven that PAHs may
form non-extractable [<inline-formula><mml:math id="M211" display="inline"><mml:msup><mml:mi/><mml:mn mathvariant="normal">14</mml:mn></mml:msup></mml:math></inline-formula>C]PAH residues in soil under the stimulation of
microbial activity, which obviously leads to unexpectedly lower results while
analyzing the concentrations of naphthalene, anthracene, pyrene and
benzo(a)pyrene in soil samples (Eschenbach et al., 1998).</p>
      <p id="d1e4253">Obtained probabilities for one-way ANOVA revealed no statistically
significant differences of total PAH concentrations in soils among
different land uses (<inline-formula><mml:math id="M212" display="inline"><mml:mrow><mml:mi>P</mml:mi><mml:mi mathvariant="italic">&lt;</mml:mi><mml:mn mathvariant="normal">0.05</mml:mn></mml:mrow></mml:math></inline-formula>). Probabilities for ANOVA are given in
Table 3.</p>
      <p id="d1e4268">The differences in levels of individual PAH compounds were tested using a
post hoc Fisher's least significant difference test. The results showed
significant differences of FLU, PHE, FLT, PYR, BaA, CHR, BbF, BaP and<?pagebreak page678?> BPE
concentrations among parkland, residential and industrial areas
(<inline-formula><mml:math id="M213" display="inline"><mml:mrow><mml:mi>p</mml:mi><mml:mo>=</mml:mo></mml:mrow></mml:math></inline-formula> 0.02<inline-formula><mml:math id="M214" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.05). The tested hypothesis suggested that PAH levels in urban
soil may differ among areas with different land utilization types, in the
following order: industrial, residential, parkland. The results of the study
proved the argument of the influence of the land use factor on the difference
of PAH levels in urban soils between studied sites. The land use factor is
intensively expressed in distribution of the dominant individual PAHs,
particularly BaP, PHE, FLT and PYR. These compounds are known to be a part of
the PAH mixtures isolated from the exhaust gases and industrial emissions
(Rehwagen et al., 2005) Thus it is not too surprising that elevated levels of
these pollutants are expected primarily in industrial and transport areas
along with surrounding areas, where maximum input of BC from air pollution
sources is noted. PHE representing low-molecular-weight PAH is a
thermodynamically stable tri-aromatic compound arising from
petroleum-hydrocarbon-based releases. Distribution of this contaminant
follows the scheme of potential sources of contamination with petroleum
product allocation (Fig. 4).</p>
</sec>
<sec id="Ch1.S3.SS3">
  <title>Health risk evaluation of PAHs in soils</title>
      <p id="d1e4294">Health risks associated with soil contamination from PAHs was assessed using
the
benzo(a)pyrene total potency equivalents approach (BaP<inline-formula><mml:math id="M215" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:math></inline-formula>). The
BaP<inline-formula><mml:math id="M216" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:math></inline-formula> for a soil sample is simply calculated by multiplying the
concentration of each PAH in the sample by its benzo(a)pyrene TEF, given in Table 6.</p>
      <p id="d1e4315">The calculated BaP<inline-formula><mml:math id="M217" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:math></inline-formula> on the average concentration of 15 PAH (here
and after referred to as BaP<inline-formula><mml:math id="M218" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:math></inline-formula>-15 PAH) varied between 0.44 and
0.66 mg kg<inline-formula><mml:math id="M219" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> of dry soil. The highest BaP<inline-formula><mml:math id="M220" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:math></inline-formula>-15PAH mean
concentrations were found in residential and industrial areas: 0.66 and
0.55 mg kg<inline-formula><mml:math id="M221" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>, respectively. Parkland areas are characterized by lower
but still considerable levels of BaPeq-15 PAH (mean 0.44 mg kg<inline-formula><mml:math id="M222" display="inline"><mml:mrow><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup><mml:mo>)</mml:mo></mml:mrow></mml:math></inline-formula>.
Note that one single sample taken from Kirovsky parkland exhibited a total
BaP<inline-formula><mml:math id="M223" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:math></inline-formula> concentration of 1.84 mg kg<inline-formula><mml:math id="M224" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> (The Park of 9th
January), which evidently shows that parkland land uses are subjected
to a high load of PAHs as well as other land uses. Obtained values are
several times higher than reported total PAH carcinogenic potencies in a
number of studies (BaP<inline-formula><mml:math id="M225" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:math></inline-formula> of total PAHs): 0.02 mg kg<inline-formula><mml:math id="M226" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> in
soils of Viseu and 0.23 mg kg<inline-formula><mml:math id="M227" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> in Lisbon, Portugal (Cachada et al.,
2012); Nadal et al., (2004) reported BaP<inline-formula><mml:math id="M228" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:math></inline-formula> concentrations varying
between 0.02 and 0.12 mg kg<inline-formula><mml:math id="M229" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> in soils of Tarragona Province, Spain;
0.18 mg kg<inline-formula><mml:math id="M230" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> in soils of Beijing and 0.24 mg kg<inline-formula><mml:math id="M231" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> in Shanghai,
China (Liu et al., 2010; Wang et al., 2013).</p>
      <p id="d1e4485">Finally, obtained BaP total potency equivalents of PAHs were compared with
soil quality guideline values for direct contact with contaminated soil with respect to particular land use (CCME, 2010), setting out the safe level of
0.6 mg kg<inline-formula><mml:math id="M232" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>BaP<inline-formula><mml:math id="M233" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:math></inline-formula> (for each land use). The reported
BaP<inline-formula><mml:math id="M234" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:math></inline-formula> of the 15 PAH concentrations was above the safe level of 0.6 mg kg<inline-formula><mml:math id="M235" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>. Exposure to these soils through direct contact
probably poses a significant risk to human health from carcinogenic effects
of PAHs, even in urban parklands. Obtained values of BaP<inline-formula><mml:math id="M236" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:math></inline-formula> were
further used to calculate the index of incremental lifetime cancer risk (ILCR).
This method provides quantitative evaluation of the human exposure to PAHs
through various exposure scenarios including ingestion, dermal contact and
inhalation of different age and gender groups.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F4"><caption><p id="d1e4541">Scale of potential sources of contamination with petroleum products (units per square kilometre) with PHE distribution plots.</p></caption>
          <?xmltex \igopts{width=236.157874pt}?><graphic xlink:href="https://se.copernicus.org/articles/9/669/2018/se-9-669-2018-f04.png"/>

        </fig>

      <p id="d1e4551">The acceptable level of ILCR is set at 10<inline-formula><mml:math id="M237" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">6</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>–10<inline-formula><mml:math id="M238" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> by the US EPA (US EPA, 2001). Risks below 10<inline-formula><mml:math id="M239" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">6</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> do
not require further action, while risks above 10<inline-formula><mml:math id="M240" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> are considered concerning and require additional action to reduce the exposure and
resulting risk (US EPA, 2004). Calculated values of TILCR are summarized in
Table 7.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T6" specific-use="star"><caption><p id="d1e4605">PAH concentrations in urban soils, expressed in BaP<inline-formula><mml:math id="M241" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">eq</mml:mi></mml:msub></mml:math></inline-formula>, mg kg<inline-formula><mml:math id="M242" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>.</p></caption><oasis:table frame="topbot"><?xmltex \begin{scaleboxenv}{.85}[.85]?><oasis:tgroup cols="11">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="right"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right" colsep="1"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:colspec colnum="7" colname="col7" align="right" colsep="1"/>
     <oasis:colspec colnum="8" colname="col8" align="right"/>
     <oasis:colspec colnum="9" colname="col9" align="right"/>
     <oasis:colspec colnum="10" colname="col10" align="right"/>
     <oasis:colspec colnum="11" colname="col11" align="right"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1">Compound</oasis:entry>  
         <oasis:entry rowsep="1" namest="col2" nameend="col4" align="center">Parkland </oasis:entry>  
         <oasis:entry rowsep="1" namest="col5" nameend="col7" align="center">Residential </oasis:entry>  
         <oasis:entry rowsep="1" namest="col8" nameend="col10" align="center">Industrial </oasis:entry>  
         <oasis:entry colname="col11">TEF<inline-formula><mml:math id="M244" display="inline"><mml:msup><mml:mi/><mml:mo>*</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">Mean <inline-formula><mml:math id="M245" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> TEF</oasis:entry>  
         <oasis:entry colname="col3">Max <inline-formula><mml:math id="M246" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> TEF</oasis:entry>  
         <oasis:entry colname="col4">Min <inline-formula><mml:math id="M247" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> TEF</oasis:entry>  
         <oasis:entry colname="col5">Mean <inline-formula><mml:math id="M248" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> TEF</oasis:entry>  
         <oasis:entry colname="col6">Max <inline-formula><mml:math id="M249" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> TEF</oasis:entry>  
         <oasis:entry colname="col7">Min <inline-formula><mml:math id="M250" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> TEF</oasis:entry>  
         <oasis:entry colname="col8">Mean <inline-formula><mml:math id="M251" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> TEF</oasis:entry>  
         <oasis:entry colname="col9">Max <inline-formula><mml:math id="M252" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> TEF</oasis:entry>  
         <oasis:entry colname="col10">Min <inline-formula><mml:math id="M253" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> TEF</oasis:entry>  
         <oasis:entry colname="col11"/>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">NAP</oasis:entry>  
         <oasis:entry colname="col2">0.00006</oasis:entry>  
         <oasis:entry colname="col3">0.00028</oasis:entry>  
         <oasis:entry colname="col4">0.00003</oasis:entry>  
         <oasis:entry colname="col5">0.00005</oasis:entry>  
         <oasis:entry colname="col6">0.00007</oasis:entry>  
         <oasis:entry colname="col7">0.00</oasis:entry>  
         <oasis:entry colname="col8">0.00009</oasis:entry>  
         <oasis:entry colname="col9">0.00021</oasis:entry>  
         <oasis:entry colname="col10">0.00</oasis:entry>  
         <oasis:entry colname="col11">0.001</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">ANA</oasis:entry>  
         <oasis:entry colname="col2">0.00002</oasis:entry>  
         <oasis:entry colname="col3">0.00018</oasis:entry>  
         <oasis:entry colname="col4">0.00</oasis:entry>  
         <oasis:entry colname="col5">0.00</oasis:entry>  
         <oasis:entry colname="col6">0.00001</oasis:entry>  
         <oasis:entry colname="col7">0.00</oasis:entry>  
         <oasis:entry colname="col8">0.00</oasis:entry>  
         <oasis:entry colname="col9">0.00003</oasis:entry>  
         <oasis:entry colname="col10">0.00</oasis:entry>  
         <oasis:entry colname="col11">0.001</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">FLU</oasis:entry>  
         <oasis:entry colname="col2">0.0001</oasis:entry>  
         <oasis:entry colname="col3">0.00023</oasis:entry>  
         <oasis:entry colname="col4">0.00005</oasis:entry>  
         <oasis:entry colname="col5">0.00017</oasis:entry>  
         <oasis:entry colname="col6">0.0004</oasis:entry>  
         <oasis:entry colname="col7">0.00003</oasis:entry>  
         <oasis:entry colname="col8">0.00017</oasis:entry>  
         <oasis:entry colname="col9">0.00031</oasis:entry>  
         <oasis:entry colname="col10">0.00006</oasis:entry>  
         <oasis:entry colname="col11">0.001</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">PHE</oasis:entry>  
         <oasis:entry colname="col2">0.00016</oasis:entry>  
         <oasis:entry colname="col3">0.00045</oasis:entry>  
         <oasis:entry colname="col4">0.00005</oasis:entry>  
         <oasis:entry colname="col5">0.00026</oasis:entry>  
         <oasis:entry colname="col6">0.00047</oasis:entry>  
         <oasis:entry colname="col7">0.00003</oasis:entry>  
         <oasis:entry colname="col8">0.00036</oasis:entry>  
         <oasis:entry colname="col9">0.00065</oasis:entry>  
         <oasis:entry colname="col10">0.00007</oasis:entry>  
         <oasis:entry colname="col11">0.001</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">ANT</oasis:entry>  
         <oasis:entry colname="col2">0.0006</oasis:entry>  
         <oasis:entry colname="col3">0.0037</oasis:entry>  
         <oasis:entry colname="col4">0.0001</oasis:entry>  
         <oasis:entry colname="col5">0.0004</oasis:entry>  
         <oasis:entry colname="col6">0.0011</oasis:entry>  
         <oasis:entry colname="col7">0.00</oasis:entry>  
         <oasis:entry colname="col8">0.0005</oasis:entry>  
         <oasis:entry colname="col9">0.0009</oasis:entry>  
         <oasis:entry colname="col10">0.0001</oasis:entry>  
         <oasis:entry colname="col11">0.01</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">FLT</oasis:entry>  
         <oasis:entry colname="col2">0.00018</oasis:entry>  
         <oasis:entry colname="col3">0.00035</oasis:entry>  
         <oasis:entry colname="col4">0.00009</oasis:entry>  
         <oasis:entry colname="col5">0.00069</oasis:entry>  
         <oasis:entry colname="col6">0.00149</oasis:entry>  
         <oasis:entry colname="col7">0.00004</oasis:entry>  
         <oasis:entry colname="col8">0.00072</oasis:entry>  
         <oasis:entry colname="col9">0.0015</oasis:entry>  
         <oasis:entry colname="col10">0.00011</oasis:entry>  
         <oasis:entry colname="col11">0.001</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">PYR</oasis:entry>  
         <oasis:entry colname="col2">0.00018</oasis:entry>  
         <oasis:entry colname="col3">0.00035</oasis:entry>  
         <oasis:entry colname="col4">0.00009</oasis:entry>  
         <oasis:entry colname="col5">0.00074</oasis:entry>  
         <oasis:entry colname="col6">0.00167</oasis:entry>  
         <oasis:entry colname="col7">0.00004</oasis:entry>  
         <oasis:entry colname="col8">0.0007</oasis:entry>  
         <oasis:entry colname="col9">0.0015</oasis:entry>  
         <oasis:entry colname="col10">0.00016</oasis:entry>  
         <oasis:entry colname="col11">0.001</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">BaA</oasis:entry>  
         <oasis:entry colname="col2">0.019</oasis:entry>  
         <oasis:entry colname="col3">0.053</oasis:entry>  
         <oasis:entry colname="col4">0.004</oasis:entry>  
         <oasis:entry colname="col5">0.035</oasis:entry>  
         <oasis:entry colname="col6">0.064</oasis:entry>  
         <oasis:entry colname="col7">0.002</oasis:entry>  
         <oasis:entry colname="col8">0.03</oasis:entry>  
         <oasis:entry colname="col9">0.067</oasis:entry>  
         <oasis:entry colname="col10">0.007</oasis:entry>  
         <oasis:entry colname="col11">0.10</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">CHR</oasis:entry>  
         <oasis:entry colname="col2">0.0015</oasis:entry>  
         <oasis:entry colname="col3">0.0044</oasis:entry>  
         <oasis:entry colname="col4">0.0001</oasis:entry>  
         <oasis:entry colname="col5">0.0031</oasis:entry>  
         <oasis:entry colname="col6">0.0069</oasis:entry>  
         <oasis:entry colname="col7">0.0002</oasis:entry>  
         <oasis:entry colname="col8">0.0028</oasis:entry>  
         <oasis:entry colname="col9">0.0054</oasis:entry>  
         <oasis:entry colname="col10">0.0007</oasis:entry>  
         <oasis:entry colname="col11">0.01</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">BbF</oasis:entry>  
         <oasis:entry colname="col2">0.023</oasis:entry>  
         <oasis:entry colname="col3">0.069</oasis:entry>  
         <oasis:entry colname="col4">0.005</oasis:entry>  
         <oasis:entry colname="col5">0.046</oasis:entry>  
         <oasis:entry colname="col6">0.084</oasis:entry>  
         <oasis:entry colname="col7">0.002</oasis:entry>  
         <oasis:entry colname="col8">0.041</oasis:entry>  
         <oasis:entry colname="col9">0.10</oasis:entry>  
         <oasis:entry colname="col10">0.01</oasis:entry>  
         <oasis:entry colname="col11">0.10</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">BkF</oasis:entry>  
         <oasis:entry colname="col2">0.015</oasis:entry>  
         <oasis:entry colname="col3">0.0560</oasis:entry>  
         <oasis:entry colname="col4">0.002</oasis:entry>  
         <oasis:entry colname="col5">0.019</oasis:entry>  
         <oasis:entry colname="col6">0.036</oasis:entry>  
         <oasis:entry colname="col7">0.001</oasis:entry>  
         <oasis:entry colname="col8">0.016</oasis:entry>  
         <oasis:entry colname="col9">0.033</oasis:entry>  
         <oasis:entry colname="col10">0.004</oasis:entry>  
         <oasis:entry colname="col11">0.10</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">BaP</oasis:entry>  
         <oasis:entry colname="col2">0.22</oasis:entry>  
         <oasis:entry colname="col3">0.7</oasis:entry>  
         <oasis:entry colname="col4">0.04</oasis:entry>  
         <oasis:entry colname="col5">0.43</oasis:entry>  
         <oasis:entry colname="col6">0.87</oasis:entry>  
         <oasis:entry colname="col7">0.02</oasis:entry>  
         <oasis:entry colname="col8">0.34</oasis:entry>  
         <oasis:entry colname="col9">0.73</oasis:entry>  
         <oasis:entry colname="col10">0.07</oasis:entry>  
         <oasis:entry colname="col11">1.00</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">DBA</oasis:entry>  
         <oasis:entry colname="col2">0.15</oasis:entry>  
         <oasis:entry colname="col3">0.90</oasis:entry>  
         <oasis:entry colname="col4">0.00</oasis:entry>  
         <oasis:entry colname="col5">0.10</oasis:entry>  
         <oasis:entry colname="col6">0.20</oasis:entry>  
         <oasis:entry colname="col7">0.00</oasis:entry>  
         <oasis:entry colname="col8">0.10</oasis:entry>  
         <oasis:entry colname="col9">0.40</oasis:entry>  
         <oasis:entry colname="col10">0.00</oasis:entry>  
         <oasis:entry colname="col11">5.00</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">BPE</oasis:entry>  
         <oasis:entry colname="col2">0.0017</oasis:entry>  
         <oasis:entry colname="col3">0.0046</oasis:entry>  
         <oasis:entry colname="col4">0.0004</oasis:entry>  
         <oasis:entry colname="col5">0.0029</oasis:entry>  
         <oasis:entry colname="col6">0.0052</oasis:entry>  
         <oasis:entry colname="col7">0.0001</oasis:entry>  
         <oasis:entry colname="col8">0.0027</oasis:entry>  
         <oasis:entry colname="col9">0.0069</oasis:entry>  
         <oasis:entry colname="col10">0.0006</oasis:entry>  
         <oasis:entry colname="col11">0.01</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">IPY</oasis:entry>  
         <oasis:entry colname="col2">0.012</oasis:entry>  
         <oasis:entry colname="col3">0.049</oasis:entry>  
         <oasis:entry colname="col4">0.00</oasis:entry>  
         <oasis:entry colname="col5">0.017</oasis:entry>  
         <oasis:entry colname="col6">0.045</oasis:entry>  
         <oasis:entry colname="col7">0.001</oasis:entry>  
         <oasis:entry colname="col8">0.015</oasis:entry>  
         <oasis:entry colname="col9">0.038</oasis:entry>  
         <oasis:entry colname="col10">0.00</oasis:entry>  
         <oasis:entry colname="col11">0.10</oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M254" display="inline"><mml:mo>∑</mml:mo></mml:math></inline-formula>15 PAH</oasis:entry>  
         <oasis:entry colname="col2">0.4435</oasis:entry>  
         <oasis:entry colname="col3">1.84154</oasis:entry>  
         <oasis:entry colname="col4">0.05191</oasis:entry>  
         <oasis:entry colname="col5">0.65531</oasis:entry>  
         <oasis:entry colname="col6">1.31631</oasis:entry>  
         <oasis:entry colname="col7">0.02644</oasis:entry>  
         <oasis:entry colname="col8">0.55004</oasis:entry>  
         <oasis:entry colname="col9">1.3854</oasis:entry>  
         <oasis:entry colname="col10">0.0928</oasis:entry>  
         <oasis:entry colname="col11"/>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1"><inline-formula><mml:math id="M255" display="inline"><mml:mo>∑</mml:mo></mml:math></inline-formula>7 PAH<inline-formula><mml:math id="M256" display="inline"><mml:msup><mml:mi/><mml:mo>*</mml:mo></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col2">0.4405</oasis:entry>  
         <oasis:entry colname="col3">1.8314</oasis:entry>  
         <oasis:entry colname="col4">0.0511</oasis:entry>  
         <oasis:entry colname="col5">0.6501</oasis:entry>  
         <oasis:entry colname="col6">1.3059</oasis:entry>  
         <oasis:entry colname="col7">0.0262</oasis:entry>  
         <oasis:entry colname="col8">0.5448</oasis:entry>  
         <oasis:entry colname="col9">1.3734</oasis:entry>  
         <oasis:entry colname="col10">0.0917</oasis:entry>  
         <oasis:entry colname="col11"/>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup><?xmltex \end{scaleboxenv}?></oasis:table><table-wrap-foot><p id="d1e4629">
<inline-formula><mml:math id="M243" display="inline"><mml:msup><mml:mi/><mml:mo>*</mml:mo></mml:msup></mml:math></inline-formula>Values of the toxic equivalency factors proposed by Nisbet and
Lagoy (1992).</p></table-wrap-foot></table-wrap>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T7" specific-use="star"><caption><p id="d1e5452">Calculated TILCRs based on different routes of exposure and land
use scenarios (sum of children and adults).</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="6">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="left"/>
     <oasis:colspec colnum="4" colname="col4" align="left"/>
     <oasis:colspec colnum="5" colname="col5" align="left"/>
     <oasis:colspec colnum="6" colname="col6" align="left"/>
     <oasis:thead>
       <oasis:row>  
         <oasis:entry colname="col1">Land use scenario</oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry rowsep="1" namest="col3" nameend="col6" align="center">Total incremental lifetime cancer risk (unitless) </oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">  
         <oasis:entry colname="col1"/>  
         <oasis:entry colname="col2">Route of exposure</oasis:entry>  
         <oasis:entry colname="col3">Ingestion</oasis:entry>  
         <oasis:entry colname="col4">Dermal</oasis:entry>  
         <oasis:entry colname="col5">Inhalation</oasis:entry>  
         <oasis:entry colname="col6">Total risk</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>  
         <oasis:entry colname="col1">Parkland</oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3">6.16 <inline-formula><mml:math id="M257" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M258" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">7</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">1.71 <inline-formula><mml:math id="M259" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M260" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">7</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col5">2.05 <inline-formula><mml:math id="M261" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M262" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">12</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6">7.77 <inline-formula><mml:math id="M263" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M264" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">7</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Residential</oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3">4.24 <inline-formula><mml:math id="M265" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M266" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">1.24 <inline-formula><mml:math id="M267" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M268" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">6</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col5">2.83 <inline-formula><mml:math id="M269" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M270" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">8</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6">4.36 <inline-formula><mml:math id="M271" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M272" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row>  
         <oasis:entry colname="col1">Industrial (composite worker)</oasis:entry>  
         <oasis:entry colname="col2"/>  
         <oasis:entry colname="col3">8.41 <inline-formula><mml:math id="M273" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M274" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">6</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col4">–</oasis:entry>  
         <oasis:entry colname="col5">1.98 <inline-formula><mml:math id="M275" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M276" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">7</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>  
         <oasis:entry colname="col6">8.61 <inline-formula><mml:math id="M277" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M278" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">6</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula></oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <p id="d1e5772">All estimated TILCRs were within the acceptable range (10<inline-formula><mml:math id="M279" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">6</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>–10<inline-formula><mml:math id="M280" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>).
The TILCRs for different exposure pathways decreased in the following order: ingestion
<inline-formula><mml:math id="M281" display="inline"><mml:mo>&gt;</mml:mo></mml:math></inline-formula> dermal contact <inline-formula><mml:math id="M282" display="inline"><mml:mo>&gt;</mml:mo></mml:math></inline-formula> inhalation for both children
and adults. The greatest TILCR value was estimated for soil ingestion in the
case of residential land use (4.25 <inline-formula><mml:math id="M283" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M284" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">5</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>), followed by
industrial land use (8.41 <inline-formula><mml:math id="M285" display="inline"><mml:mo>×</mml:mo></mml:math></inline-formula> 10<inline-formula><mml:math id="M286" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">6</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>). Soil ingestion is considered to
be the
most significant route of exposure in residential areas, particularly for
children since they are more naturally active than other age groups, which
leads to greater CR caused by soil ingestion (Wang et al., 2015).
The estimated TILCRs caused by dermal contact with soil and inhalation for
both the children and adult groups were smaller than those caused by
ingestion of soil particles, ranging from 10<inline-formula><mml:math id="M287" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">6</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> to 10<inline-formula><mml:math id="M288" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">12</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>. The
applied RAIS model does not provide an estimation of CR for youths,
though this age group is supposed to be more vulnerable for dermal contact
with contaminated soil, which accounts for 32.5 % of the exposure,
followed by the CRs for<?pagebreak page679?> children and adults, accounting for 27.6 and
21.8 %, respectively, suggesting that dermal contact could be a
significant exposure pathway for youths compared to children and adults
(Wang et al., 2015). Exposure route related to dermal contact with soil in
industrial areas was not assessed, considering that skin of the workers is
not exposed.</p>
</sec>
</sec>
<sec id="Ch1.S4" sec-type="conclusions">
  <title>Conclusions</title>
      <p id="d1e5883">Results of the study demonstrated that soils within studied urban areas are
characterized by common levels of total PAHs generally attributed to high
traffic density of the city. Considerable levels of soil contamination with
PAHs were noted. The common tendency in PAH distribution patterns between
investigated sites clearly indicates the common source of PAHs in urban
soils. A larger portion of high-molecular-weight PAHs along with determined
molecular ratios suggest the predominance of pyrogenic sources, mainly
attributed to combustion of gasoline, diesel and oil. Petrogenic sources of
PAHs also have a significant portion defining the predominance of
low-molecular-weight PAHs associated with petroleum, such as phenanthrene. Derived
concentrations of seven carcinogenic PAHs as well as calculated BaP total
potency equivalents were multiple times higher than reported in a number of
other studies, indicating a significant risk for human health in the case of
direct contact. However application of the RAIS CR evaluation module
revealed that incremental lifetime risks posed to the population are under
the
acceptable range (10<inline-formula><mml:math id="M289" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">4</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula>–10<inline-formula><mml:math id="M290" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">6</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> and lower). One-way ANOVA results
showed significant differences in levels of 15 PAHs, 7 PAHs, FLU, PHE, FLT,
PYR, BaA, CHR, BbF, BaP and BPE among parkland, residential and industrial
land uses, suggesting the influence of land use factor on distribution of
PAHs in soils of the city. Further study with an application of complex
statistical methods such as principal component analysis, which
would contribute to precision of PAH sources allocation, is needed.</p>
</sec>

      
      </body>
    <back><notes notes-type="dataavailability">

      <p id="d1e5915">Data can be accessed at <uri>https://drive.google.com/open?id=18UCcZNp0_qzXHpXsW-O3jKYqPidiozbX</uri> (Shamilishvily et al., 2018).</p>
  </notes><app-group>
        <supplementary-material position="anchor"><p id="d1e5921"><bold>The Supplement related to this article is available online at <inline-supplementary-material xlink:href="https://doi.org/10.5194/se-9-669-2018-supplement" xlink:title="zip">https://doi.org/10.5194/se-9-669-2018-supplement</inline-supplementary-material>.</bold></p></supplementary-material>
        </app-group><notes notes-type="competinginterests">

      <p id="d1e5927">The authors declare that they have no conflict of
interest.</p>
  </notes><ack><title>Acknowledgements</title><p id="d1e5933">Saint Petersburg University grant no. 1.37.151.2014 and Saint Petersburg
State University Internal Grant for the Modernization of
Scientific Equipment no. 1.40.541.2017.<?xmltex \hack{\newline}?><?xmltex \hack{\newline}?>
Edited by: Martine van der Ploeg<?xmltex \hack{\newline}?>
Reviewed by: four anonymous referees</p></ack><ref-list>
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    <!--<article-title-html>Polycyclic aromatic hydrocarbon in urban soils of an Eastern European megalopolis: distribution, source identification and cancer risk evaluation</article-title-html>
<abstract-html><p>This study explores qualitative and quantitative composition of
15 priority polycyclic aromatic hydrocarbons (PAHs) in urban soils of some parkland, residential and industrial
areas of the large industrial centre of
Saint Petersburg (Russian Federation) in Eastern Europe. The aim of the study was to test the
hypothesis on the PAH loading differences among urban territories with
different land use scenarios. Benzo(a)pyrene toxic equivalency factors (TEFs)
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risk of soil contamination with PAHs. Results of the study demonstrated that
soils within residential and industrial areas are characterized by common
loads of PAHs generally attributed to high traffic activity in the city.
Considerable levels of soil contamination with PAHs were noted. Total PAH
concentrations ranged from 0.33 to 8.10 mg kg<sup>−1</sup>. A larger portion of
high-molecular-weight PAHs along with determined molecular ratios suggest the
predominance of pyrogenic sources, mainly attributed to combustion of
gasoline, diesel and oil. Petrogenic sources of PAHs have a significant
portion and define the predominance of low-molecular-weight PAHs associated with petroleum, such as phenanthrene. Derived concentrations of seven
carcinogenic PAHs as well as calculated BaP<sub>eq</sub> were multiple times
higher than reported in a number of other studies. The obtained
BaP<sub>eq</sub> concentrations of the sum of 15 PAHs ranged from 0.05 to
1.39 mg kg<sup>−1</sup>. A vast majority of examined samples showed
concentrations above the safe value of 0.6 mg kg<sup>−1</sup> (CCME,
2010). However, estimated incremental lifetime risks posed to the population
through distinct routes of exposure were in an acceptable range. One-way
ANOVA results showed significant differences in total PAHs and the sum of
seven
carcinogenic PAH concentrations as well as in levels of FLU, PHE, FLT, PYR,
BaA, CHR, BbF, BaP and BPE among parkland, residential and industrial land
uses, suggesting the influence of the land use factor.</p></abstract-html>
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