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RESEARCH ARTICLE
Air and seawater pollution and air–sea gas exchange of persistent
toxic substances in the Aegean Sea: spatial trends of PAHs, PCBs,
OCPs and PBDEs
Gerhard Lammel
1,2
&Ondřej Audy
1
&Athanasios Besis
3
&Christos Efstathiou
1
&
Kostas Eleftheriadis
4
&Jiři Kohoutek
1
&Petr Kukučka
1
&Marie D. Mulder
1
&
Petra Přibylová
1
&Roman Prokeš
1
&Tatsiana P. Rusina
1
&Constantini Samara
3
&
Aysun Sofuoglu
5
&Sait C. Sofuoglu
5
&Yücel Taşdemir
6
&Vassiliki Vassilatou
4
&
Dimitra Voutsa
3
&Branislav Vrana
1
Received: 19 November 2014 /Accepted: 11 March 2015
#Springer-Verlag Berlin Heidelberg 2015
Abstract Near-ground air (26 substances) and surface seawa-
ter (55 substances) concentrations of persistent toxic sub-
stances (PTS) were determined in July 2012 in a coordinated
and coherent way around the Aegean Sea based on passive air
(10 sites in 5 areas) and water (4 sites in 2 areas) sampling.
The direction of air–sea exchange was determined for 18 PTS.
Identical samplers were deployed at all sites and were
analysed at one laboratory. hexachlorobenzene (HCB), hexa-
chlorocyclohexanes (HCHs) as well as dichlorodiphenyltri-
chloroethane (DDT) and its degradation products are evenly
distributed in the air of the whole region. Air concentrations of
p,p′-dichlorodiphenyldichloroethylene (p,p′-DDE) and o,p′-
DDT and seawater concentrations of p,p′-DDE and p,p′-
DDD were elevated in Thermaikos Gulf, northwestern
Aegean Sea. The polychlorinated biphenyl (PCB) congener
pattern in air is identical throughout the region, while
polybrominated diphenylether (PBDE)patterns are obviously
dissimilar between Greece and Turkey. Various pollutants,
polycyclic aromatic hydrocarbons (PAHs), PCBs, DDE, and
penta- and hexachlorobenzene are found close to phase equi-
librium or net-volatilisational (upward flux), similarly at a
remote site (on Crete) and in the more polluted Thermaikos
Gulf. The results suggest that effective passive air sampling
volumes may not be representative across sites when PAHs
significantly partitioning to the particulate phase are included.
Keywords Air–sea gas exchange .Deposition .Passive
sampling .Volatilisation .Fugacity ratios .Aegean Sea
Introduction
Persistent toxic substances (PTS) pose a hazard for ecosys-
tems and human health as they undergo long-range atmo-
spheric transport (LRT), are ubiquitous in the global environ-
ment and, through bioaccumulation along food chains, may
reach harmful levels even in remote areas (UNEP 2003;WHO
2003). PTS include organochlorine pesticides (OCPs), such as
hexachlorobenzene (HCB), hexachlorocyclohexane (HCH),
and dichlorodiphenyltrichloroethane (DDT), and banned in-
dustrial chemicals such as polychlorinated biphenyls (PCBs),
banned in Europe since the 1970s, only recently restricted
industrial chemicals, such as polybrominated diphenylethers
(PBDEs), and combustion by-products, such as polycyclic
Responsible editor: Philippe Garrigues
Electronic supplementary material The online version of this article
(doi:10.1007/s11356-015-4363-4) contains supplementary material,
which is available to authorized users.
*Gerhard Lammel
lammel@recetox.muni.cz
1
Research Centre for Toxic Compounds in the Environment, Masaryk
University, Brno, Czech Republic
2
Multiphase Chemistry Department, Max Planck Institute for
Chemistry, Mainz, Germany
3
Department of Chemistry, Environmental Pollution Control
Laboratory, Aristotle University, Thessaloniki, Greece
4
Institute of Nuclear Technology and Radiation Protection, NCSR
Demokritos Institute, Athens, Greece
5
Department of Chemical Engineering, Izmir Institute of Technology,
Urla, Izmir, Turkey
6
Environmental Engineering Department, UludağUniversity,
Nilüfer, Bursa, Turkey
Environ Sci Pollut Res
DOI 10.1007/s11356-015-4363-4
aromatic hydrocarbons (PAHs, all combustion types) and also
HCB (waste burning), which primary emissions are ongoing.
LRT of chlorinated PTS (Semeena et al. 2006;UNECE2010)
and also of PAHs (Lammel et al. 2009; Galarneau et al. 2014)
is enhanced by re-volatilisation from surfaces (multihopping;
significance of secondary sources in air). The same can be
expected for most other PTS, as they resist to degradation in
the soil and surface water and are semivolatile (vapour pres-
sures between 10
−6
and 10
−2
Pa at 298 K). Environmental fate
monitoring is needed for global PTS assessment (Klánová
et al. 2011) and part of the National Implementation Plans of
parties to the Stockholm Convention (UNEP 2014), including
Greece and Turkey. High PTS levels in air and seawater are a
concern in the Mediterranean environment (Lipiatou and
Saliot 1991; Kouimtzis et al. 2002;UNEP2002; Terzi and
Samara 2004; Biterna and Voutsa 2005; Mandalakis et al.
2005; Tsapakis et al. 2006; Chrysikou et al. 2008;Chrysikou
and Samara 2009). The Mediterranean region is characterised
by strong urban and industrial sources and adjacent source
regions (western, central and eastern Europe). Exposure to
long-range transported pollution from central and eastern
Europe is highest in summer (Lelieveld et al. 2002).
Passive air sampling (PAS) is most useful for PTS moni-
toring and mapping, although the uncertainty of concentration
measurements is within a factor of 2–3 (Harner et al. 2006;
Klánová et al. 2008). Trace contaminants in water can be
quantified using hydrophobic passive water samplers (PWS)
with an uncertainty of about a factor of 2 (Lohmann et al.
2012).
PTS concentrations were measured in air and water, and the
direction of air–sea exchange were addressed in summer
(July) 2012 in a coordinated and coherent way at sites around
the Aegean Sea using passive air and water sampling tech-
niques. Our knowledge of exposure of the marine environ-
ment towards PTS in this region is deficient, and the region
as a whole had not been addressed before in a coherent sam-
pling campaign. The aim of the study was to contribute to the
characterisation of regional environmental exposure to PTS
and identify possible sources, notably by identification of
the direction of air–sea exchange. Identical samplers were
deployed at all sites, and the samples were prepared and
analysed at one laboratory.
Methodology
Sites
Eleven sites in five areas around the Aegean Sea were selected
to cover the major conurbations (urban and residential sites),
coastal countryside and islands (rural and remote sites)
(Fig. 1). Air was sampled at two remote sites at the coast of
Crete island, in southern Greece, at seven rural/residential
sites in central and northern Greece and in western Turkey,
as well as at one urban site in Thessaloniki, northern Greece.
Surface seawater was sampled at one of the Cretan sites and at
three sites in the Thermaikos Gulf, northern Aegean Sea
(Table 1).
Sampling
Air
PTS were collected by PAS using polyurethane foam (PUF)
disks (Molitan, Gumotex, Czech Republic; density of
0.030 g cm
−3
, 150 mm diameter, 15 mm thickness): Before
use, PUF disks were cleaned through 8-h Soxhlet extraction
with acetone and dichloromethane (DCM) and placed in a
glass cartridges. PUF disks were deployed in protective cham-
bers consisting of two stainless steel bowls (upper 30 cm di-
ameter and lower 24 cm diameter; Klánová et al. 2008).
PAS were deployed during 28–30 days at each site (see
Tab le 1), except at Selles Beach (11 days, 2–13 July 2012)
and at Nilüfer-Bursa (42 days, 2 July–13 August 2012). All
PAS data are corrected for field blanks. Between one and four
field blanks were produced at each sites by leaving the PUF
disks exposed within the PAS for a few seconds and keeping
all other operations identical to sample processing. Values
below the mean of the field blank values, b, plus three relative
standard deviations (σ) of the field blank values were consid-
ered <LOQ (LOQ=b+3σ).
The effective sampling volume of PAS, V(m
3
), needed to
convert measured contaminant mass (pg) into atmospheric
concentration (pg m
−3
), is dependent on substance properties
(K
oa
; Shoeib and Harner 2002), gas-particle partitioning (very
low sampling efficiency for particles), temperature and wind
speed (Klánová et al. 2008). For our study, it cannot be de-
rived from previous side-by-side active air sampling (AAS)
and PAS (such as Bohlin et al. 2014), since no such data exist
for the Mediterranean climate. Therefore, we experimentally
estimated V carrying out side-by-side AAS and PAS during
the campaign, at site 1a, Finokalia. This procedure is detailed
in the Supplementary Material (SM), S2.
Water
Altesil silicone rubber (SR) sheets (Altec, Great Britain) were
deployed simultaneously to the PAS for sampling of free dis-
solved contaminants in water. The sampling method is based
on diffusion and absorption of hydrophobic contaminants
from water to the silicone rubber polymer (Rusina et al.
2007,2010). Each sampler consisted of six sheets (55×90 ×
0.5 mm). Briefly, before exposure SR sheets were cleaned
with ethyl acetate (24 h) in a Soxhlet extractor, and spiked
with a mix of 14 performance reference compounds (PRCs;
D10-biphenyl and 13 PCB congeners not occurring in the
Environ Sci Pollut Res
environment) according to the procedure reported by Booij
et al. 2002. Before exposure, samplers were stored (at
−20 °C) and transported to the field in amber glass 100-ml
vials with a screw cap with a stainless steel liner. SR passive
samplers were deployed for 28 days in water mounted on
stainless steel wire holders at 1-m depth using buoy and rope.
After exposure, samplers were transported in original vials in
a cooling box to the laboratory and stored at −20 °C.
Air/water fugacity ratio
For fugacity ratio calculation (diffusive air–sea exchange, see
BAir–sea diffusive gas exchange calculations^)gas-phase
concentrations, c
a
, were derived (Eq. 1) from the PAS concen-
trations using the particulate mass fraction of the contami-
nants, θ, which were determined simultaneously by two pairs
of high-volume gas and particulate phase AAS (above, mean
of two values listed in Table S3).
ca¼cPAS 28d 1−θðÞ ð1Þ
Sampling frequencies were 12 hourly for gaseous and total
particulate fractions and 24–48 hourly for size-resolved par-
ticulate fractions.
Meteorological parameters (air temperature, humidity,
wind direction and velocity) were also measured (Table 1).
Fugacity ratios from air and seawater can be derived for three
sites i.e. 1b, 2c and 2d (Table 1).
Chemical analyses
All instrumental analyses were done in the same lab using
identical methods. PUFs and SRs were extracted with DCM
and methanol, respectively, in an automatic extractor (Büchi
B-811). Surrogate recovery standards (D8-naphthalene, D10-
phenanthrene and D12-perylene, PCB congeners 30 and 185,
13
C-labelled BDE congeners 28, 47, 99, 100, 153, 154, 183
and 209) were spiked on PAS PUFs prior to extraction. SRs
were brushed before extraction to remove biofouling from the
surface. Surrogate recovery standards (D8-naphthalene, D10-
phenanthrene, D12-perylene and PCB185) were added on
SRs prior to extraction (Soxhlet, methanol, 8 h).
Volume reduced extracts were split into two portions, for
PAH analysis (10 %) and analysis of PCBs, OCPs and PBDEs
(90 %).
For the PAHs analysis, the extract was cleaned up on a
silica column, eluted (10 mL n-hexane followed by 20 mL
DCM), concentrated and transferred into an insert in a vial.
Terphenyl was added as syringe standard. Gas chromatogra-
phy–mass spectrometry (GC-MS) analysis was performed on
7890A GC (Agilent, USA), equipped with a DB5-MSUI col-
umn (Agilent, J&W, USA) and coupled to a 7000B MS
Tabl e 1 Site characterisation, sampling periods, air temperature, wind speed [mean (min–max), hourly data] and number of samples collected in five
areas around the Aegean Sea
Site no. Name (sampling period in 2012) Location Type of site Temperature
(°C)
Wind speed
(m s
−1
)
No. of
samples
Air Seawater
1a Finokalia, Crete (5 July–2 August) 35.3° N/25.7° E Remote coastal 26.1 (20.8–33.6) 8.2 (1.2–13.4) 1
1b Selles Beach, Crete (3 July–2 August)
a
35.2° N/25.4° E Remote coastal 28.2 (22.4–34.5) 4.8 (0.6–7.7) 4
b
4
c
2a Neochorouda (2–30 July) 40.6° N/22.9° E Suburban 28.9 (20.7–38.9) 2.2 (1.2–4.8) 1
2b Thessaloniki, Agia Sophia (3–31 July) Urban 29.5 (23.3–36.9) 1.5 (0.7–3.4) 1
2c Thermaikos Gulf, Michaniona (2–30 July) 40.5° N/22.8° E Residential coastal n.d. n.d. 1 2
2d Thermaikos Gulf, Loudias River
estuaries (3–31 July)
40.5° N/22.7° E Remote coastal 29.3 (21.8–38.7) 1.6 (0.8–3.7) 1 2
d
2e Thermaikos Gulf mussel cultivation Remote marine n.d. n.d. 2
e
3a Athens, Demokritos (1–29 July) 38.0° N/23.8° E Suburban 29.1 (20.7–40.5)
f
1.7 (<0.4–5.1)
f
1
3b Politikos, Euboea (1–29 July) 38.4° N/24.2° E Rural n.d. n.d. 2
4 Nilüfer, Bursa (2 July–13 August) 40.2° N/29.1° E Suburban, rural 26.2 (15.3–36.2) 0.9 (<0.4–5.4) 1
5 Gülbahçe (2–31 July) 38.3° N/26.6° E Rural 28.9 (21.6–36.5) 5.6 (<0.4–11.3) 2
a
Passive water sampling 3 July–2 August, passive and active air sampling 2–13 July
b
At three localities within 2800 m along shore
c
At two localities within 1400 m along shore
d
≈100 m off shore
e
≈1500 m off shore
f
1–18 July only
Environ Sci Pollut Res
(Agilent, USA), operated in EI+ mode with selected ion re-
cording (SIR). Injection was 1 μL splitless at 280 °C, with He
as carrier gas (1.5 mL min
−1
). The GC programme was 80 °C
(1 min hold), then 15 °C min
−1
to 180 °C, followed 5 °C min
−1
to 310 °C (20 min hold). For PBDE, PCB and OCP analysis,
the extract was cleaned up on a H
2
SO
4
modified (44 % w/w)
silica column, eluted (40 mL DCM/n-hexane mixture 1:1),
concentratedandtransferredintoaninsertinavial.
13
C
BDEs 77 and 138, and PCB 121 were added as syringe stan-
dards. For PBDEs, HRGC/HRMS analysis was performed on
a 7890A GC (Agilent, USA) equipped with an RTX-1614
column (Restek, USA) and coupled to an AutoSpec Premier
MS (Waters, Micromass, UK), operated in EI+ mode at the
resolution of >10,000. For BDE 209, the MS resolution was
set to >5000.Injection was splitless 2 μL at 280 °C, with He as
carrier gas (1 mL min
−1
). The GC temperature programme
was 80 °C (1 min hold), then 20 °C min
−1
to 250 °C, followed
by 1.5 °C min
−1
to 260 °C (2 min hold) and 25 °C min
−1
to
320 °C (4.5 min hold). For PCBs and OCP GC-MS/MS anal-
ysis was performed on a 7890A GC (Agilent, USA) equipped
with an HT8 column (SGE, USA) and coupled to a 7000B MS
(Agilent, USA), operated in EI+ MRM. Injection was splitless
3μL at 280 °C, with He as carrier gas (1.5 mL min
−1
). The GC
temperature programme was 80 °C (1 min hold), then
40 °C min
−1
to 200 °C, and finally 5 °C min
−1
to 305 °C.
Quality assurance/quality control Recoveries of PAHs in
PAS were 79–129 %, except for dibenz(a,h)anthracene, which
was 150 % in PASs and 61–101 % in SRs, except for ace-
naphthylene, anthracene and benzo(a)pyrene, which were 29,
53 and 49 %, respectively. Recoveries of PCBs and OCPs
from PASs were 80–88 % and 71–114 %, respectively, while
recoveries from SRs were 101–111 % and 77–129 %, respec-
tively. Recoveries of PBDEs were 79–159 % from PASs, and
60–107 % from SRs, except for BDE209, which was poorly
recovered (24 % from PASs and 6 % from SRs on average).
Recovery factors were not applied to calculate PAH, PCB and
OCP results, but were applied for all PBDE results. Recovery
of surrogates (deuterated substances, see above) varied from
88 to 100 % for PCB and from 72 to 102 % for PAHs. Field
blanks for various types of sample were collected along with
the samples. For each site separately, the mean of one to four
PAS field blank values was subtracted from the air sample
values.
Values below the mean plus three standard deviations of
the field blank values were considered below limit of quanti-
fication (LOQ). Field blank values of most analytes in air
samples were lower than the instrument limits of quantifica-
tion (ILOQ) at most sites. Highest LOQs for analytes in PASs,
up to 0.028 and 0.13 ng m
−3
, resulted for acenaphthene (ACE)
and fluorene (FLN), respectively, and up to 24, 8.6 and
1.2 pg m
−3
resulted for PeCB, β-HCH and γ-HCH, respec-
tively. Higher LOQs for analytes in the high-volume AASs,
up to 0.0008 and 0.011 ng m
−3
resulted for FLN and phenan-
threne (PHE), respectively, and up to 0.8 pg m
−3
resulted for
α-andγ-HCH. The ILOQs were calculated on three times the
instrument limit of detection, which is calculated as three
times the chromatogram baseline noise level. The respective
ILOQs for various types of sample are listed in the SM,
Tab le S2.
Free dissolved water concentrations of analytes in SRs
were calculated from amounts accumulated in SRs using the
exponential uptake model described in Smedes (2007). The
required sampling rates were estimated by fitting PRC dissi-
pation data from sampler to the model described by Booij and
Smedes 2010.
Air–sea diffusive gas exchange calculations
State of phase equilibrium is addressed by fugacity calcula-
tion, based on the Whitman two-film model (Liss and Slater
1974; Bidleman and McConnell 1995). The fugacity ratio
(FR) is calculated as:
FR ¼fa=fw¼caRTa=cwHTw;salt
ð2Þ
with gas-phase concentration c
a
(ng m
−3
), dissolved aqueous
concentration c
w
(ng m
−3
), universal gas constant R
(Pa m
3
mol
−1
K
−1
), water temperature and salinity corrected
Henry’s law constant H
Tw,salt
(Pa m
3
mol
−1
)andairtempera-
ture T
a
(K), which was measured continuously on site. The
water temperature was assumed to be 0.5 K lower than the air
temperature, throughout, based on discontinuous measure-
ments at site 1b, 10–30 cm below the surface, which covered
morning, noon, evening and night time measurements. Values
0.3< FR<3.0 are conservatively considered to not safely differ
from phase equilibrium, as propagating from the uncertainty
of the Henry’s law constant, H
Tw,salt
, and measured concentra-
tions (e.g. Bruhn et al. 2003; Castro-Jiménez et al. 2012;
Zhong et al. 2012). This conservative uncertainty margin is
also adopted here, while FR>3.0 indicates net deposition and
FR< 0.3 net volatilisation. The diffusive air–seawater gas ex-
change flux (F
aw
,ngm
−2
day
−1
) is calculated according to the
Whitman two-film model (Bidleman and McConnell 1995;
Schwarzenbach et al. 2003):
Faw ¼kol cwcaRTa=HTw;salt
ð3Þ
with air–water gas exchange mass transfer coefficient k
ol
(m h
−1
), accounting for resistances to mass transfer in both
water (k
w
,mh
−1
)andair(k
a
,mh
−1
)(seeBidlemanand
McConnell 1995; Zhong et al. 2012; and references therein).
Substance property data are taken from the literature (refer-
ences listed in the SM, S1).
Sampler uptake kinetics and the half-time of equilibration
of organics dissolved in water in SRs is substance dependent.
For most substances the derived concentrations reflect the
Environ Sci Pollut Res
mean over the entire exposure period, but for HCH and some
two- to three-ring PAHs only the mean of the last 12–24 days
of the exposure period. Substances which, accordingly, were
determined in air and water simultaneously only for a short
period (air sampling terminated 14 days before water sam-
pling), i.e. HCH isomers, NAP, ACE, ACY and FLN were
excluded from diffusive air–sea exchange calculations.
Results and discussion
Air mass origin
The predominant origin of air masses during the sampling
campaign was central, eastern and southeastern Europe. This
is shown as the distribution of residence time of air masses in
Fig. S1. This analysis is based on re-analysis data and back
trajectory modelling (FLEXPART model; Stohl et al. 1998).
During 2–11 July 2012 the Aegean was mostly influenced
by northerly, in its northern part easterly advection as part of a
cyclonic system, which moved from western Russia to
Romania. Under the influence of a strong westerly flow to-
wards Europe, the flow in the northern part of the Aegean
switched to westerly during the night 11–12 July, such that
air which had been residing over the SW Balkans was
advected, as well as air from beyond, i.e. central Italy, the
NW Mediterranean Sea and the Iberian Peninsula. Air from
central Europe flew to the Aegean until the night of 17–18,
and from the northeast thereon. Then, for a few days, air
arrived in the Aegean from central Europe, directed
(counter-clockwise) around a cyclonic system above Italy.
From the evening of 27 July until the beginning of August,
eastern flow arrived in the Aegean. The mean air temperatures
ranged 26–29 °C in the study area with higher temperature
maxima at the Thessaloniki and Athens sites (Table 1). No
precipitation occurred during the measurement period with
only one exception, namely on 30 July at the Thermaikos
Gulf sites.
Concentration levels
Mean concentrations of PAHs, PCBs, OCPs and PBDEs
found in near-ground air and surface seawater are shown in
Figs. 1,2and 3. Concentrations of the individual substances
targeted are provided in Tables S4–5.
Levels, trends and patterns of PTS in near-ground air
Polycyclic aromatic hydrocarbons The significance of local
primary sources and, hence, spatial variation is higher for
PAHs than for halogenated PTS (Lammel et al. 2010;
Lammel 2015). In this study, we found a trend of increasing
PAH levels from remote to rural and residential sites, with the
highest levels occurring at urban and residential sites in the
Thessaloniki area (Figs. 1and 2, Tables 2,S4–S5). PAH pat-
terns in air seem to be quite dissimilar across sites (mean
correlation coefficient r=0.60; Table S6a). However, because
of major PAHs commonly found not being included in this
Finokalia, Crete
Selles Beach, Crete
Neochorouda
Thessaloniki, Agia Sophia
Thermaikos Gulf, Michaniona
Thermaikos Gulf, Loudias River estuaries
Athens, Demokritos
Polikos, Euboea
Nilüfer, Bursa
Gülbahçe, Izmir
ng m-3
Σ5PAHs
0,0 1,0 2,0 3,0 4,0
Finokalia, Crete
Selles Beach, Crete
Neochorouda
Thessaloniki, Agia Sophia
Thermaikos Gulf, Michaniona
Thermaikos Gulf, Loudias River estuaries
Athens, Demokritos
Polikos, Euboea
Nilüfer, Bursa
Gülbahçe, Izmir
pg m-3
Σ7PCBs
050100
050100
Finokalia, Crete
Selles Beach, Crete
Neochorouda
Thessaloniki, Agia Sophia
Thermaikos Gulf, Michaniona
Thermaikos Gulf, Loudias River estuaries
Athens, Demokritos
Polikos, Euboea
Nilüfer, Bursa
Gülbahçe, Izmir
pg m-3
Σ9OCPs
0246810121416
Finokalia, Crete
Selles Beach, Crete
Neochorouda
Thessaloniki, Agia Sophia
Thermaikos Gulf, Michaniona
Thermaikos Gulf, Loudias River estuaries
Athens, Demokritos
Polikos, Euboea
Nilüfer, Bursa
Gülbahçe, Izmir
pg m-3
Σ5PBDEs
Fig. 2 Sum concentrations of PAHs, PCBs, OCPs and PBDEs found in
the air at various sites across the Aegean Sea
Environ Sci Pollut Res
analysis (but only five substances), a conclusion on source
contributions would not be justified (Dvorská et al. 2012).
Indeed, the similarity across sites is high (mean r= 0.93) if
PAH patterns are compared across sites on a pg basis (i.e.
PAS results not divided by effective sampling volume;
Tab le S7 for 10 PAHs). Then, just some dissimilarity from
the prevailing pattern is indicated for one site, Bursa (r=
0.74–0.81). This can be explained by the inclusion of sub-
stances significantly partitioning to the particulate phase in
the targeted substance class, namely FLT and PYR (as shown
in the region; Terzi and Samara 2004, besides others). Gas-
particle partitioning of semivolatiles, and hencethe effective
sampling volume, depends not only on temperature (similar
across sites) but also on the particulate phase chemical prop-
erties, which was certainly dissimilar across site types and
across sites of same type. This is related to the processes
determining gas-particle partitioning of semivolatiles, which
are dependent on particulate phase chemical properties, such
as organic and black carbon abundances (Lohmann and
Lammel 2004). The PAH levels at the remote sites 1a–bare
similar to those observed at a high mountain site in 2006
(Moussala, SW Bulgaria) and in the open eastern
Mediterranean Sea in 2010, but lower than those observed in
the Aegean Sea, eastern Mediterranean Sea, and Black Seas in
2006 (ship measurements; Table 2). Local primary sources
should also explain the levels found in Aliartos, central
Greece, in 2006 and a suburban site in the Izmir area in
2003–2004, which were more than one order of magnitude
higher (Table 2). The concentrations reported from rural sites
in the Republic of Macedonia (Stafilov et al. 2011;Table2)
are based on the same sampling and analysis methods as our
study, but V
28d
=100 m
3
was assumed throughout, which is up
to a factor of 6 below values of V
28d
used in here. This may
explain the high levels reported from there.
The levels of PAHs at the urban/residential sites in the area
of Thessaloniki (2a–c) are low among the range of levels
reported for urban and rural sites in Greece for gaseous
PAHs collected by active sampling (Manoli et al. 2011,and
references herein). For PAHs and HCHs, the differences span
more than one order of magnitude in some cases (Table 2).
Partly, this discrepancy might be explained by overestimated
sampling efficiencies (discussed in section S2).
Polychlorinated biphenyls PCBs in the Thessaloniki,
Athens and Izmir areas (sites 2a, 3a and 5), as well as in the
Bursa area, NW Turkey, in 2008–2009 (Birgül and Taşdemir
2011), are found (only) a factor of 2 higher than at the remote
sites 1a and 1b. This points to the significance of PCB sources
in urban areas for regional distribution discussed previously
(Diamond et al. 2010). Urban-to-rural PCB gradients were
also observed in the Mediterranean (Mandalakis et al. 2002;
Gasićet al. 2010). PCB patterns in air are almost identical
across all sites in the region (Table S6a). The same is found
Selles Beach, Crete
Thermaikos Gulf, Michaniona
Thermaikos Gulf, Loudias River estuaries
Thermaikos Gulf, mussel culvaons
pg L-1
Σ27PAHs and related compounds
0 2000 4000 6000
Selles Beach, Crete
Thermaikos Gulf, Michaniona
Thermaikos Gulf, Loudias River estuaries
Thermaikos Gulf, mussel culvaons
pg L-1
Σ7PCBs
02040
Selles Beach, Crete
Thermaikos Gulf, Michaniona
Thermaikos Gulf, Loudias River estuaries
Thermaikos Gulf, mussel culvaons
pg L-1
Σ10OCPs
0 200 400 600
0510
Selles Beach, Crete
Thermaikos Gulf, Michaniona
Thermaikos Gulf, Loudias River estuaries
Thermaikos Gulf, mussel culvaons
pg L-1
Σ8PBDEs
Fig. 3 Sum concentrations of PAHs and related compounds, PCBs,
OCPs and PBDEs found in surface sea water at coastal sites across the
Aegean Sea
Environ Sci Pollut Res
with slightly lower correlation coefficients if PCB
patterns are compared across sites on a pg basis
(Table S7). Selective photochemical degradability of
the congeners (Mandalakis et al. 2003) would suggest
that the pattern changes during transport from (urban)
sources to the remote site, not confirmed here.
Tabl e 2 Overview of contaminants’mean concentrations observed in near-ground air of the region in recent years (PAHs, ng m
−3
; all other, pg m
−3
).
Limited number of individual substances included for the sake of comparability
Site, year, reference ΣPAH
5
a
ΣPCB
7
b
HCB ΣHCH
c
ΣDDTs
d
ΣPBDE
3
e
Remote
Crete, remote (summer 2012, this work, sites 1a–b) 0.070–0.63 5.8–25.9 8.1–19 3.4–15.8 3.2–6.3/0.40–0.78 0.4–0.78
Crete, remote (summer 2006; Iacovidou et al. 2009)8.4
f
1.2
Thessaloniki area, coastal remote (summer 2012, this work, site 2d) 0.76 22.6 11 11.5 13.8
SW Bulgaria, remote, high mountain (Moussala, summer 2006; Halse et al. 2011) 0.63 10.3 5 5.9 1 9.7
Aegean Sea (cruise, summer 2006; Castro-Jiménez et al. 2012; Berrojalbiz et al. 2014)5.5
f
69–234 11–106 39–85
Black Sea (cruise, summer 2006; Castro-Jiménez et al. 2012)7.4
g
C and E Mediterranean (cruises, June 2006, May 2007; Castro-Jiménez et al. 2012;
Berrojalbiz et al. 2014)
4.7 29–234 5–178 <3–155
E Mediterranean (cruise summer 2010; Mulder et al. 2013,2014) 0.61 3.3 6.0 1.4 4.3
Rural, residential
Thessaloniki area, residential (summer 2012, this work, sites 2a, 2c) 2.33–3.64 26.7–47.5 9.9–10 9.3–10.4 8.4–51/0.56–1.12
Athens, suburban (summer 2012, this work, site 3a) 0.25 50.2 10.2 9.7 4.7 1.5
Central Greece, rural (summer 2012, this work, site 3b) 0.58 9.0 6.7 4.8 7.0 0.9
Izmir, suburban, W Turkey, whole year 2003–2004 (Demircioglu et al. 2011)21.9
W Greece, two rural sites, whole year 2000–2001 (Terzi and Samara 2004)2.9–13.8
j
C Greece, rural (Aliartos, summer 2006; Halse et al. 2011) 23.7 13.6 54.0 228
NW Turkey, semi-residential (summer 2012, this work, site 4) 0.23 25.6 5.5 5.7 7.9 0.7
NW Turkey, semi-rural, full year 2008–09 (Birgül and Taşdemir 2011)74
NW Turkey, rural , coastal, full year 2008–2009 (Yolsal et al. 2014)80
W Turkey, rural (summer 2012, this work, site 5) 0.27 55.3 12.3 13.8 12.8 8.5
Macedonia, two rural sites, summer 2007 (Stafilov et al. 2011)24–174 37–46 101–182 36–126
Urban, industrial
Thessaloniki area, urban (summer 2012, this work, site 2b) 2.38 85.7 9.8 14.9 42.5/6.96
W Greece, urban site, whole year 2000–2001 (Terzi and Samara 2004)21.7
h
Athens, urban, December 2006 (Mandalakis et al. 2009) 3.6
Two sites in the suburban area of Athens, June and November 2003
(Vasilakos et al. 2007)
17.5–20.1
h
Iraklion, semi-urban, 2006–2007 (Mandalakis et al. 2009) 10.7
Republic of Macedonia, four urban sites, summer 2007 (Stafilov et al. 2011)74–278 35–51 165–3033 106–246
Izmir, W Turkey, winter/summer 2005 (Pozo et al. 2009) 644/287 29/48 51/60
Izmir, W Turkey, winter 2004 (Demircioglu et al. 2011)100
Izmir, W Turkey, spring 2003 (Sofuoglu et al. 2004)22849
Aliaga, W Turkey, all seasons 2009–2010 (Kaya et al. 2012)782560
Zonguldak, N Turkey, winter/summer 2007–2008 (Akyüz and Çabuk 2010)260/21
Konya, S Turkey, full year 2006–2007 (Ozcan and Aydin 2009) 93 78 520 130
Bursa, NW Turkey, all seasons 2004–2005 (Taşdemir and Esen 2007)20
Bursa, NW Turkey, full year 2008–2009 (Birgül et al. 2011; Yolsal et al. 2014)117
h
61
a
Sum of ACE, FLN, PHE, FLT and PYR
b
PCB28, PCB52, PCB101, PCB118, PCB153, PCB138 and PCB180
c
Sum of α-andγ-HCH
d
Sum of DDT and DDE isomers
e
Sum of BDE47, BDE99 and BDE100
f
Without PCB28 and PCB138
g
With out ACE
h
Without ACE and FLN
Environ Sci Pollut Res
Organochlorine pesticides The levels of HCB, HCHs and
DDX in air at the rural and residential sites 3a–b, 4 and 5
are not elevated against the remote sites, but similar. The
highest concentrations of HCB and α-HCH are actually found
at the remote site 1a (Tables S4a,S5). The ratio α-HCH/γ-
HCH ranges widely, from 1.3 to 7.8. The lowest values of this
ratio are observed at the urban sites 2a, b, close to what was
previously found at site 2b in summer for the particle-bound
HCH isomers (Chrysikou and Samara 2009). The maximum
α-HCH/γ-HCH ratio is observed at the remote site 1a (re-
mote, 7.8) and may reflect the effect of the higher Henry
coefficient (units of Pa m
3
mol
−1
)ofα-HCH in an environ-
ment where the atmospheric levels are dominated by the
source re-volatilisation from surface seawater. OCP patterns
in air are found highly correlated across all sites except the
remote site 1a (also when compared on a pg basis, see
Tab les S6a and 7), which show different patterns, e.g. DDT/
DDX is the highest. This may also indicate substance selective
sinks (dry deposition, photochemistry) or sources (re-
volatilisation from the sea surface) active during transport
from continental sources to Crete. The prevailing spatial ho-
mogeneity of the concentration levels confirms the perception
of long-lived pollutants undergoing even distribution within a
region, or even being dominated by LRT from outside the
region. In general, they are lower than reported previously
from the same type of sites in the region (though only few
measurements available; Table 2). At the remote sites, HCB
and DDX levels are found similar to ship measurements in
2010 in the eastern Mediterranean (Mulder et al. 2013), while
DDX was much lower than at a remote high mountain site in
SW Bulgaria (Halse et al. 2011; Table 2). Furthermore, DDX
had been reported very high at a rural site in central Greece,
Aliartos, in 2006 (Halse et al. 2011; Table 2).
A fairly consistent regional distribution with rather
small urban-to-rural/residential concentration gradients
was found for HCB, HCHs and DDX, and small rural/
residential-to-remote gradients for HCB and HCHs.
Similar conclusions were drawn for HCB and HCHs
based on PAS across the entire European continent in
2006–2007 (Halse et al. 2011).
In contrast, DDXs, namely p,p′-
dichlorodiphenyldichloroethylene (p,p′-DDE) and also o,p′-
DDT, were elevated in air at the urban and coastal sites in
the Thermaikos Gulf (2b, 2c and 2d, Fig. 2, Table S4a), as
well as in seawater (namely p,p′-DDE and p,p′-DDD, sites 2c
and 2d, Fig. 2, Table S4b). The fraction of parent DDT among
the DDX compounds is low in both air and seawater (ranges
0.03–0.43 and 0.01–0.37, respectively). This indicates the ab-
sence of any fresh DDTinput to the marine environment of the
Aegean. DDT had been banned in the 1970s and 1980s
(Pacyna et al. 2003). However, the surface seawater of the
eastern Mediterranean is expected to be a source for DDT
since the 1980s (Stemmler and Lammel 2009).
Polybrominated diphenylethers BDE levels in air are found
at sites 2b (urban), 2d (remote coastal) and 5 (rural) and are
found about one order of magnitude higher than at the other
sites (Figs. 1d and 2, Tables S4a,S5). While the high levels
correspond to what was reported in 2006–2007 from Greek
urban and semi-urban sites (Mandalakis et al. 2009; Table 2),
the lower levels (sites 1a, 1b, 2a, 2c, 3b and 4; Fig. 2,
Tab les S4a,S5) are below earlier observations, including
one from Finokalia, i.e. site 1a (Iacovidou et al. 2009;
Tab le 2). The measured concentrations might be
underestimated due to overestimated sampling efficiencies
(discussed in section S2) for some sites (2a, 2b, 3a and 4).
Surprisingly, while at most Greek sites, the most abundant
congener was BDE47 followed by BDE99; it was BDE28 at
the Greek site 3b and at the two Turkish sites. PBDE patterns
in air are obviously similar among most Greek sites (even
identical, r=1.0 between sites 1 and 2, and sites 2 and 3),
but dissimilar among the Turkish sites and across the countries
(Table S6a). When PBDE PAS results are expressed as ng
rather than as ng m
−3
(Table S7), correlation coefficients are
not higher, but lower. This is noteworthy, as the targeted
PBDEs are significantly partitioning to the particulate phase
(Chen et al. 2006;CetinandOdabasi2008;Suetal.2009),
similar to targeted PAHs, for which correlation coefficients are
higher when based on ng (above). Observations suggest that
PBDE phase partitioning is largely determined by adsorption
(Cetin and Odabasi 2008;Suetal.2009). This suggests that
different aerosol chemical composition (across sites) could
hardly affect partitioning, in agreement with the finding here
(Tables S6a and S7). However, predictability of PBDE
partitioning is low, as most congeners are not expected to be
in phase equilibrium as a consequence of high K
oa
values
(Cetin and Odabasi 2008). Therefore, phase partitioning of
individual congeners could vary across sites and in different
air masses at the same site even for similar temperatures and
similar particulate phase chemical properties, determined by
aging.
Levels and trends in surface seawater
Mean levels of the sum concentrations of PAHs and related
compounds, PCBs, OCPs and PBDEs found in surface sea-
water at four coastal sites across the Aegean Sea are presented
in Fig. 3(for individual substances targeted, see Table S4).
Pollutant levels and spatial trends The concentrations of
PAHs, PCBs, HCHs and DDX compounds in surface seawa-
ter of the Thermaikos Gulf are a factor of 2–10 higher than at
the Cretan site, 1b (Figs. 1and 3, Table S4b). This concentra-
tion gradient is exceeding one order of magnitude for some
PAHs, notably PHE, RET, BBN, BGF, CHR and BEP. This
may reflect direct discharges from nearby urban activities and
from ships, or photochemical degradation during atmospheric
Environ Sci Pollut Res
transport to the remote site. A similar north–south gradient of
PCB was observed in 2006–2007, with a concentration span
of two to four between the northern and southern Aegean Sea
(dissolved fractions; Berrojalbiz et al. 2011).
For PeCB, HCB and PBDEs, no significant difference in
seawater concentrations is found across sites.
The spatial variation of seawater pollution across the three
Thermaikos Gulf sites is considerable for PAHs (highest at the
residential coastal site 2c, Michaniona) and DDX (highest at
the remote site 2d, Loudias River estuaries; Figs. 1and 3,
Table S4b). The highest OCP levels at the Loudias River
plume imply influence from agricultural activities, whereas
the highest levels of PCBs and PBDEs at the off-shore site
2e (located 1.4 km from the coastal site 2d) may indicate a
shift of contaminant partitioning from particle-bound to dis-
solved, corresponding to a negative gradient of suspended
particulate matter concentration, or influence from shipping
activities.
Comparison with previous observations Our data represent
a snapshot in time. The PAH levels in the Thermaikos Gulf are
significantly lower than those found in the northern Aegean
Sea in 1997 (10–30 ng L
−1
, however, unclear whether total or
dissolved concentrations; UNEP 2002). PCB concentrations
in two samples of seawater collected in the southern Aegean
Sea (close to Crete) was lower in 2006–2007, ΣPCB
7
=2.6
and 3.7 pg L
−1
,incontrastto7.5pgL
−1
at the Cretan site in
2012. PCB in two seawater samples collected in the northeast-
ern and central Aegean Sea 2006–2007 was somewhat lower,
7.3 and 13.8 pg L
−1
(Berrojalbiz et al. 2011), than that found in
2012 in the Thermaikos Gulf (19.6–33.4 pg L
−1
; Table S4b).
Dissolved ΣPCB
7
was also lower, 13.1 pg L
−1
,in1987in
surface seawater of the southern Aegean, Cretan and Ionian
Seas (Schulz-Bull et al. 1997). HCB is found consistently
higher by a factor of about 5 than in the northern Aegean
Sea in 2006–2007 (dissolved phase; Berrojalbiz et al. 2011).
β-andγ-HCH concentration at site 1b are also higher than in
2006–2007, namely by a factor of 3 and 5, respectively.
Concentration levels of OCPs, PCBs and PAHs in seawater
of the Thermaikos Gulf have exhibited a considerable de-
crease during the last two decades (Kamarianos et al. 2002).
Nevertheless, several PTSs have been recently detected in
sediments from Thermaikos Gulf including p,p′-DDE, α-
and β-HCH, PCBs (mainly the congeners 138, 101, 28 and
180; Terzopoulou and Voutsa 2011), PBDEs (Dosis et al.
2011), and PAHs (IKYDA 2010).
Contaminant patterns The ratio DDT/DDX, indicative for
aging, equals 0.37 in seawater of the Cretan coast, site 1b, and
much less, 0.01–0.05, in the Thermaikos Gulf. This may point
to some influence of long-range transported DDT in the south-
ern Aegean Sea as opposed to the Thermaikos Gulf environ-
ment. PAH and PBDE patterns in seawater are highly
consistent across all sites (Table S6b). PCB patterns in seawa-
ter are consistent, too, but less than in air (Table S6a, b).
However, there is also a difference in the PCB pattern along
the off-shore gradient. The OCP pattern at the remotesite 1b is
very different from the patterns found in the Thermaikos Gulf.
The ratio α-HCH/γ-HCH ranges 0.4–2.2 in seawater, lower
than in air. This is in line with the difference in Henry coeffi-
cients higher (in units of Pa m
3
mol
−1
)forα-thanγ-HCH.
Along the off-shore gradient α-/γ-HCH almost triples from
0.4 to 1.1, indicating minimal values in freshwater of the area.
This might be related to air–sea exchange of the isomers, not
effective in or close to the estuary.
Air–sea gas exchange
The direction of air–sea exchange was derived for three sites in
two areas, 1b (Crete), 2c and 2d (Thermaikos Gulf). The three-
ring PAHs ACE, FLN and PHE are found volatilisational (i.e.
upward net flux) in the Thermaikos Gulf (no measurement at
the Cretan coast) (Fig. 4). Such a result is not unexpected for
coastal waters in the vicinity of strong primary emissions and
had been observed before in coastal waters of the northeastern
USA (Lohmann et al. 2011) and even in the open southeastern
Mediterranean Sea in spring 2007 (Castro-Jiménez et al. 2012).
Some three- to four-ring parent PAHs, among them FLN, had
been reported to be close to phase equilibrium in the
Mediterranean and Black Seas (Castro-Jiménez et al. 2012).
Penta- and hexachlorinated PCBs are found with
volatilisational trends at site 2c, Michaniona in the
Thermaikos Gulf, and all seven indicator PCBs, except
PCB118, at site 1b, Selles Beach on Crete. They seem to be
close to phase equilibrium at site 2d in the Thermaikos Gulf.
PCB were concluded to be net volatilisational in the eastern
Mediterranean based on measurements in air in 2001–2002
and in seawater in the 1990s (18 congeners; Mandalakis et al.
2005) but close to phase equilibrium in the Aegean Sea in
2006–2007 (41 congeners; Berrojalbiz et al. 2014). HCB
and PeCB are found net volatilisational at all three sites.
HCB had been observed but close to phase equilibrium in
the Aegean Sea in 2006–2007 (Berrojalbiz et al. 2014). The
direction of air–water gas exchange of HCH isomers is found
depositional in the Thermaikos Gulf (Fig. 4). This is, to our
knowledge, the first observation of pentachlorobenzene fu-
gacities in European marine environments.
Among the PBDEs only BDE28 seems to approach phase
equilibrium (f
a
/f
w
=1–20 at the three sites; Fig. 4) while the
other congeners tested, BDE47, BDE66, BDE100 and
BDE99, were found to be depositional with f
a
/f
w
in the range
10
2
–10
4
(BDE66 and BDE100 at all sites, BDE47 at site 1b
on Crete) or even higher (BDE99 at all sites, BDE47 at the
Thermaikos Gulf sites), i.e. very far from phase equilibrium
(not included in Fig. 4).
Environ Sci Pollut Res
For some substances that are quickly equilibrated (within a
few days) in SR, i.e. HCH and three-ring PAHs, the fugacities
derived at the remote site 1b could not be related because, at
this site, the SR sample was collected 10 days after PAS sam-
ple collection. Assuming stable C
w
s (during these 10 days),
values of f
a
/f
w
for ACE, FLN and PHE and HCHs at site 1b
were indicated to be similar to those at the Thermaikos Gulf
sites. p,p′-DDE was found close to phase equilibrium.
Conclusions
The regional marine environment exposure to PTS was
characterised by the determination of the concentrations of
26 substances in near-ground air and 55 substances in surface
seawater. The set of substances addressed in air was reduced
as a consequence of calibration of the effective PAS sampling
volume Vbased on side-by-side AAS and PAS at one of the
sites (BAir^and BS2^). The comparison of the substance pat-
terns suggests that Vvalues may not be representative across
sites when PAHs significantly partitioning to the particulate
phase are included (FLT and PYR in this study). This is related
to the processes determining gas-particle partitioning of
semivolatiles, which are dependent on particulate phase chem-
ical properties. This is not likely relevant for PBDEs, for
which phase partitioning is expectedly less influenced by par-
ticulate phase components.
Distribution of HCB, HCHs and DDX in air is found to be
distributed fairly consistent. The urban to remote gradient of
PCBs is only about a factor of 2. PAHs and PCBs are observed
to be close to equilibrium or net volatilisational, as previously
observed or suggested in the region (Mandalakis et al. 2005;
Castro-Jiménez et al. 2012). HCB and PeCB are found net
volatilisational for the first time. No tendency is found that
f
a
/f
w
would be higher at the remote site. Instead, the fugacity
ratios of PCBs, DDE and HCB are very similar to those
derived for the more polluted Thermaikos Gulf sites. The data
basis is too sparse to conclude on long-term trends of the
ocean burdens of most pollutants addressed. However, a
long-term trend of increasing PCB seawater concentrations
is indicated in the southern Aegean Sea. This is notably re-
garding the fact that the emissions have been declining since
the 1970s, and the environmental burden in the region is ex-
pected to decline since the 1980s to 1990s (Lammel and
Stemmler 2012). It could be explained by decreasing trends
in other environmental compartments in the region (air, sedi-
ments) or advection (sea currents). More data, also from other
seasons, are needed to consolidate such a finding.
Acknowledgments We thank Giorgos Kouvarakis and Nikolas
Mihalopoulos, University of Crete, for on-site support. This research
was supported by the Granting Agency of the Czech Republic
(#312334), the Czech Ministry of Education (LO1214 and
LM2011028), by the European Social Fund (CZ.1.07/2.3.00/30.0037)
and the European Commission FP7 (#262254 ACTRIS).
Compliance with Ethical Standards No potential conflicts of interest
(financial or non-financial) exist.
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