Atmospheric Research 124 (2013) 6172

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Atmospheric Research
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Contribution of ship emissions to the ne particulate in the

community near an international port in Hong Kong
P.S. Yau a, S.C. Lee a,, Y. Cheng a, b, Y. Huang a, S.C. Lai a, c, X.H. Xu a
a
Department of Civil and Environmental Engineering, Research Center for Environmental Technology and Management, The Hong Kong Polytechnic University,
Hung Hom, Hong Kong
b
Department of Environmental Science and Technology, School of Human Settlements and Civil Engineering, Xi'an Jiaotong University, No.28 Xianning West Road,
Xi'an, Shanxi, 710049, China
c
College of Environmental Science and Engineering, South China University of Technology, Guangzhou, China

a r t i c l e i n f o a b s t r a c t

Article history: Fine particulates from ship exhaust are proved to be harmful to human health. To better
Received 11 May 2012 understand the impact of ship emissions on the particulate matter (PM) level of port-side
Received in revised form 30 November 2012 residential areas, fine particulates (PM2.5) were collected near Kwai Chung and Tsing Yi
Accepted 18 December 2012 Container Terminals (KTCT) in Hong Kong during August 2009 to March 2010. The average
PM2.5 concentration was 30.5 g/m3. The contribution of ship emissions on fine particulates
Keywords: near the container port was demonstrated by source apportionment. By positive matrix
Ship emission factorization (PMF) analysis, eight potential sources, i.e., residual oil (RO) combustion, marine
Source apportionment diesel oil (MDO) combustion, vehicle emission, coal combustion, incineration, crustal and
PMF
sea-salt, secondary sulfate and secondary nitrate were identified. Among the identified
Fine particulate
sources, RO combustion and MDO combustion were regarded as ship emissions and accounted
Container port
for 12% and 7% of PM2.5 respectively. An estimate of 1.8 g/m3 (6%) of secondary sulfate
corresponded to 3.6 g/m 3 of primary fine particulates from RO combustion. Together with
primary PM emitted from ships, the total ambient PM2.5 mass associated with ship emissions
at the sampling site was 7.6 g/m 3 (25%).
2013 Elsevier B.V. All rights reserved.

1. Introduction
Shipping is the major transportation mode of international
trade but ship emissions keep increasing the burden on air
pollutants levels especially in coastal areas. Numerous studies
have demonstrated the adverse effect on human health of the
emissions from residual oil (RO) combustion which takes place
in ship engine (Mudway et al., 2004; Roberts et al., 2003). The
particulate matter (PM) from ship exhaust is dominated by
respirable-sized particles (Lyyranen et al., 1999), which has
been widely investigated and proved to be harmful to human
health (Davidson et al., 2005; Pope and Dockery, 2006;
Schwarze et al., 2006). Along with particle size, chemical
composition also influences the toxicity of PM (Anderson,
Corresponding author. Tel.: +852 2766 6011; fax: +852 2334 6389.
E-mail address: ceslee@polyu.edu.hk (S.C. Lee).
2000). It was demonstrated that nickel and vanadium, the trace
markers of aerosols from fuel oil combustion, were positively
correlated with human cardiovascular and respiratory diseases
that potentially increase PM risk on human health (Dominici
et al., 2007; Zhang et al., 2009). In addition to increasing
morbidity, ship emissions are associated with increased
mortality. It has been assessed that 60,000 premature deaths
have been induced globally by shipping-related PM emission
annually (Corbett et al., 2007). Pollution resulting from the
combustion of sulfur-rich fuels has been observed to affect
death rates, especially respiratory and cardiovascular deaths
(Hedley et al., 2002).
Hong Kong port is a world-class shipping centre with a
high density of logistics traffic. It has been in the top three
busiest container ports in the world for over ten years in
terms of the number of container throughput handled. In
the past decade, the total container throughput handled in

0169-8095/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.atmosres.2012.12.009
62 P.S. Yau et al. / Atmospheric Research 124 (2013) 6172
Hong Kong increased by 30% from 16,211,000 TEUs (20-foot
equivalent units) in 1999 to 21,040,000 TEUs in 2009 (Marine
Department, 2010). Kwai Chung and Tsing Yi Container
Terminals (KTCT) is the major port facility in Hong Kong and
responsible for over 70% of the containers handled in the
territory. However, different from many other overseas ports
which are distant from residential areas, KTCT is in the
proximity of the densely populated residential area. In
consequence, the emissions from ships with huge engines
running on heavy fuel oil may seriously affect local communi-
ties. According to the emission inventory from the HKEPD,
416 ton of respirable suspended particulate (RSP), i.e., PM10,
emitted from ship emissions contributed to 7% of the total RSP
emissions in Hong Kong (HKEPD, 2008). While the RSP
emissions from other sources, such as power generation and
vehicles, keep declining, an increasing trend has been observed
for ship emissions. Receptor modelings of aerosols in some
specific sites such as residential areas and roadsides have been
studied (Guo et al., 2009; Yuan et al., 2006), however; PM
source apportionment near to shipping port has not been
conducted. For overseas regions, PM source apportionments
have been studied for the ports at Cork, Seattle, and Tarragona
(Alastuey et al., 2007; Healy et al., 2010; Minguillon et al.,
2008).
Receptor models are commonly applied to evaluate the
contributions of the PM sources at the receptor sites using
multivariate measurements of particle chemical and physical
properties (Watson et al., 2002). There are various kinds of
receptor models, including chemical mass balance (CMB),
positive matrix factorization (PMF), principal component
analysis (PCA) and cluster analysis (CA). The fundamental
principle of receptor models is the assumption of mass
conservation, and thus a mass balance analysis can be used to
identify and apportion sources of PM in the atmosphere
(Hopke, 1991).
PMF has been used extensively for source apportionment
of ambient PM in many studies (Huang et al., 1999; Kim et al.,
2004; Krecl et al., 2008; Liu et al., 2003; Santoso et al., 2008).
The present study aims to apportion the sources of fine
particulates (PM2.5) collected by a sampling program near
KTCT. Crustal enrichment factors were used to examine the
anthropogenicity of elements. The contributions from various
sources, with a particular emphasis on the contribution of
ship emissions, were resolved using PMF. For the comparison,
principal component analysis/absolute principal component
scores (PCA/APCS) was performed.
2. Methodology
2.1. Site description
The sampling site was located on the rooftop of a six-storey
building (approximately 18 m above ground) with latitude
2220 31 N and longitude 1146 23 E, on the Tsing Yi Island as
shown in Fig. 1. It was adjacent to a busy port, the Kwai Chung
and Tsing Yi Container Terminals (KTCT) consisting of nine
container terminals with total 24 berths. The port operates
24 h a day and seven days a week. It is located in the
southeastern part of the sampling site with a minimal distance
of 700 m. Every ship entering the terminals has to pass the
shipping lane within 2 km to the south of sampling site. Ship
traffic is very heavy with averagely 42 ocean-going container
vessels berthing at KTCT per day in 2009 (Marine Department,
2010). A chemical waste treatment plant is located 1250 m
from the south. There was a small construction work at about
100 m away from the site during sampling period in winter. To
the immediate north of the sampling site is a densely populated
residential area. Meteorological data, such as wind speed and
wind direction, at Tsing Yi were obtained from the Hong Kong
Observatory. The meteorological station is located in the west
of Tsing Yi as shown in Fig. 1. The height of the sensors in the
meteorological station is 43 m and the height of the sampling
site is 18 m. Despite of the 150 m elevated terrain between two
sites, the short-term wind measurement at sampling site
shows a high agreement of wind data at two sites.
2.2. Sampling
The monitoring program for PM2.5 was performed during
the two study periods of (1) August 14 to October 2, 2009 for
summer and (2) January 26 to March 1, 2010 for winter.
Filter-based PM samples were collected during daytime (0700
to 1800) and nighttime (1830 to 0530 the following day), with
an 11 h sampling duration. The gaps between the periods were
for changing filter and preparation. A total of 85 PM2.5 samples
were collected using a high-volume sampler manufactured
by Andersen Instruments/GMW with 8 10 in2 quartz fiber
filters (Whatman Grade QM-A quartz filters). The filters were
pretreated at 550 C for 3 h before use. The high-volume
sampler operated at flow rates of 1.07 m 3 min1 to
1.18 m 3 min1. After the collection, loaded filters were
transported in a cooler filled with ice pack and were stored in
a refrigerator at 4 C to prevent the evaporation of volatile
components before chemical analysis.
2.3. Chemical analysis
Carbonaceous analysis (OC and EC) were performed by
using a Desert Research Institute (DRI) Model 2001 Thermal/
Optical Carbon Analyzer with the IMPROVE_A thermal/
optical reflectance (TOR) protocol (DRI, 2005). A small
portion with 0.526 cm 2 area of a loaded quartz filter was
cut with a standard puncher for carbonaceous analysis. The
samples were heated and evolved stepwise at temperatures
of 140 C (OC1), 280 C (OC2), 480 C (OC3), and 580 C
(OC4) in He-only atmosphere for OC and at temperatures of
580 C (EC1), 740 C (EC2), and 840 C (EC3) in 98% He/2%
O2 atmosphere for EC. The OP value corrects pyrolysis
charring of OC compounds to EC to prevent the underesti-
mation of OC and overestimation of EC. OP represents the
carbon evolved from the time that the carrier gas flow
changes from He to 98% He/2% O2 at 580 C to the time that
the laser-measured filter reflectance (OPR) reaches its initial
value. The correction for pyrolysis is made by continuously
monitoring the reflectance of filter (via a helium-neon laser
and a photodetector) throughout an analysis cycle. The
portion of the EC peak corresponding to pyrolyzed OC
can be accurately assigned to the OC fraction. OC is defined
as OC1 + OC2 + OC3 + OC4 + OP, while EC is defined as
EC1 + EC2 + EC3 OP.
Ions including chloride (Cl), nitrate (NO3), sulfate (SO42),
sodium (Na+), potassium (K+), and ammonium (NH4+) were
 P.S. Yau et al. / Atmospheric Research 124 (2013) 6172
Fig. 1. Sampling locations at Tsing Yi near the Kwai Chung and Tsing Yi Container Terminals (KTCT).
analyzed by ion chromatography (IC). A fixed area (2.63 cm2) of
the loaded filter sample was extracted with distilleddeionized
water by sonication. The extracted solutions were filtered and
used for IC analysis. The concentrations of elements in aerosols
were analyzed by inductively coupled plasma-atomic emission
spectroscopy (ICP-AES). Filter samples of 78.5 cm2 were
digested with nitric acid (HNO3) and perchloric acid (HClO4)
in a programmed heating block. The elements measured include
Al, As, Ca, Cd, Co, Cr, Cu, Fe, Li, Mg, Mn, Mo, Ni, P, Pb, S, Sb, Se, Sr,
Ti, Tl, V, and Zn.
2.4. Data analysis and receptor modeling
Upper Continental Crust (UCC) Enrichment factors (EFs)
of trace elements in the aerosol relative to the earth's crust
were obtained to indicate the extent of contribution of
sources, probably anthropogenic sources, other than crustal
crust in ambient elemental levels (Manoli et al., 2002). In this
study, Al, one of the common choices of reference elements,
was selected as reference. The EF of element X in an aerosol
sample defined as
EFcrust;X X=Alair =X=Alcrust 1 instructions specified in the USEPA user guide were closely
where EFcrust,X is the EF of X, ([X]/[Al])air is the concentration
ratio of X to Al in the aerosol sample, and ([X]/[Al])crust is the
concentration ratio of X to Al in the crust. The higher EF
implies the higher extent of anthropogenic origin of a given
element (Ntziachristos et al., 2007).
The model EPA PMF 3.0 was adopted for the source
apportionment of PM2.5 collected at the portside monitoring
site. Similar to other multivariate receptor modeling, PMF is
63
based on a mass balance equation (Eq. (2)) to estimate the
source profiles and their contributions.
p
X ij p1 Cip Sjp Eij 2
where Xij is the measured concentration of the ith species in
the jth sample, Cip is the concentration of the ith species in the
material emitted by pth source, and Sjp is the airborne mass
contribution of material from the pth source contributing to
the jth sample. Eij represents random errors in the measure-
ment of Cip and Sjp or the unaccounted sources. PMF solves the
general receptor modeling problem using constrained non-
negative source compositions and contributions, weighted and
least-squares (Paatero and Tapper, 1994). The non-negativity
constraint is natural and more realistic in receptor modeling of
environmental data. Also, a point-by-point weighting scheme,
for error estimates for each data value, allows the inclusion of
uncertain data in the analysis by giving them low weights
(Ramadan et al., 2000).
85 filter samples (43 for daytime and 42 for nighttime; 41
for summer and 44 for winter) were used for the modeling. The
followed (USEPA, 2008). The measured concentrations of the
chemical species in fine particulates (concentration file) and
their uncertainty (equation-based uncertainty file) were used
as inputs to the model. For the choice of chemical species, based
on the recommendation of S.L. Huang et al. (1999), species with
more than 50% of samples below method detection limit (MDL)
were screened out. Otherwise, values below the detection limit
were replaced by half of the MDL. As described in the USEPA
user guide, the species were categorized as Strong, Weak,
64 P.S. Yau et al. / Atmospheric Research 124 (2013) 6172

and Bad based on the signal-to-noise ratio (S/N ratio) and % of
data above MDL (Hopke and Paatero, 2003). If the S/N ratio was
less than 0.2, the species were regarded as Bad. Species with
an S/N ratio between 0.2 and 2 were categorized as Weak,
and those species with an S/N ratio higher than 2 were
categorized as Strong. Other than the statistical consider-
ation, other aspects such as species present in sources in the
area as well as the problems with the collection or analysis of
the species were considered for the categorization (USEPA,
2008). Finally, 19 species, including OC, EC, NO3, SO42, Na +,
K +, NH4+, Al, As, Ca, Cd, Cr, Cu, Fe, Mg, Ni, Pb, V and Zn, were
selected for this receptor modeling. To estimate the contribu-
tions, PM2.5 was included as a species in the data matrix to be
analyzed with PMF and so that it would be apportioned to each
factor just as the other species.
The number of factors to be chosen depends on the
understanding of the sources affecting the air shed, number
of samples, sampling frequency, and species characteristics
(USEPA, 2008). For a good fit, theoretical Q values, goodness-
of-fit parameters, should be approximately equal to the
number of degree of freedom or approximately equal to the
total number of data points in the data array (Polissar et al.,
1998). The theoretical Q was estimated as nm p(n + m),
where n is the number of species, m is the number of samples,
and p is the number of factors fitted by the model. Solutions in
which Q(true) [including all points] is greater than Q(robust)
[excluding outliers] by 1.5 times were avoided to prevent the
disproportionate influence of peak events on the model.
3. Results and discussion
The PM2.5 levels were 32.8 11.5 g/m 3 and 28.2
12.3 g/m 3 for daytime and nighttime, respectively. Fine
particulate level was higher in day-time than that in night-
time could be due to the more anthropogenic activity such
as road traffic during the day-time (Lau et al., 2008; Lu and
Wang, 2008). For the seasonal variation, the average PM2.5
level was higher during winter than summer regardless day
or night time because of the regional meteorology of the
Asiatic monsoon (Ho et al., 2003). In Hong Kong, easterly
winds prevail in summer, whereas north to northeasterly
winds prevail in winter. Dominating northeasterly winds
bring emissions from the Asian continent to Hong Kong in
winter. Moreover, the higher precipitation in summer
lowers the PM level.
The concentrations of chemical species were analyzed to
generate a chemical mass closure of PM2.5 which has been an
accepted method for aerosol analysis (Ma et al., 2001). The
chemical species were classified into eight categories, namely,
organic matter (OM), elemental carbon (EC), sulfate, nitrate,
ammonium, sea-salt, crustal matter, and other elements. As
organic carbon (OC) has not been accounted for oxygen,
hydrogen, sulfur, and nitrogen in organic matter, a conversion
factor of 1.6, commonly used in other studies (Cao et al., 2007;
Keywood et al., 2011), was applied for OM conversion (i.e.,
OM= 1.6 OC). Fig. 2 shows the chemical mass closure chart.
The dominant species was sulfate (33%), followed by OM (19%)
and EC (12%). These three major constituents contributed 64%
of the total fine particulate mass. Ammonium, nitrate, sea-salt,
crustal matter, other elements, and unidentified species shared
the remaining portion (36%).

3.1. PM2.5 level and chemical mass closure 3.2. EF of elements in PM2.5

Table 1 shows the statistical summary of PM2.5 mass UCC EFs of elements in PM2.5 collected at KTCT relative to
concentration. The average PM2.5 mass concentration was the Earth's crust, with Al as the reference element, were
30.5 12.0 g/m 3 in the range of 8.4 g/m 3 to 63.0 g/m 3. calculated to indicate the extent of contributions of sources
Compared with the PM2.5 levels observed in past studies, the other than natural crust to the ambient elemental levels. As
PM2.5 levels in the area near the shipping port are com- there is a certain extent of uncertainty of EFs of the elements
parable with those in a general urban monitoring station caused by the variations of the earth crustal composition, EFs
(37.1 g/m 3) but lower than those in a roadside environment higher than 10 are considered to have anthropogenic origin.
(52.3 g/m 3) (Lee et al., 2006; Louie et al., 2005). The PM2.5 The EFs of 22 elements in PM2.5 determined by ICP-AES analysis
level has not been included in the air quality objectives were calculated as shown in Fig. 3. The EFs for Al, Ti, Mg, Fe, Sr,
(AQOs) in Hong Kong. Unfortunately, the average PM2.5 level and Ca were less than 10 and those elements were interpreted
observed in the present study was double the criterion of to have crustal origin (Contini et al., 2010). The results agree
the PM2.5 annual average level (15 g/m 3) of the National with the findings of a previous study of Ho et al. (2006). Cd had
Ambient Air Quality Standard (NAAQS) of United States. the highest EFs (EF= 5503), indicating that it was the most
anthropogenic and it probably came from an industrial source
Table 1 or coal combustion. The EFs of V and Ni combustion were 1035
Summary statistics of PM2.5 measurement (g/m3). and 979, respectively. Their high EFs indicate that V and Ni,
Min. Max. Mean S.D. present in the Earth crust as minor constituents as well, had a
high degree of anthropogenic origin and were less likely from
Daytime
Summer 16.8 53.4 28.6 10.0
crustal source. The relatively lower (ranging from 20 to 140)
Winter 17.5 63.0 36.8 11.5 EFs of Mn, Co, Se, Li, Cr, P, and Mo suggest that natural
All 16.8 63.0 32.8 11.5 emissions played more role in origins of these elements
Nighttime compared with those of the elements with higher EFs.
Summer 8.4 39.6 21.6 9.4
Winter 21.3 57.8 34.3 11.6
All 8.4 57.8 28.2 12.3 3.3. Source apportionment by receptor modeling
Both
Summer 8.4 53.4 25.2 10.2 3.3.1. Source identication
Winter 17.5 63.0 35.5 11.5 PMF was used to resolve the potential sources by
All 8.4 63.0 30.5 12.0
multivariate factor analysis. The resolved sources can be
 P.S. Yau et al. / Atmospheric Research 124 (2013) 6172 65

Unidentifed ,
Other elements, 2.3, 7% OM (OC*1.6),
1.6, 5% 5.8, 19%
Crustal matter,
1.5, 5%

Sea-salt, 1.6, 5%

EC, 3.6, 12%

Nitrate, 1.1, 4%

Sulfate, 10.2,
33% Ammonium,
2.9, 10%
Unit: g/m3

Fig. 2. Chemical mass closure of PM2.5 collected at the sampling site.

qualitatively identified by the trace markers shown in the
mass profiles, with the aid of the profile of the contribution to
the species total for each source. Fig. 4 shows the mass
profiles of the sources, and Fig. 5 presents their correspond-
ing profiles of the contribution to the species total. Eight
potential sources identified by the trace markers were
residual oil (RO) combustion, marine diesel oil (MDO)
combustion, vehicle emission, coal combustion, incineration,
crustal and sea-salt, secondary sulfate and secondary nitrate.
Fig. 6 shows the average mass concentrations and the con-
tribution percentages of the identified sources to the total
mass of fine particulates.
Two sources, RO combustion and MDO combustion, were
regarded as ship emissions. Similar to other combustion
systems, ship engines consume fuel for power generation.
The main engines (MEs) are used for propulsion and the
10000
Anthropogenic
1000
Enrichment Factor
auxiliary engines (AEs) are mainly used for electricity supply.
A wide range of marine fuels is consumed by ships and the
type of fuel used depends mainly on ship types and engine
types. Marine fuels are categorized into residual oil (RO) and
marine distillate (MD) primarily by their viscosity, and the
latter is further classified into marine diesel oil (MDO) and
marine gas oil (MGO) (ICF, 1999). MD is usually consumed by
main engines in small vessels such as fishing and recreational
vessels or by auxiliary engines in ocean-going vessels for
power generation, whereas the RO is commonly used by
commercial container vessels for propulsion (Reders and
Mundt, 2007; USEPA, 2006). The particulate emissions from
ships consist of sulfate, elemental carbon (EC), organic
carbon (OC) and trace chemical elements, including vanadi-
um (V), sodium (Na), calcium (Ca), nickel (Ni), aluminum
(Al), iron (Fe), etc. (Agrawal et al., 2008a). Compared with
the vehicular emissions, combustion of marine fuel in ships
produces greater amount of heavy metals and soot than that
> Crustal
of gasoline and diesel in vehicles (Ault et al., 2009).
The RO combustion was recognized with abundant V and
Ni, the major trace markers (Agrawal et al., 2009; Almeida et
al., 2005). As there is no other potential source of residual oil
combustion in Hong Kong, ship running on residual oil are

identified as the major source of V and Ni in Hong Kong. Based

on the mass profile, other than that of V and Ni, the high
100
contents of sulfate and carbon were found, that is consistent
with the findings of an emission study of a container vessel
running on RO (Agrawal et al., 2008a). For MDO combustion,
10 although V and Ni contents were not as high as that for RO
combustion, they were still highly noticeable in the source
profile. In addition to high sulfate and carbon contents,
1
significant concentrations of calcium and zinc, which are a
constituent of the lube oil used with sulfurous fuels and an
Cd
Sb
As
Zn
Tl
Cu
V
Pb
Ni
Mo
P
Cr
Li
Se
Co
Mn
Ca
Sr
Fe
Mg
Ti
Al

antiwear element in the lube oil respectively (Agrawal et al.,

Fig. 3. Enrichment factors of elements in portside PM2.5. 2008b), were found in the source profile of MDO combustion.
66 P.S. Yau et al. / Atmospheric Research 124 (2013) 6172

Fig. 4. Mass concentration profiles for the sources.

The separation of emissions from RO and MDO combus-
tions in the source apportionment was not observed in
previous studies. In this portside monitoring site, as there
were many container ships maneuvering nearby and
hotelling at the terminals, the influence of emissions from
the combustion of marine fuel, usually MDO, used in AE was
sufficiently observed and could be separated from RO
combustion. The contributions of RO combustion and MDO
combustion to fine particulates at the sampling site were 12%
(3.6 g/m 3) and 7% (2.3 g/m 3) respectively, and the total of
which was higher than the contribution of oil combustion
(1% to 4%) observed in other urban areas (Ho et al., 2006).
Vehicle emissions were characterized by high carbon (OC
and EC) concentration (Kim and Hopke, 2008). Both diesel-
and gasoline-powered vehicles generate a large amount of
carbonaceous compounds and a certain amount of sulfate
 P.S. Yau et al. / Atmospheric Research 124 (2013) 6172 67

Fig. 5. Profiles of the contribution to species total for the sources.

(Cheng et al., 2010). The average contribution of vehicle
emissions to PM2.5 was 11%. Coal combustion was identified
by high quantities of sulfate and OC, and certain amounts of
trace elements such as Pb, As, and Cd (Furimsky, 2000;
Watson et al., 2001; Zhang et al., 2008). In Hong Kong, the
major source of coal combustion is coal-fired power plants,
which were estimated to contribute 20% to fine particulates.
The Zn-dominated source could be classified as incineration
(Huang et al., 2001; Yoo et al., 2002), or as industrial source
such as metal smelter (Lee et al., 1999). A chemical waste
treatment plant with an incinerator is located 1.25 km away
from the sampling site. The Zn-dominated source, which
contributed 3% to PM2.5 mass, was more likely to be
incineration. The sixth source had large contributions from
Al, Ca, Mg, and Na +, suggesting its association with crustal
dust and sea-salt (Hwang and Hopke, 2007; Yuan et al.,
2006). The construction activity nearby would increase the
contribution from crustal aerosols. The seventh source
profile included a high concentration of SO42 and NH4+,
and some carbon, which was revealed as secondary sulfate
(Kim et al., 2003). The oxidation of sulfur dioxide in ambient
air forms secondary sulfate aerosols. The eighth source was
distinguished by NO3, NH4+, and OC, suggesting its associ-
ation with secondary nitrate aerosol. Both seventh and
eighth sources were secondary aerosols and they contribut-
ed 29% and 13% to the measured fine particulates respec-
tively. In total, secondary aerosols contributed 13 g/m 3
PM2.5 mass (42%).
3.3.2. Comparison with source apportionment from PCA/APCS
PCA/APCS analysis for the data of the 85 samples was
performed by using SPSS. The detailed principle and
procedure of the analysis were described in the study of
Thurston and Spengler (1985). In this analysis, only those 14
68 P.S. Yau et al. / Atmospheric Research 124 (2013) 6172

Secondary Residue oil,

nitrate, 4.0, 3.6, 12%
13%
Marine diesel
oil, 2.3, 7%

Secondary
sulfate, 9.0,
Vehicle
29%
emission, 3.4,
11%

Crustal / sea-
Coal
salt, 1.4, 5%
Incineration, combustion,
1.0, 3% 5.9, 20%

Fig. 6. Average mass concentrations (g/m3) and contribution percentages of the identified sources for fine particulates.

species categorized as Strong were involved to avoid the
bias in the results due to the uncertain data of Weak
species. They were OC, EC, NO3, SO42, K +, NH4+, Al, Ca, Cu,
Fe, Ni, Pb, V and Zn.
Table 2 presents the results for PCA analysis of PM2.5 at
the sampling site. Total six factors were identified. Factors 1
to 5, namely secondary sulfate, RO combustion, vehicle
emissions, crustal, secondary nitrate and industrial, were
identified by the same tracers as in PMF analysis. Factor 6
dominated by Cu can be identified as an industrial source
(Sweet et al., 1993). More factors could be identified by PMF
analysis because it allows the inclusion of weak species by
giving them low weights. Using the grouping results of PCA,
source contributions were calculated by multiple linear
regression of PM mass concentration on absolute principal
component scores (APCS). The source contribution percent-
ages derived from PCA/APCS and PMF analysis were com-
pared as shown in Table 3. Concerning the ship emissions, RO
combustion and MDO combustion were differentiated in PMF
analysis but only RO combustion could be identified in PCA/
APCS analysis. The contribution of RO combustion from PCA/
APCS analysis was 25% which is slightly higher than the total
contribution of RO combustion and MDO combustion (19%)
from PMF analysis.
3.3.3. Ship emission contributions in different wind directions
Fig. 7 shows the wind data at Tsing Yi Island obtained from
the Hong Kong Observatory. Wind data during the sampling

Table 2
Results of PCA analysis of PM2.5 at TY site.

Species Rotated component matrix component

Factor 1 Factor 2 Factor 3 Factor 4 Factor 5 Factor 6

OC 0.545 0.197 0.555 0.044 0.429 0.106

EC 0.398 0.571 0.536 0.152 0.130
NO3 0.111 0.155 0.017 0.006 0.947 0.016
SO42 0.911 0.299 0.112 0.079 0.034
K+ 0.601 0.386 0.534 0.058
NH4+ 0.879 0.308 0.148 0.012 0.245 0.000
Al 0.295 0.152 0.852 0.157 0.118
Ca 0.123 0.769 0.341
Cu 0.081 0.098 0.180 0.300 0.022 0.904
Fe 0.418 0.129 0.671 0.479 0.185 0.087
Ni 0.146 0.956 0.042 0.092 0.065
Pb 0.647 0.416 0.116 0.267 0.473
V 0.129 0.964 0.032 0.048
Zn 0.090 0.931 0.007 0.195
% of variance 23.28 18.12 16.62 12.05 11.81 9.02
Cumulative % 23.28 41.41 58.02 70.08 81.89 90.90
Source Secondary sulfate Ship Emission Vehicle Emission Crustal Secondary Nitrate Industrial

Extraction method: Principal Component Analysis; Rotation method: Varimax with Kaiser Normalization. (Only positive values are shown).
 P.S. Yau et al. / Atmospheric Research 124 (2013) 6172 69

Table 3 plotted as Fig. 8(a). The ship contribution to fine particulates

Comparison of source contribution percentages derived from PMF and PCA/ was significantly higher during the period in the downwind
APCS.
position (6.5 g/m3) compared with that in the non-downwind
PMF PCA/APCS position (3.5 g/m3). The difference was even greater if it was
compared with that when westerly to northerly wind dominat-
RO combustion 12% 25%
MDO combustion 7% ed (1.7 g/m3). As shown in Fig. 8(b), the association of
Vehicle emission 11% 8% secondary nitrate contributions and the wind direction was
Coal combustion 20% different from that for ship emissions. It demonstrated that the
Incineration 3%
higher ship contribution in the downwind position did not
Crustal/sea-salt 5% 7%
Industrial 2% because that was where the wind coming from most of the time.
Secondary sulfate 29% 44%
Secondary nitrate 13% 14%
3.3.4. Secondary sulfate associated with primary ship emissions
In the PMF analysis, the contributions of different sources
were supposed to be independent from each other. However,
period was presented in wind rose. The prevailing wind was a relationship between the contributions of RO combustion
easterly to south-easterly, with an average speed of 2.46 m/s and secondary sulfate was found. Fig. 9 shows the scatter
during the sampling periods at Tsing Yi. From the wind rose plots (G-plots) of the PM from RO combustion against the
analysis, around 70% of the sampling time had easterly to secondary sulfate. From the graph, an edge line with a slope
southerly wind, in which the sampling site was in the of 2 was observed. The solid line represents an edge
downwind position from the container port. With the wind demonstrating that whenever the concentration of PM from
data, the relationship between the ship emission contribution RO combustion is large, the concentration of secondary
and wind direction can be investigated. The contributions to sulfate cannot be small. It implies the contribution of oil
PM2.5 mass from RO combustion and MDO combustion were combustion source to the secondary sulfate (Henry, 2003;
combined and were regarded as the contribution from ship Kim and Hopke, 2008). This relationship was also obtained in
emissions. The average ship contributions to PM mass in previous studies (Kim and Hopke, 2008; Pandolfi et al., 2011;
different wind directions were calculated and the results are Viana et al., 2009). According to this relationship, the

Fig. 7. Wind rose at Tsing Yi Island during sampling periods.

70 P.S. Yau et al. / Atmospheric Research 124 (2013) 6172
Fig. 8. Average contributions of (a) ships and (b) secondary nitrate to PM mass in g/m3 in different wind directions.
secondary sulfate associated with the RO combustion could
be quantified. Based on the obtained slope of 2 of the edge
line, 0.5 g/m 3 of secondary sulfate corresponded to every
g/m 3 of primary RO combustion PM2.5. Therefore, total
1.8 g/m 3 of secondary sulfate was estimated to be formed
from 3.6 g/m3 primary fine particulates from RO combustion
in this study. As fuel oil is high in sulfur content, the calculated
sulfate is potentially to represent direct SO3 emission from
ships appearing as particulate sulfate after the condensation
(Amato et al., 2009). Together with the primary ship emissions,
the total ambient PM2.5 mass associated with ship emissions
near KTCT was 7.6 g/m3 (25%). Therefore, ship emissions
significantly affect the ambient fine particulate levels and air
quality especially in places close to the container port.
3.3.5. Potential mitigation measures
There are some existing mitigation measures for maritime
emission reduction in Hong Kong. Marine fuel quality has
been regulated under the Merchant Shipping (Prevention of
Air Pollution) Regulation based on the Marine Pollution
Convention Annex VI. The sulfur content in marine fuel oil
used on board should not exceed 3.5% m/m. In addition,
vessel speed has been limited to 8 kn or 15 kn in Victoria
Harbor and some waters in Harbor East and West for traffic
safety and emission reduction purposes.
Although there are some existing control measures, our
study demonstrates that ship emissions are still significant in
Hong Kong. To alleviate the effect of ship emissions on the local
community, further mitigation measures are essential. The
current limit of sulfur content in fuel oil is 3.5%, but the
worldwide average sulfur content of RO in 2009 was 2.35%. The
sulfur content limit should be tightened further. Moreover,
other control measures adopted in the ports in other countries
should be introduced. Shoreside power implemented in the
ports of Long Beach and Los Angeles can be referenced and
adopted. Using shoreside power can reduce over 90% of NOx,
 P.S. Yau et al. / Atmospheric Research 124 (2013) 6172
Fig. 9. Scatter plot of the RO combustion contributions vs. secondary sulfate
contributions at the sampling site.
SO2, and PM emissions from ship AEs while berthing (ICCT,
2007). With proper and sufficient control measures and
policies, Hong Kong can achieve a sustainable development of
its shipping industry.
4. Conclusions
The contribution of ship emissions on fine particulates near
the container port was demonstrated by source apportion-
ment. Among eight identified sources from the PMF analysis,
RO combustion and MDO combustion regarded as ship emis-
sions accounted for 12% and 7% of fine particulates respectively.
An estimate of 1.8 g/m3 of secondary sulfate corresponded to
primary PM2.5 from RO combustion. The total contributions,
directly and indirectly, from ship emissions to ambient PM2.5
mass at the sampling site was 7.6 g/m 3 (25%). Therefore, ship
emissions significantly affect the ambient fine particulate levels
in the port-side area. In order to improve the regional and local
air quality, further mitigation measures on ship emission are
essential.
Acknowledgments
This project was financially supported by the grant from
the Research Grants Council of Hong Kong (RGC earmarked
grant, PolyU 5210/06E) and the Fundamental Research Funds
for the Central Universities (No. 2011ZM0050). We thank
Mr. W. F. Tam for his technical support and preparation.
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