Atmospheric Environment 89 (2014) 358e366

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Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv

Characteristics of volatile organic compounds (VOCs) emitted from a

petroleum renery in Beijing, China
Wei Wei a, b, Shuiyuan Cheng a, *, Guohao Li a, Gang Wang a, Haiyan Wang a
a
Department of Environmental Science and Engineering, Beijing University of Technology, Beijing 100124, China
b
State Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex, Beijing 100084, China

h i g h l i g h t s

We measured the ambient VOCs for a petroleum renery in China.

We obtained the chemical proles of VOCs emitted from the whole renery and from its inner devices.

The contributions of these devices to downwind measured VOCs were analyzed by PMF method.

The photochemical ozone potentials of these devices related to VOCs were calculated.

Catalytic cracking units were identied as the largest contributor.

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

Article history: This study made a eld VOCs (volatile organic compounds) measurement for a petroleum renery in
Received 28 September 2013 Beijing by determining 56 PAMS VOCs, which are demanded for photochemical assessment in US, and
Received in revised form obtained the characteristics of VOCs emitted from the whole renery and from its inner main devices.
14 January 2014
During the monitoring period, this renery brought about an average increase of 61 ppbv in the ambient
Accepted 20 January 2014
Available online 28 January 2014
TVOCs (sum of the PAMS VOCs) at the renery surrounding area, while the background of TVOCs there
was only 10e30 ppbv. In chemical prole, the VOCs emitted from the whole renery was characteristic
by isobutane (8.7%), n-butane (7.9%), isopentane (6.3%), n-pentane (4.9%%), n-hexane (7.6%), C6 branched
Keywords:
Volatile organic compounds
alkanes (6.0%), propene (12.7%), 1-butene (4.1%), benzene (7.8%), and toluene (5.9%). On the other hand,
Petroleum renery the measurement for the inner 5 devices, catalytic cracking units (CCU2 and CCU3), catalytic reforming
Source apportionment unit (CRU), tank farm (TF), and wastewater treatment(WT), revealed the higher level of VOCs pollutions
Ozone formation potential (about several hundred ppbv of TVOCs), and the individual differences in VOCs chemical proles. Based
on the measured speciated VOCs data at the surrounding downwind area, PMF receptor model was
applied to identify the VOCs sources in the renery. Then, coupling with the VOCs chemical proles
measured at the device areas, we concluded that CCU1/3 contributes to 25.9% of the TVOCs at the sur-
rounding downwind area by volume, followed by CCU2 (24.7%), CRU (18.9%), TF (18.3%) and WT (12.0%),
which was accordant with the research of US EPA (2008). Finally, ozone formation potentials of the 5
devices were also calculated by MIR technique, which showed that catalytic cracking units, accounting
for about 55.6% to photochemical ozone formation, should be given the consideration of VOCs control
rstly.
2014 Elsevier Ltd. All rights reserved.

1. Introduction quality and human health. Up to now, surface O3 pollution has

Volatile organic compounds (VOCs) play an important role in
the tropospheric atmospheric chemistry, for the production of
photochemical ozone (O3) and other oxidants, which increasing the
atmospheric oxidizing ability and adversely inuencing the air
* Corresponding author. Tel.: 86 10 67391656.
E-mail addresses: chengsy@bjut.edu.cn, bjutpaper@gmail.com (S. Cheng).
become a problem in China. It was reported that the surface O3
concentrations continuously increased in last decade by 0.5e
1.0 ppbv yr1 in eastern China and by 0.2e0.4 ppbv yr1 in western
China (Shen and Wang, 2012; Tang et al., 2009; Wang et al., 2009a);
and O3 pollution episodes also frequently occurred in Chinas urban
areas, the annual days over 1-h average Chinese national O3 stan-
dard (93 ppbv) arriving at 40e80 in Beijing and Shanghai (An et al.,
2008; Geng et al., 2010). The studies based on air quality model
simulation for Beijing area, Yangtze River Delta and Pearl River

1352-2310/$ e see front matter 2014 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.atmosenv.2014.01.038
 W. Wei et al. / Atmospheric Environment 89 (2014) 358e366
Delta, believed that the increasing VOCs emissions from anthro-
pogenic sources was an important reason for the elevated O3 con-
centrations, which reaction rates with OH radical primarily
controlled the photochemical O3 formation processes in these re-
gions (Cheng et al., 2013a; Itahashi et al., 2013; Liu et al., 2010;
Wang et al., 2010, 2011). And the studies based on the ambient
observations of O3 and its precursors in Beijing, Shanghai and
Guangzhou, calculated some indicator ratios, such as VOCs/NOx,
OO3/ONOz, etc., and concluded that these cities were under the
VOCs-sensitive regime (Han et al., 2013; Lam et al., 2013; Ran et al.,
2009; Shao et al., 2009).
Consequently, VOCs emissions from anthropogenic sources
have been an increasing concern. Some researches established
the national and regional VOCs emission inventories with high
sectoral, temporal, spatial and chemical-prole resolutions, and
found road gasoline vehicles, biomass burning, paint coating,
petroleum industry as the top 4 emission sources, with the na-
tional contribution of 23e30%, 18e20%, 8e10%, and 7e9%,
respectively (Wei et al., 2008; Bo et al., 2008). Normally, biomass
burning contributes VOCs emissions in rural region and other
three sources mainly occur in urban region. The studies on the
source apportionment of Beijing photochemical O3 identied
road vehicles and Yanshan petroleum industry (including oil re-
nery section and chemical industry section) as the two largest
contributors, respectively with the contribution of 20e30% and
15e28% (Song et al., 2008; Wang et al., 2009b). In addition, with
the rapid economic development, energy structure optimization,
and the advancement of legislative standards for vehicle exhaust
gases, the VOCs emissions from industrial process would become
more and more important in future, which was forecasted to be
the second largest contributor in 2020 in China by Wei et al.
(2011).
Some studies focused on VOCs pollutions near the industrial
sources (Kabir and Kim, 2010; Kim et al., 2013; Pal et al., 2008; Pan
et al., 2011; Shie and Chan, 2013). In general, they rstly selected
the target compounds according to their concerns (e.g. odorant
compounds, toxic compounds, photochemical reactive compounds,
etc.), measured their ambient concentrations by on-line or off-line
monitors, concluded their pollution levels and temporal variation
patterns, calculated the correlations between different groups or
individual compounds, determined the tracer indicators for
different industrial sources, and made the potential health risk
assessment. For Chinas petroleum industry, only two researches of
Liu et al. (2008) and Cheng et al.( 2013b) were reported recently.
And they only provided the chemical proles of VOCs emitted from
the whole factory by the surrounding measurements, but never
considered its inner emission devices, among which great differ-
ences in VOCs emission rates and in VOCs chemical proles exit. It
would be hard to identify the key emission sources for the possible
emission control in future. This unknown has been a big disad-
vantage for the assessment of Chinas VOCs emission amounts, for
the knowledge of atmospheric photochemical pollution in Chinas
cities, and for the control policy making of air quality assurance in
future.
In this regard, we performed a eld VOCs measurement
campaign for a petroleum renery in Beijing in 2011, by moni-
toring 56 PAMS VOCs, which are determined by Photochemical
Assessment Monitoring Stations in US, not only at the renerys
surrounding area, but also at the inner device sources area. This
measurement tried to obtain the characteristics and source
apportionment of VOCs emitted from a petroleum renery. And
we believed that this study would be helpful for Chinas petro-
leum renery to understand the characteristics of VOCs emis-
sions, and to support policy-making with respect to emission
control.
359
2. Methodology
2.1. Field measurement protocol
Yanshan petroleum renery, located in 40 km southwest of
Beijing city center, was researched in this study, which annually
renes 10 million tons of crude oil and mainly produces
2.4 million tons of gasoline, 3.1 million tons of diesel oil and
1.3 million tons of kerosene. These products are processed through
different units, such as the crude distillation unit (CDU)/vacuum
distillation unit (VDU), catalytic cracking unit (CCU), catalytic
reforming unit (CRU). Their locations are signed in Fig. 1. In this
renery, there are three CCUs, CCU1 and CCU3 mainly further
rening the hot residual oil produced from CDU/VDU, while CCU2
mainly extracting gasoline and diesel oil from cold residual oil of
heavy oil tanks and catalytic material tanks. According to the
relevant researches in developed countries (Pandya et al., 2006; US
EPA, 2008; US EPA, 2011; Vega et al., 2011), distillation process,
catalytic cracking process, oil storage and wastewater treatment are
thought of as the major emission sources of VOCs in a renery. In
Yanshan renery, the exhaust gas from the roof of CDU/VDU is
vented to boiler as fuels through an exhaust gas recycle system.
According to the research of US EPA (2008, 2011), the VOCs emis-
sions from the controlled CDU/VDU could be negligible. Finally, we
selected 5 main emission devices to make VOCs measurement,
including CCU2, CCU3, CRU, Tank Farm (TF), wastewater treatment
(WT).
The VOCs measurement was conducted by the vacuum summa
canister sampling and laboratory instrument analyzing, so the
multi-sites air sampling could be carried out at the same time,
which assured the comparability of the VOCs concentrations at
various locations. In this study, we totally designed 8 observation
sites (AeH), as shown in Fig. 1.
The monitoring at surrounding area was taken at sites AeC
during JuneeSeptember of 2011. Considering that the south winds
prevail in daytime of the monitoring period, and that the complex
terrain of the renery area, where Yan Mountain with the height of
700e1300 m marks the western and northern edges of the renery,
would make the southern winds take a bend to the east along the
mountain valley, we designed site A at 0.5 km southwest of the
Fig. 1. Design of observation sites in this measurement.
360 W. Wei et al. / Atmospheric Environment 89 (2014) 358e366

renery as the background, and designed site B and site C respec-
tively at the north gate of the renery and at 0.5 km northeast of the
renery as the downwind receptors. During the monitoring,
continuous ve-days observation was made in each month, and
four 1-h samples were concurrently collected at sites A-C in each
observation day. The details were introduced in Table 1.
The monitoring at source areas was arranged at sites D-H. For
the distances between two neighboring devices were normally less
than 200 m, it was hard to make upwind vs downwind observa-
tions for a certain device. So, we put the observation sites at the
center of the device area. In the initial tests, the sum of 56 PAMS
VOCs concentrations at these device areas mostly arrived at several
hundred ppbv, greatly higher than those at other area. It implied
that the air samples collected at device area could represent the air
pollution produced by the device. The source monitoring was taken
in January, April, August, and September of 2011. Monthly samples
were taken on three days for two 1-h periods. More details were
also showed in Table 1. Unlike the surrounding monitoring, the
sampling at these device areas were not carried out at the same
time, for only two operators were permitted to enter the renery
each time, and the VOCs concentrations at these device areas could
not be comparable.
diluted to 4 different concentrations (2, 5, 10 and 20 ppbv) by a
dilution system (model 4600A, Entech Inc.) for the quantication of
target compounds. For each target compound, a calibration curve
was drawn based on the relationship between the integrated peak
area and the corresponding concentration (5 levels: 0, 2, 5, 10 and
20 ppbv); the resulting calibration curves generally yielded good
correlation coefcient values of above 0.99. For QA/QC, the cryo-
genic preconcentrator was baked after each analysis, and the GC
column was also baked after analysis of every 20 samples.
The concentrations of ethane, ethene, acetylene, and propane in
the samples were further analyzed by Gas ChromatographeFlame
Ionization Detector (GCeFID), which were provided by state joint
key Laboratory of environmental simulation and pollution control
in Peking University. The VOCs species measured by the GCeMS
system and GCeFID system were listed in Table 2. The samples of
the source monitoring were analyzed by both GCeMS and GCeFID,
and obtained the integral 56 PAMS VOCs concentrations; but for the
samples of the surrounding monitoring, only GCeMS in our labo-
ratory was available, and 52 PAMS VOCs (never including ethane,
ethene, acetylene, and propane) were determined.
2.3. PMF analysis method

2.2. VOCs measurement method Positive Matrix Factorization (PMF), as an advanced receptor
model, could solve a constrained and weighted least-squares
The gaseous samples collected in summa canister were analyzed optimization equation to decompose a matrix of speciated sample
by Gas ChromatographeMass Spectrometer (GCeMS, Model data into two matrices, source contributions and source proles, as
7890A/5975C, Agilent Inc.) in our laboratory to determine VOCs shown in Equation (1).
concentrations, according to EPA TO-15 Method (US EPA, 1999). X
Before the 400 ml sample was injected into GCeMS, a pre-process Cik pij fjk eik (1)
was needed to remove N2, O2, CO2, CO and H20 in sample and to j

further concentrate sample in volume by cryogenic preconcen-

trator (Model 7100, Entech Inc.). The GCeMS analyzer system could where, Cik means the concentration of VOC i in kth sampling, pij
detect all PAMS VOCs except ethane, ethene, acetylene, and pro- means the chemical prole of VOC i at jth sources, fjk means the
pane with the detection limits of about 1e3 ppbv (about several ng contribution of jth source at kth sampling, and eik is the residual
of absolute detectable quality). Then, PAMS certied gas was factor for VOC i at kth sampling.
It is widely applied in the identication of VOCs contributing
sources at the scale of city by many researches (Brown et al., 2007;
Table 1 Cai et al., 2011; Lau et al., 2010; Leuchner and Rappengluck, 2010;
Field measurement protocol. Ling et al., 2011; Yuan et al., 2013). In this study, we thought that
Site Location Monitor days Monitor diurnal time Sample the VOCs at the surrounding sites BeC were the combining results
numbers of air mass polluted by the inner VOCs-emission devices in the
Site A Renery 5 days each month, 8:00e9:00 41 renery, and the chemical speciation and contribution of VOCs
Background JuneeSeptember, 2011 12:00e13:00 from these devices could be analyzed by PMF based on the VOCs
14:30e15:30 data measured at downwind sites.
17:00e18:00
In our PMF application, i was 21, including 12 saturated, 4 un-
Site B Renery 5 days each month, 8:00e9:00 62
Downwind JuneeSeptember, 2011 12:00e13:00
saturated, 5 aromatic VOCs, which were marked in Table 2, and they
14:30e15:30 accounted for more than 70% of the total 52 VOCs detected. And k
17:00e18:00 was 94, which 21 VOCs concentration data (Cik) were directly from
Site C Renery 5 days each month, 8:00e9:00 48 the surrounding monitoring at sites BeC. Norris and Vedantham
Downwind JuneeSeptember, 2011 12:00e13:00
(2008) suggested the determination of uncertainty values of the
14:30e15:30
17:00e18:00 concentration data, as shown in Equation (2). For the number of
Site D WT 3 days each month, 12:00e13:00 22 sources j, different numbers (5, 6, 7) were tested. Finally the source
January, April, August, 17:00e18:00 apportionment results with 6 sources could match with VOCs
September, 2011
speciation measured at the device areas most sufciently, which
Site E CCU3 3 days each month, 12:00e13:00 22
January, April, August, 17:00e18:00
will be further discussed in Section 3.0. So, here j was 6.
September, 2011 q
Site F CCU2 3 days each month, 12:00e13:00 22 Uik EF  Cik 2 MDL2i if Cik  MDLi
January, April, August, 17:00e18:00 (2)
September, 2011 5
Uik 6  MDLi if Cik < MDLi
Site G CRU 3 days each month, 12:00e13:00 21
January, April, August, 17:00e18:00
September, 2011 where Uik means the uncertainty value of Cik; MDLi means the
Site H TF 3 days each month, 12:00e13:00 20 method detection limit of VOC i, which values were presented in
January, April, August, 17:00e18:00 Table 2; and EF means error fraction, which was suggested as 10%
September, 2011
by Paatero (2000).
 W. Wei et al. / Atmospheric Environment 89 (2014) 358e366 361

Table 2
PAMS hydrocarbons detected in this study.

No. Hydrocarbons No. Hydrocarbons No. Hydrocarbons No. Hydrocarbons

1 Ethanea 15 Cyclohexaneb DL0.8 29 n-Dodecane 43 Ethylbenzeneb DL1.8

2 n-Propanea 16 2-Methylhexaneb DL0.7 30 Ethenea 44 m,p-Xyleneb DL3.0
3 Isobutaneb DL2.0 17 2,3-Dimethylpentane 31 Acetylenea 45 Styrene
4 n-Butaneb DL2.0 18 3-Methylhexaneb DL0.5 32 Propeneb DL2.0 46 o-Xyleneb DL1.3
5 Isopentaneb DL2.0 19 2,2,4-Trimethylpentane 33 1-Buteneb DL2.0 47 Isopropylbenzene
6 n-Pentaneb DL2.0 20 n-Heptaneb DL0.8 34 t-2-Buteneb DL2.0 48 n-Propylbenzene
7 2,2-dimethylbutane 21 Methylcyclohexane 35 c-2-Buteneb DL2.0 49 m-Ethyltoluene
8 Cyclopentane 22 2,3,4-Trimethylpentane 36 1-Pentene 50 p-Ethyltoluene
9 2,3-Dimethylbutane 23 2-Methylheptane 37 Isoprene 51 1,3,5-Trimetylbenzene
10 2-Methylpentaneb DL1.1 24 3-Mehtylheptane 38 t-2-Pentene 52 o-Ethyltoluene
11 3-Methylpentaneb DL1.9 25 n-Octane 39 c-2-Pentene 53 1,2,4-Trimethylbenzene
12 n-Hexaneb DL1.1 26 n-Nonane 40 1-Hexene 54 1,2,3-Trimethylbenzene
13 Methylcyclopentaneb DL0.8 27 n-Decane 41 Benzeneb DL1.0 55 m-Diethylbenzene
14 2,4-Dimethylpentane 28 n-Undecane 42 Tolueneb DL0.8 56 p-Diethylbenzene
a
The VOCs were measured by GCeFID.
b
The VOCs were used in PMF analysis, which DL (detection limit) unit is ppbv.

The scaled residuals in Base Model Results for the all 21 VOCs
were between 2 and 2, except o-xylene with the value range from
5 to 5. And the Q values in the robust mode were calculated to be
about 1388, approximately equal to the expected degrees of free-
doms. These features demonstrated that our model simulation re-
sults were acceptable.
3. Results and discussion
3.1. Characteristics of ambient VOCs at surrounding area
In the monitoring at the surrounding area, totally 52 VOCs were
detected by GCeMS system. It needs to be noted that the lack of
ethane, ethene, acetylene, and propane was due to the deciency of
GCeMS system, but not to their inexistence in the ambient air.
Then, total VOCs (TVOCs) dened as the sum of detected PAMS
VOCs, was calculated. Fig. 2 concluded the TVOCs concentrations at
sites A-C in four different times, in which the points at one line
meant the simultaneous observations at three sites in a monitor
day. It can be seen that in 8:00e9:00 high-level TVOCs of several
hundred ppbv were measured at three sites, and the differences
between site A and site B/C were not obvious, which was caused by
the fact that the prevailing winds are variable in the early morning
of Beijings summertime, gradually changing from north to south.
However, after the noon, winds from south and southwest become
dominant, and site A and site B/C would become the background
and the receptor, respectively. Monitoring data revealed that TVOCs
at site A in those hours except 8:00e9:00 was in the range of 10e
30 ppbv, greatly lower than the simultaneous TVOCs concentra-
tions at site B (50e200 ppbv) and site C (20e100 ppbv). This
obvious difference approved the great inuence of the renery on
the ambient surrounding VOCs.
Then, through subtracting the VOCs concentrations at site A
from the simultaneous VOCs concentrations at site B/C individually,
the VOCs purely produced by the renery were calculated, which
sum was in the range of 10e200 ppbv with the average value of
61 ppbv. The wide range was caused by the variation of wind di-
rection and wind speed. So, we further calculated its chemical
prole by volume, which obtained a good reliability with the lower
standard deviations, as shown in Fig. 3. The VOCs emitted from the
renery were characteristic by isobutane, n-butane, isopentane, n-
pentane, n-hexane, C6 branched alkanes, propene, 1-butene, ben-
zene and toluene, with the average volume mixing ratios of 8.7%,
7.9%, 6.3%, 4.9%, 7.6%, 6.0%, 12.7%, 4.1%, 7.8% and 5.9%, respectively.
Liu et al. (2008) also reported a chemical prole of 56 PAMS VOCs
(including ethane, propane, ethene, and acetylene) for a petroleum
renery in south of China. In order to compare both research re-
sults, we recalculated the chemical prole of 52 PAMS VOCs of Liu
et al. (2008) by deleting ethane, ethene, acetylene and propane,
which result was concluded in Fig. 3. A good similarity in chemical
prole of 52 VOCs was presented between both researches. In
addition, Shie and Chan (2013) also detected ethane, propane, iso-
butane, n-butane, ethene, propene, benzene and toluene as the
most related VOCs with the petroleum renery, which was accor-
dant with our measurement.
Then, we used the 94 samples at sites BeC in 12:00e13:00,
14:30e15:30, 17:00e18:00, when we believed that sites BeC were
greatly inuenced by the VOCs emissions from the renery, to
make the source apportionment through PMF method. Six Factors
were derived, among which the obvious differences in chemical
speciation were presented. Fig. 4 concluded the allocated volume
concentrations of 21 VOCs in the six Factors. It can been that Factor
1 had the high values of butanes, n-hexane, methylcyclopentane,
propene and 1-butene; Factor 2 owned the high values of butanes
and C3eC4 alkenes; Factor 3 contained most C6eC7 linear and
branched alkanes; Factor 4 mainly consisted of C4eC5 alkanes and
propene; Factor 5 was characteristic by aromatic VOCs; and Factor 6
was dominated by n-hexane, propene, benzene and toluene. Their
volume contributions to the measured 21 VOCs at sites BeC were
18.0% (F1), 15.5% (F2), 11.7% (F3), 16.4% (F4), 11.0% (F5), and 27.4%
(F6).
3.2. Characteristics of ambient VOCs at device-source areas
The VOCs pollution at 5 main device areas (CCU2, CCU3, CRU, TF
and WT) was also measured in this study, by both GCeMS system
and GCeFID system. And, the concentrations of 56 PAMS VOCs
were all obtained here. TVOCs concentrations (sum of 56 PAMS
VOCs) at the source areas were very high, about 65e434 ppbv, 57e
1924 ppbv, 63e1448 ppbv, 40e2244 ppbv, 38e768 ppbv respec-
tively for CCU2, CCU3, CRU, TF and WT. So, we ignored the inuence
of background VOCs and the VOCs transmission from other devices,
and assumed that the measured VOCs at the device area were
purely produced by the device. The chemical proles of VOCs by
volume at these source areas were calculated and introduced in
Fig. 5 (by individual species) and in Table 3 (by functional groups).
Generally, saturated alkanes were the dominant components at
these source areas, with the highest volume percentage at TF area;
unsaturated alkenes accounted for higher proportions at CCU areas;
and aromatics presented richest at WT area.
In detail, for CCU2, propene was most abundant with the highest
volume mixing ratio of 9.5%, followed by C2eC4 alkanes, n-hexane,
362 W. Wei et al. / Atmospheric Environment 89 (2014) 358e366

Fig. 2. TVOCs concentrations in the monitoring at the surrounding area.

Fig. 3. Chemical proles of 52 VOCs emitted from the renery.

Fig. 4. Allocated volume concentrations of 21 VOCs in 6 Factors analyzed by PMF.

 W. Wei et al. / Atmospheric Environment 89 (2014) 358e366 363

Fig. 5. Chemical proles of 56 VOCs measured at device areas.

364 W. Wei et al. / Atmospheric Environment 89 (2014) 358e366
Table 3
Volume percentage of functional groups of VOCs at various device areas (%).
CCU2 CCU3 CRU TF
Alkanes 62.4 67.1 75.6 79.2
Alkenes and Acetylene 19.4 23.9 16.7 16.4
Aromatics 18.2 9.0 7.7 4.4
cyclohexane, benzene and toluene, each with the volume ratio of
4.0e6.0%. These 9 VOCs accounted for about half of the total VOCs.
It could match with Factor 6 for the 21 selected VOCs in the
application of PMF analysis.
For CRU, propane and ethane were in the rst grade, with the
volume mixing ratios of 19.0% and 14.4% respectively; followed by
propene (9.1%), and n-butane(6.6%), isobutane(5.4%), n-
pentane(4.5%), isopentane(4.4%) and n-hexane (5.2%). These 8
VOCs accounted for about 70% of the total VOCs. And aromatic
compounds were little measured in the ambient air of this device.
The chemical proles of 21 VOCs at CRU area better matched with
Factor 4.
For TF, about 80% VOCs by volume were alkanes, in which pro-
pane were richest with the volume mixing ratio of 15.3%, followed
by n-butane (11.0%), ethane (9.6%), isobutane (8.4%), n-pentane
(6.6%), isopentane (5.8%), and n-hexane (4.7%). In addition, the
proportions of ethene and propene were also high, both being
about 5.0%. It could be better matched by Factor 1.
For WT, the volume mixing ratios of alkanes and aromatics were
in the same level, about 49.0% and 35.9% respectively. Among these
VOCs species, benzene and toluene provided the biggest volume
contributions (both about 8.3%), followed by n-hexane (5.5%),
propene (4.2%), m,p-xylene (4.6%). In addition, there existed a lot of
C3eC12 linear and branched alkanes with the volume contribu-
tions of 1e2%. Factor 5 could match with this device in the chemical
proles of the 21 VOCs.
Finally, for CCU3, alkanes were most components, taking up
about 67% of the total VOCs by volume, and mainly consisted of C2e
C5 linear and branched members. And alkenes gave the volume
mixing ratio of 24%, of which propene were the richest, repre-
senting about 10.8%. Of aromatics, benzene and toluene were most
abundant. However, no Factors analyzed by PMF could directly
match it in chemical prole of 21 VOCs. Then, we made another
PMF analysis based on the measured VOCs data at CCU3 area
(k 22 and j 3 here), and hoped to nd its principal components.
In result, three factors (factor I, factor II, factor III) were further
analyzed, which matched with Factor 1, Factor 2 and Factor 3
(analyzed based on the VOCs data at sites BeC) by coincidence, as
shown in Fig. 6. Because CCU3 neighbors with tank farm, a group of
VOCs in Factor 1, considered as the VOCs fugitive emissions of tank
farm, were identied here. So, we assumed that the VOCs combi-
nation of Factor II and Factor III (or the combination of factor 2 and
factor 3) could represent the characteristics of VOCs emitted from
CCU3. In addition, the 21 VOCs volume concentration ratio of Factor
2 to Factor 3 was 1.3, in the same level with that value of factor II to
factor III (0.95), which also approved our above assumption.
3.3. Contributions of 5 devices to surrounding VOCs and to
photochemical ozone formation
As a result, 5 sources were identied by PMF analysis results
coupled with the VOCs measured at the device areas, including
CCU2 (F6), CCU1/3 (F2 F3), CRU (F4), TF (F1) and WT (F5). Because
the PMF analysis only included 21 VOCs and lost three important
components (ethane, ethene and propane), we further calculated
their volume contributions and mass contributions for 56 PAMS
VOCs, as shown in Fig. 7(a) and (b). It can be seen that the most
signicant source was the catalytic cracking process, three CCUs
WT totally contributing about 50.7% by volume and 51.5% by mass to
49.0
the surrounding downwind VOCs, followed by Catalytic reforming
15.1 process, tank farm and wastewater treatment process. The report
35.9 from US EPA (2008) had provided the emission factors of THC (total
hydrocarbon) for various units of the petroleum renery, concluded
in Table 4, which also implied that uid catalytic cracking units had
the highest emission rate, followed by oil/water separators in
wastewater treatment system, and storage of crude oil or gasoline
in tanks. However, due to the lack of the pertinent information for
the Yanshan renery, such as the amounts of fresh feed rened by
CCUs, the amount of wastewater treated, etc., we could not directly
calculate the VOCs emission amounts of these devices based on the
emission factors in Table 4.
Finally, with the knowledge of Maximum Increment Reactivity
(MIR) of 56 PAMS VOCs (Carter, 2009), the contributions of 5 de-
vices to photochemical ozone formation related to the VOCs
emissions were estimated in Fig. 7(c). The result showed that three
catalytic cracking units were still the most important contributors,
totally accounting for about 55.6%, followed by wastewater treat-
ment process (16.5%), catalytic reforming unit (14.7%) and the
storage of oil in tanks (13.2%). Thus, synthetically considering the
contributions of 5 devices to surrounding VOCs and to ozone for-
mation potentials, catalytic cracking units were suggested to be
given the VOCs control rstly.
However, the source apportionment results also carried some
uncertainties. As mentioned above, the Factor number of 6 in the
application of PMF was determined by the match of decomposed
Factor proles with the measured data, but not by the count of
actual sources. It seemed to miss some sources, such as the back-
ground VOCs, the exhaust gas of boilers and engines which con-
taining VOCs, and so on. Here, considering the VOCs contributions
of these unidentied sources were very little, our results concluded
above were still thought to be acceptable.
4. Conclusions
A eld VOCs measurement for a petroleum renery in Beijing
was conducted in this study, and the characteristics of VOCs
emitted both from the whole renery and from its inner main de-
vices were obtained. The results showed that the inuence of the
renery on the surrounding ambient VOCs was greatly important,
with the average TVOCs increase of 61 ppbv during the monitoring
period. The VOCs emitted from the whole renery were charac-
teristic by isobutane (8.7%), n-butane (7.9%), isopentane (6.3%), n-
pentane (4.9%), n-hexane (7.6%), C6 branched alkanes (6.0%), pro-
pene (12.7%), 1-butene (4.1%), benzene (7.8%), and toluene (5.9%) by
volume, which could be comparable with the research results of Liu
et al. (2008) on another renery in south of China. On the other
hand, 5 devices (CCU2, CCU3, CRU, TF, WT) related to VOCs emis-
sions also received attentions in this study. Several hundred ppbv of
ambient TVOCs at these device areas were measured. And the
obvious differences in VOCs chemical proles among these devices
were found, CCUs with the higher proportions of C2eC5 alkanes,
C3eC4 alkenes, and BT (benzene and toluene), CRF with the higher
proportions of C2eC3 alkanes and propene, TF with the higher
proportions of C2eC6 n-alkanes, WT with the higher proportions of
BTEX (benzene, toluene, ethylbenzene, m,p,o-xylene).
Then, PMF model was applied based on the 94 measured VOCs
data at the surrounding downwind sites, for the source appor-
tionment of VOCs in the renery. Totally, six Factors were identied,
which chemical proles could better match with the measured data
at the device areas. Thus, the Factor contributions decomposed
were thought of as the emission contributions from the
 W. Wei et al. / Atmospheric Environment 89 (2014) 358e366 365

Fig. 6. Three factors analyzed by PMF based on ambient VOCs at CCU3 area.

corresponding devices. Considering the PMF only included 21
VOCs, we had to calculate the volume and mass contributions of 5
devices to 56 PAMS VOCs at the surrounding downwind area, CCUs
identied as the biggest contributors. This result was accordant
with the research of US EPA (2008), which implied that catalytic
cracking process had the highest VOCs emission rate. In addition,
for VOCs as the important precursors for the photochemical ozone,
the ozone formation potentials of the 5 devices were also calculated
by MIR technique. CCU2, CCU1/3, CRU, TF, WT, accounting for about
29.6%, 26.0%, 14.7%, 13.2% and 16.5%, respectively. It suggested that

Fig. 7. (a), Volume contributions of 5 devices to 56 surrounding downwind VOCs (b), mass contributions of 5 devices to 56 surrounding downwind VOCs (c), contributions of 5
devices to photochemical ozone formation.
366 W. Wei et al. / Atmospheric Environment 89 (2014) 358e366

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This research was supported by National Natural Science
representative regions of China observed from space by the Tropospheric
Foundation of China (No. 51108006), Ph.D. Programs Foundation of Emission Spectrometer (TES), 2005e2010. Chin. Sci. Bull. 57, 1454e1461.
Ministry of Education of China (No. 20111103120008), and the State Shie, R.-H., Chan, C.-C., 2013. Tracking hazardous air pollutants from a renery re
by applying on-line and off-line air monitoring and back trajectory modeling.
Environmental Protection Key Laboratory of Sources and Control of
J. Hazard. Mater. 261, 72e82.
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for providing VOCs measurement by using GC-FID analyzer system. of receptor models for source apportionment of volatile organic compounds in
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Tang, G., Li, X., Wang, Y., Xin, J., Ren, X., 2009. Surface ozone trend details and in-
terpretations in Beijing, 2001e2006. Atmos. Chem. Phys. 9 (22), 8813e8823.
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