ARTICLE IN PRESS

Atmospheric Environment 42 (2008) 29482958

www.elsevier.com/locate/atmosenv

Seasonal trends in vegetation and atmospheric concentrations of

PAHs and PBDEs near a sanitary landll
Annick D. St-Amanda, Paul M. Mayera, Jules M. Blaisb,
a

Department of Chemistry, University of Ottawa, 10 Marie-Curie, Ottawa, Ontario, Canada K1N 6N5
b
Department of Biology, University of Ottawa, 30 Marie-Curie, Ottawa, Ontario, Canada K1N 6N5
Received 1 July 2007; received in revised form 18 December 2007; accepted 20 December 2007

Abstract
Spruce needle and atmospheric (gaseous and particulate-bound) concentrations were surveyed near a sanitary landll
from February 2004 to June 2005. The inuence of several parameters such as temperature, relative humidity, wind speed
and direction, as well as increased domestic heating during the winter was assessed. In general, polybrominated diphenyl
ethers (PBDE) and polycyclic aromatic hydrocarbons (PAH) concentrations in spruce needles increased over time and
decreased following snowmelt with a minimum coinciding with bud burst of deciduous trees. Atmospheric concentrations
of PBDE and PAH, both particulate-bound and gaseous phase, were linked to daily weather events and thus showed more
variability than those in spruce needles. Highest PAH concentrations were encountered during the winter, likely reecting
increased emission from heating homes. Pseudo Clausius-Clapeyron plots revealed higher PBDE gaseous concentrations
with increasing temperature, but showed no correlation between PAH gaseous concentrations and temperature as this
effect was obscured by seasonal emission patterns. Finally, air mass back trajectories and local wind directions revealed
that particulate-bound PBDEs, along with both gaseous and particulate-bound PAHs were from local sources, whereas
gaseous PBDEs were likely from distant sources.
r 2007 Elsevier Ltd. All rights reserved.
Keywords: PBDE; PAH; Sanitary landll; Atmospheric; Vegetation; Temperature; Wind

1. Introduction
Both polybrominated diphenyl ethers (PBDEs)
and polycyclic aromatic hydrocarbons (PAHs) are
considered ubiquitous contaminants quantied in a
variety of environmental media throughout the
world, including very remote pristine ecosystems
(Hale et al., 2003; de Wit et al., 2006; Simcik and
Corresponding author. Tel.: +1 613 562 5800x6650;
fax: +1 613 562 5486.
E-mail address: jules.blais@uottawa.ca (J.M. Blais).

1352-2310/$ - see front matter r 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2007.12.050

Offenberg, 2006). PBDEs are used as ame-retardants in a variety of consumables (Alaee et al.,
2003) and increased usage is reected in rising
concentrations in the environment (de Wit et al.,
2006; Hale et al., 2006). It has also been demonstrated that PBDEs are toxic and persistent (de Wit,
2002; de Wit et al., 2006; Hale et al., 2006); recent
modeling studies have shown that the more volatile
congeners have a moderate long-range atmospheric
transport potential (Palm et al., 2002; Gouin and
Harner, 2003). As they are simply mixed with
materials during the manufacturing process and are

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A.D. St-Amand et al. / Atmospheric Environment 42 (2008) 29482958

not chemically bonded, PBDEs can leach in the

environment from consumer products (Alaee et al.,
2003; Osako et al., 2004). PAHs are also persistent
organic pollutants considered toxic and lipophilic,
with a wide range of volatility; acenaphthylene is
highly volatile (supercooled liquid vapor pressure of
4.14 Pa at 25 1C), whereas benzo(ghi)perylene has a
negligible vapor pressure (supercooled liquid vapor
pressure of 2.25  105 Pa at 25 1C) (Mackay et al.,
2006). Some are considered highly carcinogenic and
their potential impact on human health may be due
to their association with particulates (de Kok et al.,
2005). They can be released in the environment from
both natural (forest res and domestic wood
burning) and anthropogenic sources (industrial
activities, incomplete combustion of petroleum
and coal, and waste incineration) (Simcik and
Offenberg, 2006).
Sanitary landlls accumulate vast quantities of a
wide variety of consumables, including general and
hazardous wastes, electric and electronic equipment
and compost. Several studies have considered the
environmental fate and atmospheric release of
volatile organic compounds from landlls (Agrell
et al., 2004; Osako et al., 2004; Wichmann et al.,
2006). For semi-volatile organic compounds, like
polychlorinated biphenyls (PCBs), PAHs or
PBDEs, most studies focus on leachate concentrations and the impact of incineration facilities (Agrell
et al., 2004; Osako et al., 2004; Wichmann et al.,
2006). Studies have shown that PBDEs, along with
a wide array of brominated ame-retardants, are
found in waste electrical and electronic equipment
and that these can leach in the environment (Osako
et al., 2004). Furthermore, the presence of composting facilities could also contribute to the overall
release of semi-volatile organic compounds
(SVOCs) from sanitary landlls (Deportes et al.,
1995).
In this study, concentrations of PBDEs and
PAHs in environmental media were surveyed at a
sanitary landll for 16 months (February 2004June
2005). Atmospheric (gaseous and particulatebound) and spruce needle samples were collected
on a bi-weekly basis. Norway spruce (Picea abies)
was considered for this study since these conifers
have previously been shown to be efcient passive
air samplers for SVOCs (Schroter-Kermani et al.,
2006; St-Amand et al., 2007). Temporal trends of
PBDEs and PAHs in these three media were studied
and inuence of environmental and meteorological
parameters along with seasonal effects were as-

2949

sessed. These observations were then used to

identify emission sources and release patterns.
2. Experimental procedure
2.1. Sampling site and techniques
Samples were collected at the Trail Waste Facility
(situated at 451130 N, 751460 W), a sanitary landll
for the city of Ottawa, ON, Canada. This landll is
divided into two major areas: general waste and
compost. Hazardous waste, tires and appliances are
also collected and eventually sent elsewhere. It is
located close to a major highway in a mostly
residential agricultural area with little industrial
activity. During the study period, wind direction
was predominantly from the west at an average
wind speed of 3.62 m s1. Temperatures ranged
from 30.7 1C (15 January 2004) to 32.4 1C (11
July 2005) with lowest temperatures generally
encountered in January and highest temperatures
in July. Maximum precipitation for a 24 h period
was 135.4 mm on 9 September 2004, which was due
to a tropical storm remnant. Maximum snowfall for
a 24 h period was recorded on 7 March 2005
(15.4 cm) which contributed to a 40 cm maximum
snow cover observed between 8 and 10 March 2005.
Atmospheric and spruce needle samples were
collected bi-weekly from February 2004 to June
2005. Full details on sampling techniques have been
presented previously (St-Amand et al., 2007).
Briey, a high-volume air sampler was deployed
for approximately 18 h to collect particulates and
gaseous species, which were retained with a glass
membrane lter and polyurethane foam (PUF),
respectively. Filters were stored in solvent-cleaned
aluminum foil and PUFs were kept in solventcleaned jars. Norway spruce needles were collected
and placed in solvent-cleaned aluminum foil. All
samples were kept at 80 1C until extraction (less
than 3 months).
2.2. Extraction procedure
Details about the extraction procedures for
atmospheric and spruce needle samples are also
described previously (St-Amand et al., 2007). Before
extraction, the lters were dried and weighed to
determine total suspended particulate (TSP). All
samples were spiked with two surrogate standards
(BDE-77 and BDE-118) before extraction to
assess recovery. Filters and PUFs were extracted

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A.D. St-Amand et al. / Atmospheric Environment 42 (2008) 29482958

separately with hexane using a Soxhlet apparatus

for approximately 18 h and extracts were concentrated using a rotary evaporator. Dried spruce
needles were extracted using an accelerated solvent
extraction module (Dionex ASE-200) at 140 1C
using 1:1 hexane:dichloromethane mixture. Extracts
were concentrated using a TurboVap (Zymark) and
a 10% aliquot was removed for lipid determination.
These were then put through a small-deactivated
silica column, which was eluted with hexane and
concentrated to approximately 200 mL using a
TurboVap. Final extract volume was 500 mL for
all samples.
2.3. Instrumental analysis
An Agilent HP 6890 gas chromatograph coupled
with a quadrupole mass selective detector HP
5973N was used for all analyses. PBDEs were
analyzed using chemical ionization mass spectrometry (GCCIMS). Injections of 2 mL were made in
pulsed splitless mode at 280 1C. A fused-silica
capillary column (15 m  0.25 mm) coated with
0.25 mm chemically bonded HP-5MS phase (5%
phenyl methyl siloxane) was used. Initial oven
temperature was set at 120 1C, followed by an initial
ramp of 60 1C min1 to 180 1C and a second ramp of
25 1C min1 to 300 1C which was maintained for
5.20 min for a total run time of 11 min. Column
carrier gas helium was set at a constant ow of
1.1 mL min1 for lower PBDE congeners (tri to
hepta) to ensure optimal resolution between chromatographic peaks. This was increased to
3 mL min1 for BDE-209 analysis and the nal
temperature of 300 1C was kept for 10.20 min for a
total run of 16 min.
The mass spectrometry parameters were the same
for all PBDE congeners. The GCMS interface and
source were kept at 300 and 250 1C, respectively, to
ensure maximum sensitivity and methane was used
as reagent gas. The following mass fragments were
monitored in SIM mode: m/z 79 and 81, for
quantication and qualication of PBDEs, respectively, and m/z 404 for internal standard (octachloronaphthalene) monitoring. The following
PBDEs were separated and quantied: tri-BDE 17
and 28, tetra-BDE 47, 66, 71 and 77 (surrogate),
penta-BDE 85, 99, 100 and 118 (surrogate), hexaBDE 138, 153, and 154, hepta-BDE 183 and 190
and deca-BDE 209.
PAHs were analyzed using electron ionization
mass spectrometry (GCEIMS). Injections of 1 mL

were made in pulsed splitless mode at 280 1C. GC

separation was realized using the same column as
described above (with column guard). Initial oven
temperature was set at 150 1C and held for 2 min,
followed by a rst ramp of 10 1C min1 to 240 1C
and second ramp of 5 1C min1 to 300 1C, which was
held for 5 min. The GCMS interface was kept at
300 1C and the source at 150 1C. The following
fragments were monitored in SIM mode: m/z 152
for acenaphthylene (AceN), m/z 166 for uorene
(Flu), m/z 178 for phenanthrene (Phe) and anthracene (Ant), m/z 202 for pyrene (Pyr), m/z 228 for
benz(a)anthracene and chrysene (BaA+Chr), m/z
240 for chrysene-d12 (internal standard), m/z 252
for benzo(b)uoranthene and benzo(k)uoranthene
(BbF+BkF), and m/z 276 for indeno(123-cd)pyrene
(IndP) and benzo(ghi)perylene (BghiP). Benz(a)anthracene and chrysene as well as benzo(b)uoranthene and benzo(k)uoranthene were combined
because of poor peak resolution. Ratios of the
peak areas of the analytes and the internal standard
were used for quantication. Calibration curves constructed using 10 standards for PBDEs (05 pg mL1)
and ve standards for PAHs (00.1 ng mL1) gave
0.99 or higher coefcients of determination.

2.4. Quality control

All non-graduated glassware was triple-washed
with laboratory grade detergent, triple-rinsed with
distilled water, rinsed with ACS grade acetone and
hexane before placing in an oven at 200 1C for
several hours. Graduated glassware was washed as
described, but rinsed with Omnisolv grade acetone
and hexane and was not oven-dried. Blanks (PUFs,
lters, and ASE) were processed to check for
laboratory contamination and concentrations of
most compounds (PBDEs and PAHs) were below
detection limit; BDE-47 and -99 were found at very
low concentrations and thus the samples were not
blank corrected. PUF breakthrough artifacts were
also assessed by cutting PUFs in half and comparing contribution of the top and bottom halves.
Average total concentration breakthrough to the
second PUF half was generally less than 10% and
was highest for acenaphthylene (average below
30%). Sample recovery was evaluated for all
samples using two surrogate standards (BDE-77
and -118). Average recoveries for spruce needle,
lter and PUF samples were 70.975%, 86.377%,
and 89.078%, respectively. If recovery fell outside

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these ranges, samples were recovery corrected to

mean values.
Recovery was also evaluated on a compound basis
by spiking blanks with a low- concentration standard. For PBDEs these were found to be 93.874%
for spruce needle samples (n 6), 87.275% for lter
samples (n 3) and 83.574% for PUF samples
(n 9). For PAHs these generally ranged from 30%
to 80% for spruce needle samples (n 5), from 60%
to 110% for lter samples (n 5) and above 90% for
PUF samples (n 5). PAH sample concentrations
were adjusted accordingly. Method detection limits
were determined using both the standard deviation of
several injections (nX7) of a low-concentration
standard and the error of the regression. For PBDEs
detection limits ranged from 0.002 to 0.056 pg m3
for atmospheric samples (assuming a sample volume
of 800 m3), and 0.25 to 5.3 pg g1 for spruce samples
(assuming a sample mass of 8 g). For PAHs these
ranged from 0.001 to 0.007 ng m3 for atmospheric
samples and from 0.13 to 0.67 pg g1 for spruce
needles.
3. Results and discussion
3.1. PBDE and PAH spruce needle concentrations
Spruce needles showed gradual accumulation of
both PBDEs and PAHs starting at bud burst (as

2951

shown in Fig. 1). For PBDEs, total concentrations generally ranged from 210 to 9940 pg g1
dry weight with an average of 2370 pg g1. Table
1S presents a summary of spruce needle concentrations for selected PBDEs. Without BDE-209
total PBDE concentrations were much lower ranging from 20 to 3750 pg g1 with an average
920 pg g1 dry weight. It should also be noted that
BDE-71 was not detected in spruce needle samples.
Predominant PBDE congeners quantied in spruce
needles were BDE-209, 99 and 47 which account
for more than 85% of the total PBDE burden in
spruce needles (Fig. 1S) and reect current usage
of Penta and DecaBDE technical formulations
(Hale et al., 2003). PBDE vegetation congener
proles remained fairly constant throughout the
study period.
Total PAH spruce needle concentrations were
signicantly higher than PBDEs (paired t-test,
po0.05) ranging from 10.7 to 608 ng g1 dry weight
with an average 82.8 ng g1 and were within values
reported in the literature (Schroter-Kermani et al.,
2006). Table 1S also presents a summary of spruce
needle concentrations for selected PAHs. Contributing over 80% of the total PAH spruce needles
burden were benzo(b)uoranthene+benzo(k) uoranthene, benzo(a)pyrene and indeno(123-cd)pyrene
(Fig. 2S). PAH congener proles were also fairly
constant throughout the study period.

Fig. 1. Spruce needles total concentration of PAHs and PBDEs (ng g1 dry weight) from February 2004 to June 2005 (2003 and 2004
buds).

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PBDE spruce needle concentrations generally

increased during the warmer summer months
stabilizing in November. This trend is however;
largely inuenced by BDE-209 one of the predominant congeners present in spruce needles, and
lighter PBDEs show a more gradual increase.
PAH spruce needle concentrations increased slowly
starting at bud burst until November, at which
point there was a sudden increase in concentration.
This is most probably due to increased fuel
consumption for domestic heating at the arrival of
colder temperatures, causing higher PAH atmospheric concentrations (see below). Although a
similar increase can also be noted for PBDEs, this
is limited to a few data points, and applies
exclusively to BDE-209, which, as mentioned
previously, is the largest contributor to total PBDE
vegetation concentration. With the arrival of spring,
a decrease in total PBDE and PAH concentrations
is seen following snowmelt (February and March)
with a minimum at spring bud burst. Similar trends
have also been observed for DDT (and to some
extent HCHs) in pine needles (Kylin and Sjodin,
2003). This was suggested to be due to the
degradation and abrasion of the wax matrix during
the winter-to-spring transition. In fact, the winter
season brings forth stressful conditions for conifers,
such as low water apportionment, windy conditions,
and sun radiation. During winter cold temperature
progress and the protective layer on conifer needles
thin out. This layer can thin rapidly with the arrival
of spring, especially if this transition is dramatic,
such as a few days of elevated temperatures
(Larcher, 1996; Fitter and Hay, 2003). With the
arrival of spring, it has also been suggested
that PBDEs could be re-released from the melting
snowpack followed by subsequent deposition
onto available surfaces (Gouin and Harner, 2003).
The new leaves of the deciduous trees could offer
new deposition surfaces resulting in competitive
uptake.
3.2. PBDE and PAH atmospheric concentrations
As seen in Fig. 2, gaseous and particulate-bound
total PBDE concentrations were generally below 2
and 20 pg m3, and ranged from 0.36 to 6.9 pg m3
and 0.72 to 145 pg m3, respectively, and are
comparable to PBDE atmospheric concentrations
reported in the region (Butt et al., 2004; Wilford
et al., 2004). Table 2S presents a summary of the
atmospheric concentrations for selected com-

pounds. Volatile congeners were predominantly

found in the gaseous fraction, with BDE-28, -47
and -99 accounting, on average, for more than 80%
of the total concentration (Fig. 1S). PBDEs
associated to particulates generally had a higher
log KOA; BDE-183 and -209 were found exclusively
associated to particulates. BDE-209 contributed on
average 55% to the total PBDE particulate burden,
with BDE-47 and -99 also present in signicant
amounts (Fig. 1S). The omnipresence of BDE-47,
-99 and -209 in all media studied (spruce needles,
gaseous and particulate-bound) reects the current
usage pattern of PentaBDE and DecaBDE technical
PBDE formulations in North America (Hale et al.,
2003).
Atmospheric PAH concentrations were an order
of magnitude higher than those of PBDEs. As
shown in Fig. 2, total gaseous PAHs ranged from
244 to 3680 pg m3 (generally below 2000 pg m3)
while particulate-bound concentrations ranged from
28 to 1870 pg m3 (generally below 500 pg/m3) and
fell within values reported in the literature for
Canada (Sanderson et al., 2004). The three-ring
PAHs (acenaphthylene, uorene, phenanthrene,
and anthracene) constituted more than 90% of
the total gaseous concentrations. Almost all PAHs
were found in appreciable amounts in particulates,
except for acenaphthylene, uorene and anthracene
(Fig. 2S).
PBDE vegetation uptake occurs through both
particulate-bound and gaseous depositions. The
relative importance of these processes is affected
by their log KOA and particulate-gas partitioning
behavior (St-Amand et al., 2007).
Particulate-gas partitioning was assessed by
calculating KP for each sampling sessions as
described by
KP

C P =TSP
,
CG

(1)

where CP and CG are the particulate-bound and

gaseous concentrations, respectively (pg m3) and
TSP is the total suspended particulates (mg m3).
Measured TSP values are presented in Fig. 2.
As shown in Fig. 3, particulate-gas partitioning of
both PBDEs and PAHs were strongly correlated
to log KOA (po0.001), as the proportion of
SVOCs associated to particulates increased with
decreasing volatility. On average, penta-BDE and
higher congeners (log KOA above 11) were mostly
associated to particulates (above 70%) which
corroborates previous results (Shoeib et al., 2004).

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2953

Fig. 2. Atmospheric total PBDE and PAH concentrations (pg m3) and total suspended particulates (mg m3) for each sampling session.

PAHs containing at least four rings with a log KOA

above 10 (benzo(a)anthracene+chrysene, benzo(b)uoranthene+benzo(k)uoranthene, benzo(a)pyrene,
indeno(123-cd)pyrene, and benzo(ghi)perylene) were
also found predominantly associated to particulates

(average also above 70%). This corroborates

other studies, except for benzo(a)anthracene+
chrysene, which has been found to split more evenly
between the gas phase and particulates (Su et al.,
2006).

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2954

3.3. Seasonal variations in atmospheric PBDE

concentrations

Fig. 3. Particulate-gas partitioning of PBDEs and PAHs studied.

Individual compounds are indicated. Error bars: standard error
of the mean (n 36 PBDEs and n 35 PAHs).

Gaseous concentrations of PBDEs, although

relatively low, were generally higher in the summer
and were signicantly correlated with temperature
(po0.001) (Table 1). Pseudo ClausiusClapeyron
plots were constructed and results are presented in
Table 2, as well as Fig. 3S, which illustrates the
results for BDE-28, -47, -99 and -153. For most
PBDEs, the natural logarithm of partial pressure
correlates signicantly (po0.05) with the reciprocal
temperature. Exceptions are BDE-17, -85 and -183
and this may be due to their very low concentrations
in the gas phase, which very often were below
detection limit. Clausius-Clapeyron plots can also
be used to calculate air-surface exchange enthalpies,
if the system considered is at equilibrium. These

Table 1
Calculated p-values for the correlation of total PBDE and PAH gaseous and particulate-bound concentrations with meteorological
parameters
PBDE

Meteorological parameters

Temperature (K)
Relative humidity (%)
Air masses backward trajectories (categorical)
Air masses backward trajectories (numerical)
Wind direction (categorical)
Wind direction (numerical)
Wind speed (km/h)

PAH

Gaseous

Particulate-bound

Gaseous

Particulate-bound

0.000*(+)
0.953
0.001*
0.048*
0.353
0.283
0.423

0.064
0.905
0.045*
0.010*
0.222
0.004*
0.652

0.184
0.110
0.771
0.471
0.005*
0.002*
0.189

0.001*()
0.048*()
0.956
0.587
0.311
0.113
0.457

Presence of an asterisk indicates signicant correlation (po0.05). Sign of correlation is also indicated.

Table 2
Summary of regression slopes, correlation coefcients and p-values from pseudo Clausius-Clapeyron plots used to calculate enthalpies for
selected PBDEs
Compound

Slope

R2

p-values

DHcalc (kJ/mol)

DHVAPa (kJ/mol)

DHOAb (kJ/mol)

BDE-17
BDE-28
BDE-47
BDE-66
BDE-85
BDE-99
BDE-100
BDE-138
BDE-153
BDE-154
BDE-183

6.44
5.50
4.83
4.76
2.97
2.83
3.33
5.27
2.92
2.24
2.86

0.52
0.59
0.72
0.43
0.19
0.42
0.45
0.28
0.18
0.12
0.18

po0.5
po0.001
po0.001
po0.001
po0.1
po0.001
po0.001

po0.01
po0.05
po0.1

53.5712.4
45.876.6
40.174.2
39.579.6
24.7711.8
23.574.8
27.775.3
43.8725.0
24.3711.4
18.6711.2
23.8713.0

79.7
94.6
97.8

108.0
102.0
118.5
110.0
113.0
118.0

72.8
74.5
97.0
107.0
102.0
91.1
105.0

98.2
94.4
89.5

(Tittlemier et al., 2002).

(Harner and Shoeib, 2002).

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2955

were calculated using their respective pseudo

Clausius-Clapeyron plots regression slopes and were
smaller than DHOA and DHVAP reported in the
literature (Harner and Shoeib, 2002; Tittlemier
et al., 2002). However, it has been suggested by
Hoff et al. (1998) that ClausiusClapeyron plots
and corresponding slopes can also be used to assess
the input of SVOCs from long-range transport and
local volatilization. Slopes similar to DHOA or
DHVAP slopes would indicate that local sources
are important, whereas shallower slopes would
indicate that long-range transport is the dominant
contribution process to the gaseous concentration
(Hoff et al., 1998). In this study, the Clausius
Clapeyron plots drawn for PBDEs present slopes
(and pseudo enthalpies) that are shallower than
those predicted by the known vaporization enthalpies. Furthermore, slopes for lighter PBDEs are
highly linear (high R2, low p-values) thus demonstrating that one process is dominant. These
observations indicate that long-range transport is
the dominant process contributing to gaseous
concentrations.
Particulate-bound PBDE concentrations were
generally highest in the fall and spring seasons and
were not signicantly correlated to temperature
(Table 1). The lower concentrations encountered in
winter could be due to the atmospheric scavenging
by snowfall, and could be re-released during the
snowmelt, thus causing an increased concentration
in air during the spring snowmelt (Gouin and
Harner, 2003).

than 0.1 suggesting combustion sources. In fact,

particulate-bound PAH concentrations were generally higher in the colder winter months as domestic
heating increases (Fig. 2), and correlated signicantly and negatively with temperature (po0.001)
(Table 1). Furthermore, ve and six rings PAHs
have been linked to heating emissions (Schauer
et al., 2003) which constituted, on average, 23 of
particulate-bound PAH burden.
PAH gaseous concentrations were found to be
more variable and were not signicantly correlated
with temperature (Table 1). For gaseous PAH
concentrations, the above diagnostic ratio was
lower than 0.1 from February to mid-July 2004,
then higher than 0.1 until December, when it
decreased below 0.1 until the end of April 2005,
indicating both pyrogenic and petroleum origins.
Pseudo ClausiusClapeyron plots were also constructed, even though gaseous acenaphthylene was
the only PAH to correlate signicantly with 1000/T,
though positively (R2 0.31, po0.001). This may
be due to an increase in PAH emissions encountered
at colder temperatures. Other gaseous PAHs did not
correlate signicantly with temperature. Although
higher gaseous concentrations are usually expected
at higher temperatures, it is possible that the
increase emission during the winter season conceals
this effect. Pyrene is used in Fig. 3S to represent a
typical PAH.

3.4. Seasonal variations in atmospheric PAH

concentrations

To distinguish between long-range and local

emissions and meteorologically related effects, and
explain some of the variability encountered in
atmospheric concentrations for both PBDEs and
PAHs, back trajectories using HYSPLIT (Draxler
and Rolph, 2003) and wind roses were constructed
for each sampling sessions. Air mass back trajectories were computed for 96 h starting at the end of
each sampling sessions. Their overall trajectories
were then categorized according to 16 cardinal
points: N, ENE, NE, NEE, E, ESE, SE, SSE, S,
SSW, SW, WSW, W, WNW, NW, and NNW. Wind
roses were compiled using hourly weather data
collected at the Ottawa International Airport for the
duration of the sampling period. Predominant wind
directions were also categorized according to 16
cardinal points. A thorough statistical analysis
using SYSTAT was performed to study the impact
of air masses and wind direction. Both were not

Seasonal trends for gaseous and particulatebound PAH concentrations are not as straightforward since meteorological effects are combined to
usage patterns. Prior investigations have used mass
concentration ratios (diagnostic ratios) to identify
possible atmospheric PAH sources (Schauer et al.,
2003; Blasco et al., 2006). For example, the ratio of
concentrations of anthracene/(anthracene+phenanthrene) can be used to assess possible combustion
(incomplete combustion of organic matter) versus
petroleum sources (geochemical alterations of organic matter). If this ratio is higher than 0.1 then
combustion sources dominate, whereas a ratio
lower than 0.1 indicates prevalence of petroleum
sources (Blasco et al., 2006). For particulate-bound
PAH concentrations this ratio was always higher

3.5. Other meteorological effects and emissions

sources

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A.D. St-Amand et al. / Atmospheric Environment 42 (2008) 29482958

only dened categorically as above, but also

numerically (degrees). These were also considered
with other meteorological parameters such as
temperature, relative humidity and wind speed to
assess their impact (Table 1).
Gaseous PBDE concentrations were found to be
linked to long-range air masses. In general, air
masses deriving from northerly directions resulted
in lower PBDE gaseous concentrations, whereas
those deriving from the west and south had high
PBDE gaseous concentration. These were found to
correlate signicantly with air mass directions both
categorically (po0.001) and numerically (po0.05).
These observations demonstrate that gaseous
PBDEs found at the sanitary landll could be from
long-range transport, thus corroborating the observations made using pseudo ClausiusClapeyron
plots. PBDE gaseous concentrations did not correlate signicantly with local wind direction, relative
humidity, and wind speed.
Particulate-bound PBDE concentrations correlated signicantly with local wind direction (numerical po0.005) and to a lesser extent with air mass
back trajectories. Previous studies indicate that
SVOCs in the gas phase should travel farther and
possibly undergo long-range atmospheric transport
to a larger extent than compounds associated to
particulates which are more prone to deposit onto
available surfaces (Palm et al., 2002; Shoeib and
Harner, 2002). Winds from the north, west and east
were linked to highest particulate-bound SVOCs
concentrations demonstrating the possible impact of
local sources such as the city center and the
composting, electronic refuse and general waste
areas at the sanitary landll which are situated
north, west and east, respectively, from the sampling station. Temperature, relative humidity and
wind speed did not correlate signicantly with the
particulate-bound PBDE concentrations; however,
particulate-gas partitioning of most PBDEs was
shown to be temperature dependent (most compounds po0.001) (Fig. 4S found in Appendix). As
temperature decreases, exchange is thus shifted
towards particulates reducing the overall mobility
and long-range transport potential.
Gaseous PAH concentrations were found to
correlate signicantly with local wind direction
(po0.005), possibly indicating a local source. In
general, winds blowing from the north and east
showed highest gaseous PAH concentrations corresponding with the general direction of the highway
and suburbs of the city. No signicant correlations

were found with temperature, relative humidity, air

mass back trajectories or wind speed. Particulatebound PAH concentrations did not correlate
signicantly with local wind direction, air mass
back trajectories or wind speed (p40.05). Particulate-bound PAH concentrations correlated negatively with temperature (po0.001) which may be
due to an increased association with particulates
encountered at lower temperatures (as seen with the
vant Hoff plots in Fig. 4S). A signicant correlation
was also observed between PAH concentration and
relative humidity (po0.05).
It is difcult to study the possible trends in
concentrations in environmental media for PAHs
by only looking at meteorological effects, without
considering usage patterns and potential emission
sources. Not only there is a possible inuence from
temperature, wind direction may also play an
important role in the concentration of SVOCs as
they transport contaminants from the sources to the
sampling site. These parameters may inuence the
particulate-bound and gaseous concentrations with
greater impact than the spruce needle concentrations as SVOCs are accumulated through time in
spruce needles and thus a sudden short-lived rise
in atmospheric concentrations may not be reected
in the spruce needle.
4. Conclusions
This study was designed not only to survey PBDE
and PAH concentrations in the environment at a
sanitary landll, but also to consider the inuence of
temperature, wind direction and emissions on these
concentrations. Seasonal effects were noted in all
media, which were due to weather related phenomena and/or usage patterns (higher concentration in
air during the colder months, due to increased
domestic heating and fuel consumption). Pseudo
ClausiusClapeyron plots showed a high correlation
between gaseous concentration and temperature for
PBDEs; corresponding slopes were shallower than
those predicted from known DHOA or DHVAP values
thus indicating that long-range transport is the
dominant process contributing to gaseous concentrations. Pseudo ClausiusClapeyron plots failed to
show a temperature effect for PAHs because they
were overshadowed by increased emission to air
during the colder months. Finally, using statistical
analysis with air mass back trajectories, wind roses
and meteorological parameters, it was possible to
demonstrate that particulate-bound PBDEs, as well

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A.D. St-Amand et al. / Atmospheric Environment 42 (2008) 29482958

as particulate-bound and gaseous PAHs were from

local sources (sanitary landll, highway, and suburbs), whereas gaseous PBDEs were mainly from
long-range transport.
Acknowledgments
A.D.S. acknowledges the following: the Natural
Sciences and Engineering Research Council of
Canada, the Ontario Graduate Scholarships in
Science and Technology and the University of
Ottawa for the nancial support; and H. Shaw for
the help with sample preparation. P.M.M. and
J.M.B. thank the Natural Sciences Research Council of Canada for continuing support. The authors
thank the city of Ottawa for access to sampling site
and the NOAA Air Resources Laboratory (ARL)
for the provision of the HYSPLIT transport and
dispersion model used in this publication.
Appendix A. Supplementary materials
The online version of this article contains additional supplementary data. Please visit doi:10.1016/
j.atmosenv.2007.12.050

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