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Distribution of Polycyclic Aromatic Hydrocarbons in Urban Stormwater in Queensland Australia 2010 Environmental Pollution
Distribution of Polycyclic Aromatic Hydrocarbons in Urban Stormwater in Queensland Australia 2010 Environmental Pollution
Distribution of Polycyclic Aromatic Hydrocarbons in Urban Stormwater in Queensland Australia 2010 Environmental Pollution
Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol
School of Urban Development, Queensland University of Technology, GPO Box 2434, Brisbane QLD 4001, Australia
Chemistry Discipline, Queensland University of Technology, GPO Box 2434, Brisbane QLD 4001, Australia
The presence of organic carbon on impervious surfaces and rainfall duration plays a dominant role in the distribution of PAHs in urban
stormwater.
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 18 February 2010
Received in revised form
8 June 2010
Accepted 12 June 2010
This paper reports the distribution of Polycyclic Aromatic Hydrocarbons (PAHs) in wash-off in urban
stormwater in Gold Coast, Australia. Runoff samples collected from residential, industrial and commercial
sites were separated into a dissolved fraction (<0.45 mm), and three particulate fractions (0.45e75 mm,
75e150 mm and >150 mm). Patterns in the distribution of PAHs in the fractions were investigated using
Principal Component Analysis. Regardless of the land use and particle size fraction characteristics, the
presence of organic carbon plays a dominant role in the distribution of PAHs. The PAHs concentrations
were also found to decrease with rainfall duration. Generally, the 1- and 2-year average recurrence
interval rainfall events were associated with the majority of the PAHs and the wash-off was a source
limiting process. In the context of stormwater quality mitigation, targeting the initial part of the rainfall
event is the most effective treatment strategy. The implications of the study results for urban stormwater
quality management are also discussed.
2010 Elsevier Ltd. All rights reserved.
Keywords:
PAHs
Pollutant wash-off
Urban water quality
Rainfall simulation
Stormwater pollution
1. Introduction
Many urban areas around the world are currently experiencing
water scarcity due to population growth and industrialisation. In
particular, parts of Australia have experienced acute water shortage
in the past ve years (Hurlimann and Dolnicar, 2010; Williams,
2010). Under these circumstances, stormwater runoff can be
considered as a potential water source for potable and non-potable
use in order to strengthen the long-term sustainability of urban
areas. Unfortunately, urban stormwater runoff is a signicant nonpoint pollutant source as it acts as the medium for the transport of
a wide variety of pollutants and plays a key role in the degradation
of aquatic environments in urban areas. Researchers such as
Haiping and Yamada (1998) found that the pollution loading in
urban stormwater can be appreciably higher than treated domestic
sewage. Among the various pollutants, substances such as Polycyclic Aromatic Hydrocarbons (PAHs), which are detrimental to
human and ecosystem health are commonly found in urban
stormwater runoff (Estebe et al., 1997).
* Corresponding author.
E-mail address: g.ayoko@qut.edu.au (G.A. Ayoko).
0269-7491/$ e see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2010.06.015
The study sites were in the Gold Coast region, which is located south of the
Queensland State capital, Brisbane, Australia. Site 1 was an access road (Millswyn
Crescent) located in a typical urban residential area (Residential A) with detached
2849
Table 1
Priority PAHs as listed by US EPA together with their aqueous solubilities (adapted
from Manoli and Samara, 1999).
PAH compound
Solubility [mg/L]
Naphthalene, NAP
Acenaphthene, ACE
Acenaphthylene, ACY
Fluorene, FLU
Anthracene, ANT
Phenanthrene, PHE
Fluoranthene, FLA
Benzo[a]anthracene, BaA
Benzo[b]uoranthene, BbF
Benzo[k]uoranthene, BkF
Chrysene, CHR
Pyrene, PYR
Benzo[a]pyrene, BaP
Dibenzo[a,h]anthracene, DbA
Benzo[ghi]perylene, BgP
Indeno[1,2,3-cd]pyrene, IND
32
3.4
3.93
1.9
0.05e0.07
1.0e1.3
0.26
0.01
e
e
0.002
0.14
0.0038
0.0005
0.00026
e
specied by the US EPA (1991). The particulate fractions (0.45e75 mm, 75e150 mm
and >150 mm) were extracted using ultrasonication. Ultrasonication was chosen due
to the reduced extraction time compared to methods such as Soxhlet extraction. The
technique used is outlined in US EPA Method 3550 (US EPA, 1986). However, the
method does not specify the preferred solvent or the extraction time. Guerin (1999)
found that a mixture of dichloromethane (DCM) and acetone provided the most
efcient extraction, and that 1 h was sufcient for the extraction of 2- and 3-ring
PAHs. After this time, the recoveries decreased due to loss by volatilisation. Zhou and
Maskaoui (2003) successfully extracted the 16 priority PAHs using two 30 min
ultrasonication intervals. Therefore, in the current study, a DCM:acetone (3:1) mix
was used as the solvent and three 20 min extractions by ultrasonication was
employed.
12 mL of DCM:acetone (3:1) were used in each extraction interval. After each
extraction, the extract was transferred to a 100 mL glass beaker. The combined
extract was ltered into a 50 mL glass beaker using a GF/C glass microbre lter
(Whatman) which was puried by column chromatography using activated silica gel
and sodium sulphate (Na2SO4). The silica gel and Na2SO4 were activated in a furnace
at 100 C for 24 h and allowed to cool to room temperature in a vacuum desiccator
prior to use. The clean-up process removed any interfering compounds. Following
purication, the PAH extract was concentrated under vacuum to less than 5 mL
using a rotary evaporator (35 C temperature) and further concentrated to
approximately 0.5 mL using a gentle stream of ultra pure nitrogen gas. The samples
were then analysed using a HP5972 Gas Chromatograph e Mass Spectrometer
(GCeMS) which was calibrated using deuterated PAH internal standards obtained
from SigmaeAldrich.
2.5. Data analysis
2.5.1. Descriptive statistics analysis
The mean and standard deviation of the primary water quality parameters
obtained for the three study areas were estimated using descriptive statistics. These
parameters provided an insight into the trends and patterns of variation in water
quality with land use. Furthermore, the results derived also provided information
that would underpin the outcomes from the more detailed data analysis.
2.5.2. Multivariate statistical analysis
Several recent studies (see for example Settle et al., 2007 and references therein)
have shown that multivariate statistical techniques are useful tools for the analysis
of data with large numbers of variables and objects. Consequently, Principal
Component Analysis (PCA) was carried out on the data using MatLab software
developed by Kramer (1993). This data analysis method for example has been
successfully used for process identication in river water quality data (Petersen
et al., 2001), identication of parameter relationships of lake polluted sediments
(De Bartolomeo et al., 2004) and investigation of relationships between heavy
metals and suspended solids in urban stormwater runoff (Herngren et al., 2005b).
Nevertheless, its application to urban stormwater quality research has been limited.
Each object (wash-off samples in this research) has a score on each Principal
Component (PC), and each variable is characterised by a loading or weighting on
each PC. The PCs are extracted in such a way that the rst PC (PC1) describes most of
the data variance, and the second (PC2) describes the second highest amount of data
variance and so on. The advantage of this method is that most of the data variance is
usually described by the rst few PCs. In this study, the appropriate number of
principal components (PCs) were estimated from a Scree plot (Cattell, 1966), and the
reduced data were presented as biplots, which show the relationships among the
objects and the variables.
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Table 2
Mean concentrations [mg/kg] in the different particle size classes in wash-off samples at the study sites.
PAH
NAP
ACY
ACE
FLU
PHE
ANT
FLA
PYR
BaA
CHR
BbFa
BaP
IND
DbA
BgP
TOC (DOC)
TSS (TDS)
<0.45 mm
0.45e75 mm
75e150 mm
>150 mm
Res.
Ind.
Com.
Res.
Ind.
Com.
Res.
Ind.
Com.
Res.
Ind.
Com.
0.05
0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
<0.01
<0.01
7.45
77.78
0.07
0.02
0.02
0.01
<0.01
<0.01
0.01
<0.01
0.01
<0.01
<0.01
0.04
<0.01
<0.01
0.01
7.18
174.54
0.13
0.04
0.02
0.01
0.02
0.02
0.03
0.01
0.02
0.01
0.01
0.06
0.01
<0.01
0.01
5.54
26.67
0.94
0.12
0.07
0.08
0.12
0.09
0.18
0.14
0.13
0.10
0.12
0.11
<0.01
<0.01
<0.01
1.02
29.29
1.91
0.19
0.28
0.08
0.12
0.05
0.17
0.20
0.12
0.24
0.07
0.11
0.02
<0.01
0.02
0.38
35.75
5.18
0.55
0.21
0.30
0.55
0.11
0.36
0.32
0.38
0.20
0.39
0.26
0.09
0.04
0.04
1.35
19.14
1.01
0.12
0.13
0.11
0.16
0.15
0.20
0.17
0.18
0.16
<0.01
0.17
<0.01
<0.01
<0.01
1.07
8.43
1.77
0.20
0.22
0.05
0.06
0.06
0.09
0.07
0.09
0.10
0.04
0.07
<0.01
<0.01
0.02
0.60
14.87
1.58
0.37
0.11
0.09
0.23
0.03
0.16
0.07
0.18
0.14
0.14
0.13
0.03
<0.01
0.03
0.32
19.67
0.93
0.12
0.07
<0.01
<0.01
<0.01
0.18
0.15
0.06
<0.01
0.12
0.13
<0.01
<0.01
<0.01
2.50
5.05
0.71
0.11
0.05
0.03
0.01
<0.01
0.08
0.07
0.06
0.07
0.02
0.08
<0.01
<0.01
<0.01
1.28
15.96
0.99
0.22
0.08
0.07
0.05
0.05
0.11
0.14
0.08
0.10
0.09
0.09
0.07
0.02
<0.01
1.31
47.87
IC
Cluster 3
TSS
P C A 2 (1 2 . 8 % )
TOC
Cluster 2
EC
0
NAP pH
DbA
FLA
PYR
BgP
ANT
IND
BaP
ACY
ACE
FLU
BaA
CHR
BbF
PHE
-1
TDS
Loadings of 16 PAHs
-2
Cluster 1
-3
-4
-5
10
PCA 1 (68.9%)
Fig. 1. Biplot derived from applying PCA to the complete dataset (128 objects),
showing three distinct clusters on PC1 and PC2.
2851
2852
the data regardless of the land use. At the industrial and residential
sites particularly, PVP (particulate volume percentage) and INT
(rainfall intensity) vectors were almost independent of each other
suggesting that higher intensity rainfall had no effect on the
percentage of dissolved solids (compared to suspended solids) in
the runoff. At the commercial and industrial sites in particular,
rainfall duration (DUR) was generally opposed to the PAHs in the
biplot. This suggests that the PAH concentrations generally
decreased with increased duration, possibly due to dilution in the
runoff.
Several of the PAHs (e.g. BaP and BgP) detected in the dissolved
fraction at the commercial and industrial sites had concentrations
above their aqueous solubilities (Table 2). This generally occurred
when the PAHs were correlated with DOC as can be seen in Fig. 2,
thus conrming the occurrence of the solubility enhancement
effect described by Warren et al. (2003) and discussed above.
Correlations among the PAHs and different rainfall events
(where 1y10 indicates 1 year ARI (Average Recurrence Interval)
10 min duration event) is also evident in the biplots. Consequently,
this highlights the need to separate urban water quality mitigation
from urban water quantity mitigation measures. Measures instigated to reduce the impact of stormwater quantity may prove to be
inefcient in removing the dissolved fraction of PAHs.
2853
2854
The vectors for rainfall duration and the PAHs in the biplot are
generally in opposite directions suggesting that the longer the
duration of the rainfall events, the less the PAHs concentrations.
Therefore it can be concluded that PAHs wash-off with stormwater is a pollution source limiting process. In the context of
stormwater quality mitigation, targeting the initial part of the
rainfall event will be an effective strategy. This conclusion is
further strengthened by the fact that the 1- and 2-year ARI
rainfall events were associated with majority of the PAHs and
hence, these are the most important events in terms of water
quality treatment.
3.2.3. Particle size fraction 75e150 mm
As observed for the particle size fraction 0.45e75 mm, most of
the data variance in this particle size fraction was accounted for
using three principal components. However, the third component
did not provide additional information on the distribution of PAHs.
Hence, PC1 and PC2 were used to explore the data.
Interestingly, the relationships observed among PAHs, TOC
and IC in this particle size fraction (Fig. 4) were similar to those
identied in the 0.45e75 mm fraction. Hence, it is postulated that
similar processes are governing the distribution of PAHs in the
0.45e75 mm and 75e150 mm particle size fractions. Furthermore,
regardless of the land use characteristics, 1- and 2-year ARI
rainfall events were again associated with the majority of PAHs.
Therefore, in the context of stormwater quality mitigation, the
4. Conclusions
In this paper, the distribution of PAHs in different particle size
fractions in urban stormwater from three different land uses in the
Gold Coast, Australia is discussed. The major ndings from the
study are outlined below:
Regardless of the land use and rainfall characteristics, the
highest PAH concentrations occurred in the particles between
0.45 mm and 150 mm;
Up to 85% of the total particle volume distribution was found in
the 0.45e75 mm size class conrming that high PAH concentrations in combination with high particle volume distribution
give rise to a signicant PAHs load in this particle size fraction;
Several PAHs were consistently found to be in concentrations
above their aqueous solubilities which was attributed to the
dissolved colloidal organic carbon present;
Rainfall intensity and duration did not signicantly inuence
the distribution of PAHs into different particle size fractions;
and
pH and EC could potentially inuence PAHs sorption to
particulates.
The primary implications of these ndings in relation to urban
stormwater quality treatment are:
The inuence of parameters such as rainfall intensity, duration
and land use characteristics on PAH distribution is less significant than those of parameters such as organic carbon, EC and
to a limited extent IC;
PAH concentrations generally decreased with rainfall duration
suggesting that the pollutants become diluted, thus conrming
that the wash-off with stormwater is a source limiting process;
The 1- and 2-year ARI rainfall events were associated with
majority of the PAHs and hence, these are the most important
events in terms of water quality treatment;
PAHs adsorbed to ne particles (<150 mm) are easily transported by urban stormwater. Consequently they pose a signicant threat to the quality of receiving waters. Hence, structural
devices used for water quality improvement should have the
capability to remove this specic particle size fraction;
In the context of stormwater quality mitigation, targeting the
initial part of the rainfall event will be the most effective
treatment strategy: and
Strategies undertaken to improve stormwater quality should
not be heavily inuenced by rainfall characteristics such as
rainfall volume, as often is the case when water quantity and
water quality treatment measures are combined.
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