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Atmospheric Research 124 (2013) 6172

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Atmospheric Research
journal homepage: www.elsevier.com/locate/atmos

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 2000). It was demonstrated that nickel and vanadium, the trace
markers of aerosols from fuel oil combustion, were positively
Shipping is the major transportation mode of international correlated with human cardiovascular and respiratory diseases
trade but ship emissions keep increasing the burden on air that potentially increase PM risk on human health (Dominici
pollutants levels especially in coastal areas. Numerous studies et al., 2007; Zhang et al., 2009). In addition to increasing
have demonstrated the adverse effect on human health of the morbidity, ship emissions are associated with increased
emissions from residual oil (RO) combustion which takes place mortality. It has been assessed that 60,000 premature deaths
in ship engine (Mudway et al., 2004; Roberts et al., 2003). The have been induced globally by shipping-related PM emission
particulate matter (PM) from ship exhaust is dominated by annually (Corbett et al., 2007). Pollution resulting from the
respirable-sized particles (Lyyranen et al., 1999), which has combustion of sulfur-rich fuels has been observed to affect
been widely investigated and proved to be harmful to human death rates, especially respiratory and cardiovascular deaths
health (Davidson et al., 2005; Pope and Dockery, 2006; (Hedley et al., 2002).
Schwarze et al., 2006). Along with particle size, chemical Hong Kong port is a world-class shipping centre with a
composition also influences the toxicity of PM (Anderson, high density of logistics traffic. It has been in the top three
busiest container ports in the world for over ten years in
Corresponding author. Tel.: +852 2766 6011; fax: +852 2334 6389. terms of the number of container throughput handled. In
E-mail address: ceslee@polyu.edu.hk (S.C. Lee). 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 traffic is very heavy with averagely 42 ocean-going container
equivalent units) in 1999 to 21,040,000 TEUs in 2009 (Marine vessels berthing at KTCT per day in 2009 (Marine Department,
Department, 2010). Kwai Chung and Tsing Yi Container 2010). A chemical waste treatment plant is located 1250 m
Terminals (KTCT) is the major port facility in Hong Kong and from the south. There was a small construction work at about
responsible for over 70% of the containers handled in the 100 m away from the site during sampling period in winter. To
territory. However, different from many other overseas ports the immediate north of the sampling site is a densely populated
which are distant from residential areas, KTCT is in the residential area. Meteorological data, such as wind speed and
proximity of the densely populated residential area. In wind direction, at Tsing Yi were obtained from the Hong Kong
consequence, the emissions from ships with huge engines Observatory. The meteorological station is located in the west
running on heavy fuel oil may seriously affect local communi- of Tsing Yi as shown in Fig. 1. The height of the sensors in the
ties. According to the emission inventory from the HKEPD, meteorological station is 43 m and the height of the sampling
416 ton of respirable suspended particulate (RSP), i.e., PM10, site is 18 m. Despite of the 150 m elevated terrain between two
emitted from ship emissions contributed to 7% of the total RSP sites, the short-term wind measurement at sampling site
emissions in Hong Kong (HKEPD, 2008). While the RSP shows a high agreement of wind data at two sites.
emissions from other sources, such as power generation and
vehicles, keep declining, an increasing trend has been observed 2.2. Sampling
for ship emissions. Receptor modelings of aerosols in some
specific sites such as residential areas and roadsides have been The monitoring program for PM2.5 was performed during
studied (Guo et al., 2009; Yuan et al., 2006), however; PM the two study periods of (1) August 14 to October 2, 2009 for
source apportionment near to shipping port has not been summer and (2) January 26 to March 1, 2010 for winter.
conducted. For overseas regions, PM source apportionments Filter-based PM samples were collected during daytime (0700
have been studied for the ports at Cork, Seattle, and Tarragona to 1800) and nighttime (1830 to 0530 the following day), with
(Alastuey et al., 2007; Healy et al., 2010; Minguillon et al., an 11 h sampling duration. The gaps between the periods were
2008). for changing filter and preparation. A total of 85 PM2.5 samples
Receptor models are commonly applied to evaluate the were collected using a high-volume sampler manufactured
contributions of the PM sources at the receptor sites using by Andersen Instruments/GMW with 8 10 in2 quartz fiber
multivariate measurements of particle chemical and physical filters (Whatman Grade QM-A quartz filters). The filters were
properties (Watson et al., 2002). There are various kinds of pretreated at 550 C for 3 h before use. The high-volume
receptor models, including chemical mass balance (CMB), sampler operated at flow rates of 1.07 m 3 min1 to
positive matrix factorization (PMF), principal component 1.18 m 3 min1. After the collection, loaded filters were
analysis (PCA) and cluster analysis (CA). The fundamental transported in a cooler filled with ice pack and were stored in
principle of receptor models is the assumption of mass a refrigerator at 4 C to prevent the evaporation of volatile
conservation, and thus a mass balance analysis can be used to components before chemical analysis.
identify and apportion sources of PM in the atmosphere
(Hopke, 1991). 2.3. Chemical analysis
PMF has been used extensively for source apportionment
of ambient PM in many studies (Huang et al., 1999; Kim et al., Carbonaceous analysis (OC and EC) were performed by
2004; Krecl et al., 2008; Liu et al., 2003; Santoso et al., 2008). using a Desert Research Institute (DRI) Model 2001 Thermal/
The present study aims to apportion the sources of fine Optical Carbon Analyzer with the IMPROVE_A thermal/
particulates (PM2.5) collected by a sampling program near optical reflectance (TOR) protocol (DRI, 2005). A small
KTCT. Crustal enrichment factors were used to examine the portion with 0.526 cm 2 area of a loaded quartz filter was
anthropogenicity of elements. The contributions from various cut with a standard puncher for carbonaceous analysis. The
sources, with a particular emphasis on the contribution of samples were heated and evolved stepwise at temperatures
ship emissions, were resolved using PMF. For the comparison, of 140 C (OC1), 280 C (OC2), 480 C (OC3), and 580 C
principal component analysis/absolute principal component (OC4) in He-only atmosphere for OC and at temperatures of
scores (PCA/APCS) was performed. 580 C (EC1), 740 C (EC2), and 840 C (EC3) in 98% He/2%
O2 atmosphere for EC. The OP value corrects pyrolysis
2. Methodology charring of OC compounds to EC to prevent the underesti-
mation of OC and overestimation of EC. OP represents the
2.1. Site description 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 sampling site was located on the rooftop of a six-storey the laser-measured filter reflectance (OPR) reaches its initial
building (approximately 18 m above ground) with latitude value. The correction for pyrolysis is made by continuously
2220 31 N and longitude 1146 23 E, on the Tsing Yi Island as monitoring the reflectance of filter (via a helium-neon laser
shown in Fig. 1. It was adjacent to a busy port, the Kwai Chung and a photodetector) throughout an analysis cycle. The
and Tsing Yi Container Terminals (KTCT) consisting of nine portion of the EC peak corresponding to pyrolyzed OC
container terminals with total 24 berths. The port operates can be accurately assigned to the OC fraction. OC is defined
24 h a day and seven days a week. It is located in the as OC1 + OC2 + OC3 + OC4 + OP, while EC is defined as
southeastern part of the sampling site with a minimal distance EC1 + EC2 + EC3 OP.
of 700 m. Every ship entering the terminals has to pass the Ions including chloride (Cl), nitrate (NO3), sulfate (SO42),
shipping lane within 2 km to the south of sampling site. Ship sodium (Na+), potassium (K+), and ammonium (NH4+) were
P.S. Yau et al. / Atmospheric Research 124 (2013) 6172 63

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 based on a mass balance equation (Eq. (2)) to estimate the
the loaded filter sample was extracted with distilleddeionized source profiles and their contributions.
water by sonication. The extracted solutions were filtered and
used for IC analysis. The concentrations of elements in aerosols p
X ij p1 Cip Sjp Eij 2
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) where Xij is the measured concentration of the ith species in
in a programmed heating block. The elements measured include the jth sample, Cip is the concentration of the ith species in the
Al, As, Ca, Cd, Co, Cr, Cu, Fe, Li, Mg, Mn, Mo, Ni, P, Pb, S, Sb, Se, Sr, material emitted by pth source, and Sjp is the airborne mass
Ti, Tl, V, and Zn. contribution of material from the pth source contributing to
the jth sample. Eij represents random errors in the measure-
2.4. Data analysis and receptor modeling ment of Cip and Sjp or the unaccounted sources. PMF solves the
general receptor modeling problem using constrained non-
Upper Continental Crust (UCC) Enrichment factors (EFs) negative source compositions and contributions, weighted and
of trace elements in the aerosol relative to the earth's crust least-squares (Paatero and Tapper, 1994). The non-negativity
were obtained to indicate the extent of contribution of constraint is natural and more realistic in receptor modeling of
sources, probably anthropogenic sources, other than crustal environmental data. Also, a point-by-point weighting scheme,
crust in ambient elemental levels (Manoli et al., 2002). In this for error estimates for each data value, allows the inclusion of
study, Al, one of the common choices of reference elements, uncertain data in the analysis by giving them low weights
was selected as reference. The EF of element X in an aerosol (Ramadan et al., 2000).
sample defined as 85 filter samples (43 for daytime and 42 for nighttime; 41
for summer and 44 for winter) were used for the modeling. The
EFcrust;X X=Alair =X=Alcrust 1 instructions specified in the USEPA user guide were closely
followed (USEPA, 2008). The measured concentrations of the
where EFcrust,X is the EF of X, ([X]/[Al])air is the concentration chemical species in fine particulates (concentration file) and
ratio of X to Al in the aerosol sample, and ([X]/[Al])crust is the their uncertainty (equation-based uncertainty file) were used
concentration ratio of X to Al in the crust. The higher EF as inputs to the model. For the choice of chemical species, based
implies the higher extent of anthropogenic origin of a given on the recommendation of S.L. Huang et al. (1999), species with
element (Ntziachristos et al., 2007). more than 50% of samples below method detection limit (MDL)
The model EPA PMF 3.0 was adopted for the source were screened out. Otherwise, values below the detection limit
apportionment of PM2.5 collected at the portside monitoring were replaced by half of the MDL. As described in the USEPA
site. Similar to other multivariate receptor modeling, PMF is 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 The PM2.5 levels were 32.8 11.5 g/m 3 and 28.2
data above MDL (Hopke and Paatero, 2003). If the S/N ratio was 12.3 g/m 3 for daytime and nighttime, respectively. Fine
less than 0.2, the species were regarded as Bad. Species with particulate level was higher in day-time than that in night-
an S/N ratio between 0.2 and 2 were categorized as Weak, time could be due to the more anthropogenic activity such
and those species with an S/N ratio higher than 2 were as road traffic during the day-time (Lau et al., 2008; Lu and
categorized as Strong. Other than the statistical consider- Wang, 2008). For the seasonal variation, the average PM2.5
ation, other aspects such as species present in sources in the level was higher during winter than summer regardless day
area as well as the problems with the collection or analysis of or night time because of the regional meteorology of the
the species were considered for the categorization (USEPA, Asiatic monsoon (Ho et al., 2003). In Hong Kong, easterly
2008). Finally, 19 species, including OC, EC, NO3, SO42, Na +, winds prevail in summer, whereas north to northeasterly
K +, NH4+, Al, As, Ca, Cd, Cr, Cu, Fe, Mg, Ni, Pb, V and Zn, were winds prevail in winter. Dominating northeasterly winds
selected for this receptor modeling. To estimate the contribu- bring emissions from the Asian continent to Hong Kong in
tions, PM2.5 was included as a species in the data matrix to be winter. Moreover, the higher precipitation in summer
analyzed with PMF and so that it would be apportioned to each lowers the PM level.
factor just as the other species. The concentrations of chemical species were analyzed to
The number of factors to be chosen depends on the generate a chemical mass closure of PM2.5 which has been an
understanding of the sources affecting the air shed, number accepted method for aerosol analysis (Ma et al., 2001). The
of samples, sampling frequency, and species characteristics chemical species were classified into eight categories, namely,
(USEPA, 2008). For a good fit, theoretical Q values, goodness- organic matter (OM), elemental carbon (EC), sulfate, nitrate,
of-fit parameters, should be approximately equal to the ammonium, sea-salt, crustal matter, and other elements. As
number of degree of freedom or approximately equal to the organic carbon (OC) has not been accounted for oxygen,
total number of data points in the data array (Polissar et al., hydrogen, sulfur, and nitrogen in organic matter, a conversion
1998). The theoretical Q was estimated as nm p(n + m), factor of 1.6, commonly used in other studies (Cao et al., 2007;
where n is the number of species, m is the number of samples, Keywood et al., 2011), was applied for OM conversion (i.e.,
and p is the number of factors fitted by the model. Solutions in OM= 1.6 OC). Fig. 2 shows the chemical mass closure chart.
which Q(true) [including all points] is greater than Q(robust) The dominant species was sulfate (33%), followed by OM (19%)
[excluding outliers] by 1.5 times were avoided to prevent the and EC (12%). These three major constituents contributed 64%
disproportionate influence of peak events on the model. of the total fine particulate mass. Ammonium, nitrate, sea-salt,
crustal matter, other elements, and unidentified species shared
3. Results and discussion 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 auxiliary engines (AEs) are mainly used for electricity supply.
mass profiles, with the aid of the profile of the contribution to A wide range of marine fuels is consumed by ships and the
the species total for each source. Fig. 4 shows the mass type of fuel used depends mainly on ship types and engine
profiles of the sources, and Fig. 5 presents their correspond- types. Marine fuels are categorized into residual oil (RO) and
ing profiles of the contribution to the species total. Eight marine distillate (MD) primarily by their viscosity, and the
potential sources identified by the trace markers were latter is further classified into marine diesel oil (MDO) and
residual oil (RO) combustion, marine diesel oil (MDO) marine gas oil (MGO) (ICF, 1999). MD is usually consumed by
combustion, vehicle emission, coal combustion, incineration, main engines in small vessels such as fishing and recreational
crustal and sea-salt, secondary sulfate and secondary nitrate. vessels or by auxiliary engines in ocean-going vessels for
Fig. 6 shows the average mass concentrations and the con- power generation, whereas the RO is commonly used by
tribution percentages of the identified sources to the total commercial container vessels for propulsion (Reders and
mass of fine particulates. Mundt, 2007; USEPA, 2006). The particulate emissions from
Two sources, RO combustion and MDO combustion, were ships consist of sulfate, elemental carbon (EC), organic
regarded as ship emissions. Similar to other combustion carbon (OC) and trace chemical elements, including vanadi-
systems, ship engines consume fuel for power generation. um (V), sodium (Na), calcium (Ca), nickel (Ni), aluminum
The main engines (MEs) are used for propulsion and the (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
10000
Anthropogenic > 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
1000 al., 2005). As there is no other potential source of residual oil
combustion in Hong Kong, ship running on residual oil are
Enrichment Factor

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- combustion to fine particulates at the sampling site were 12%
tions in the source apportionment was not observed in (3.6 g/m 3) and 7% (2.3 g/m 3) respectively, and the total of
previous studies. In this portside monitoring site, as there which was higher than the contribution of oil combustion
were many container ships maneuvering nearby and (1% to 4%) observed in other urban areas (Ho et al., 2006).
hotelling at the terminals, the influence of emissions from Vehicle emissions were characterized by high carbon (OC
the combustion of marine fuel, usually MDO, used in AE was and EC) concentration (Kim and Hopke, 2008). Both diesel-
sufficiently observed and could be separated from RO and gasoline-powered vehicles generate a large amount of
combustion. The contributions of RO combustion and MDO 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 contribution from crustal aerosols. The seventh source
emissions to PM2.5 was 11%. Coal combustion was identified profile included a high concentration of SO42 and NH4+,
by high quantities of sulfate and OC, and certain amounts of and some carbon, which was revealed as secondary sulfate
trace elements such as Pb, As, and Cd (Furimsky, 2000; (Kim et al., 2003). The oxidation of sulfur dioxide in ambient
Watson et al., 2001; Zhang et al., 2008). In Hong Kong, the air forms secondary sulfate aerosols. The eighth source was
major source of coal combustion is coal-fired power plants, distinguished by NO3, NH4+, and OC, suggesting its associ-
which were estimated to contribute 20% to fine particulates. ation with secondary nitrate aerosol. Both seventh and
The Zn-dominated source could be classified as incineration eighth sources were secondary aerosols and they contribut-
(Huang et al., 2001; Yoo et al., 2002), or as industrial source ed 29% and 13% to the measured fine particulates respec-
such as metal smelter (Lee et al., 1999). A chemical waste tively. In total, secondary aerosols contributed 13 g/m 3
treatment plant with an incinerator is located 1.25 km away PM2.5 mass (42%).
from the sampling site. The Zn-dominated source, which
contributed 3% to PM2.5 mass, was more likely to be 3.3.2. Comparison with source apportionment from PCA/APCS
incineration. The sixth source had large contributions from PCA/APCS analysis for the data of the 85 samples was
Al, Ca, Mg, and Na +, suggesting its association with crustal performed by using SPSS. The detailed principle and
dust and sea-salt (Hwang and Hopke, 2007; Yuan et al., procedure of the analysis were described in the study of
2006). The construction activity nearby would increase the 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 regression of PM mass concentration on absolute principal
bias in the results due to the uncertain data of Weak component scores (APCS). The source contribution percent-
species. They were OC, EC, NO3, SO42, K +, NH4+, Al, Ca, Cu, ages derived from PCA/APCS and PMF analysis were com-
Fe, Ni, Pb, V and Zn. pared as shown in Table 3. Concerning the ship emissions, RO
Table 2 presents the results for PCA analysis of PM2.5 at combustion and MDO combustion were differentiated in PMF
the sampling site. Total six factors were identified. Factors 1 analysis but only RO combustion could be identified in PCA/
to 5, namely secondary sulfate, RO combustion, vehicle APCS analysis. The contribution of RO combustion from PCA/
emissions, crustal, secondary nitrate and industrial, were APCS analysis was 25% which is slightly higher than the total
identified by the same tracers as in PMF analysis. Factor 6 contribution of RO combustion and MDO combustion (19%)
dominated by Cu can be identified as an industrial source from PMF analysis.
(Sweet et al., 1993). More factors could be identified by PMF
analysis because it allows the inclusion of weak species by 3.3.3. Ship emission contributions in different wind directions
giving them low weights. Using the grouping results of PCA, Fig. 7 shows the wind data at Tsing Yi Island obtained from
source contributions were calculated by multiple linear 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 been regulated under the Merchant Shipping (Prevention of
be quantified. Based on the obtained slope of 2 of the edge Air Pollution) Regulation based on the Marine Pollution
line, 0.5 g/m 3 of secondary sulfate corresponded to every Convention Annex VI. The sulfur content in marine fuel oil
g/m 3 of primary RO combustion PM2.5. Therefore, total used on board should not exceed 3.5% m/m. In addition,
1.8 g/m 3 of secondary sulfate was estimated to be formed vessel speed has been limited to 8 kn or 15 kn in Victoria
from 3.6 g/m3 primary fine particulates from RO combustion Harbor and some waters in Harbor East and West for traffic
in this study. As fuel oil is high in sulfur content, the calculated safety and emission reduction purposes.
sulfate is potentially to represent direct SO3 emission from Although there are some existing control measures, our
ships appearing as particulate sulfate after the condensation study demonstrates that ship emissions are still significant in
(Amato et al., 2009). Together with the primary ship emissions, Hong Kong. To alleviate the effect of ship emissions on the local
the total ambient PM2.5 mass associated with ship emissions community, further mitigation measures are essential. The
near KTCT was 7.6 g/m3 (25%). Therefore, ship emissions current limit of sulfur content in fuel oil is 3.5%, but the
significantly affect the ambient fine particulate levels and air worldwide average sulfur content of RO in 2009 was 2.35%. The
quality especially in places close to the container port. sulfur content limit should be tightened further. Moreover,
other control measures adopted in the ports in other countries
3.3.5. Potential mitigation measures should be introduced. Shoreside power implemented in the
There are some existing mitigation measures for maritime ports of Long Beach and Los Angeles can be referenced and
emission reduction in Hong Kong. Marine fuel quality has adopted. Using shoreside power can reduce over 90% of NOx,
P.S. Yau et al. / Atmospheric Research 124 (2013) 6172 71

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