Volatile Emissions from Hot
Bitumen Storage Tanks
François Deygout
SHELL Bitumen, Immeuble ‘‘Portes de la Défense’’, 307 rue Estienne d’ORVES, 92700 Colombes,
France; francois.deygout@shell.com (for correspondence)
Published online 1 June 2010 in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ep.10444
The purpose of this study is to estimate the fugitive
volatile organic compounds (VOCs) emitted from hot
stored bitumen and to assess the contribution of these
VOCs on the overall emissions in refinery processes.
All the usual information regarding VOC emissions
from tank storage is based on the storage of petro-
leum products at ambient temperature (mainly vola-
tile streams such as fuels), and all the calculation sys-
tems used to predict or estimate the emissions are
based on daily or seasonal temperature variations.
Consequently, a dedicated protocol for hot bitumen
storage using measurement-based estimations was
established. Tank headspace compositions were also
determined. Some annual emissions were estimated
and comparisons were made with current emission
factor-based methods.
The atmospheric VOC emissions from hot stored bi-
tumen were shown to be made of residual petroleum
compounds. The experiments demonstrated that vola-
tile emissions are more bitumen related than temper-
ature dependent in the studied temperature range.
The experiments also showed VOC depletion over
time. Storage duration is the predominant factor
affecting VOC emission levels. Another main outcome
concerns the influence of differences in the manufac-
turing process between oxidized and nonoxidized
bitumens, with the blowing operation decreasing the
VOC contents by stripping. Finally, it is shown that
hot bitumen storage tanks make a low contribution to
the overall fugitive VOC emissions in a refinery pro-
cess. Ó 2010 American Institute of Chemical Engineers En-
viron Prog, 30: 102–112, 2011
Keywords: VOC, fugitive emissions, bitumen stor-
age tanks, ozone precursor
Ó 2010 American Institute of Chemical Engineers
102 April 2011 Environmental Progress & Sustainable Energy (Vol.30, No.1) DOI 10.1002/ep
INTRODUCTION
Reduction of nonmethane volatile organic compound
(NMVOC) emissions is on the agenda of several Euro-
pean forums and is the objective of several protocols
and policy plans [1]. NMVOCs are known to have a det-
rimental impact on the environment, mainly as tropo-
spheric ozone precursors. EU policy on air quality is
aimed at implementing the control of emissions from
stationary industrial sources, and promoting and inte-
grating environmental protection requirements in the
industrial, transport, and energy sectors is part of these
aims. Refineries are regarded as sources of NMVOCs
due to fugitive emissions from piping systems (leakage),
wastewater systems, storage tanks (evaporation, breath-
ing), and loading and unloading systems [2]. Industrial
companies such as Shell have issued technical guides
for assessment, monitoring, and control of pollutants
and VOCs [3]. These guides are mainly dedicated to
emission losses from streams stored at ambient tempera-
tures, such as fuels, and not for hot stored streams,
such as bitumen/asphalt. All the calculation systems
used to predict or estimate the emissions are based on
temperature variations to calculate average emission fac-
tors. Usually, evaporation losses from hot bitumen stor-
age are not regarded as fugitive emissions, even though
tanks for the hot storage of hydrocarbon liquids pro-
duce emissions to atmosphere either from vent ports,
imperfect sealing arrangements or tank fittings. Accord-
ing to US Environmental Protection Agency (EPA)
reports [4], the major direct process emission sources of
airborne compounds from bitumen-related operations
in refinery processes are vacuum distillation, catalytic
cracking, coking, and asphalt blowing. Can evaporative
losses from refinery bitumen tankage represent a signifi-
cant proportion of the total loss? There is little informa-
tion in the literature about actual values, and it is the
purpose of this study to estimate where there are signifi-
cant emissions of NMVOC from hot stored bitumen and
to characterize the main emitted materials.
STRATEGIES FOR ASSESSING STATIONARY VOC EMISSIONS: MODEL
AND SAMPLING
As there is no dedicated protocol for such work,
some scouting investigations were conducted on the
environmental legislation. The European Network for
the Implementation and Enforcement of Environmen-
tal Law (IMPEL) is an informal network of European
regulators concerned with the implementation and
enforcement of environmental legislation. IMPEL has
issued a relevant VOC-related document [5]. The
IMPEL guidance report reviews estimation methods
and focuses on methods to identify leaks and meth-
ods to estimate annual emissions. According to the
IMPEL recommendations, the best protocol is a com-
bination of calculations and actual experiments: (i)
VOC sampling and analysis (quantification and char-
acterization) by using portable monitoring equip-
ment, e.g., air sampling or FID analyzers, (ii) calcula-
tions of the standing storage losses by using the
results of the measurements, and (iii) overall assess-
ment with calculation methods. This was the method
used for the present work: with the help of the meas-
ured concentrations for typical bitumen representa-
tives, the annual emissions for a given location can
be estimated by calculation. In addition, as previously
described in the literature [6], the process used to
make bitumen was also thought to have an impact
on emitted NMVOCs. This led to the selection of sev-
eral current bitumens manufactured from different
processes: a straight-run bitumen (SR) resulting from
the distillation process; an oxidized bitumen (OB),
which is air blown after distillation: and a visbreaker-
cracked residue (CR).
Depending on the storage temperature, bitumen
storage tank can be either free venting or blanketed
with an inert atmosphere for safety reasons (e.g.,
steam commonly available in a refinery). All the bitu-
men storage tanks of the studied location were steam
blanketed. Since the steam flow rate is known, this
made the emission quantification easier. For nonblan-
keted tanks, fugitive emissions are due to ‘‘breathing’’
losses (also called standing losses). The latter corre-
spond to the expulsion of vapor from a tank through
vapor expansion caused by changes in temperature
and pressure (storage tanks used to store heated liq-
uid bitumen are usually equipped with fixed roofs).
Emissions certainly depend on the ventilation system,
such as forced systems (steam or nitrogen blanket-
ing). However, it was assessed that the breathing rate
could lead to similar emissions as forced ventilation,
since the changes in ambient conditions also result in
in-breathing and out-breathing especially for large
nonventilated tanks.
This study was also an opportunity to make com-
parisons between field measurements and calculation
methods using breathing emission factors, as this had
already been done in the same area [6]. These calcu-
lations based on daily or seasonal temperature varia-
tions are specifically dedicated to cold storage for
tanks with nonforced ventilation (tank size-related
emissions). IMPEL highlights the AP-42 guidelines of
the US EPA [7], which are widely used in the EC, as
well as the emission-estimating equations that have
Environmental Progress & Sustainable Energy (Vol.30, No.1) DOI 10.1002/ep
Figure 1. Sampling train for field analysis.
been developed by the American Petroleum Institute
(API) [8]. The AP-42 document recommends the use
of a specific procedure to calculate emission factors
from storage tanks [9]. However, for these calcula-
tions, the vapor pressure of hot bitumen is required.
Based on AP-42, the US company Owens Corning
developed an in-house method in 1998 [6] to estimate
their bitumen tank emissions. Owens Corning made
some additions to more accurately calculate the vapor
pressure of hot bitumen, which is difficult to assess
(blend of many single compounds). Similarly, the
original API equation about breathing losses for pas-
sive fixed roof tanks [see Refs. 7 and 10 (Chapter 4)]
was used with the vapor pressure estimates from
Owens Corning. This API breathing loss equation has
been used historically. It is based on the assumption
that the breathing loss is a function of the vapor pres-
sure of the stored liquid, tank diameter, vapor space
outage, ambient temperature, and the tank paint
color and conditions. In addition, further investiga-
tions were conducted on the laboratory scale. This
laboratory work was thought to confirm some ten-
dencies observed in the field such as the VOC deple-
tion phenomenon, as will be seen later in the article.
The idea was to mirror actual storage conditions to
examine the emission behavior.
EXPERIMENTAL PROCEDURES
Field VOC Collection and Characterization
The technique described in the literature to collect
volatile compounds is commonly based on a sam-
pling train using an adsorbent cartridge followed
by thermal desorption and chromatographic analysis
(gas chromatography with FID or mass spectrometry
detection, GC/FID/MS). Therefore, the measurements
consisted in an online measurement of the emitted
component/hydrocarbon concentrations currently
blown into the environment from the vents. The sam-
pling train used here for VOC collection and mea-
surement is shown in Figure 1. As the tanks were
blanketed, a ‘‘condensation train’’ was added: two
flasks filled with chilled distilled water. The sampling
lines were not heated. The gas flow was around
300 L/h to collect steam. Pumping duration was
about 10 min. The flasks were weighed at room tem-
April 2011 103
perature before and after collection. VOC collection
was performed by using two adsorption tubes
(Supelco Carbotrap 300, 4 mm in internal diameter,
and 17.8 cm in length) packed with specific adsorb-
ent beds (Carbosieve S-III, Carbotrap B, and Carbo-
trap C). A second tube in line was used to check for
any breakthrough. The gas flow was 50 mL/min. The
temperature after cooling down in the line was 258C.
An oxygen meter was used to verify the oxygen con-
centration level in the dried atmosphere. It was found
to be around 19.5/20 vol %, which normalizes the
collected volume in the absence of steam (Nm3).
The total VOC content was online determined with
the help of an FID analyzer (Graphite 730 from
Cosma) after removing the adsorption tubes. These
online measurements were expressed at the ppm
level in dry atmosphere. FID calibration was done in
accordance with the supplier’s instructions using a
methane standard (0.41 vol % of CH4 in the air).
Some trapped VOCs were further characterized by
GC-MS, which consists of thermal desorption (Gerstel
TDS2), a PTV injector (Gerstel CIS4) and a gas chro-
matograph (Varian VF 5MS column, 60 m 3 0.32 mm
3 1.0 lm) coupled with a mass spectrometer (Agilent
6890/Agilent MS 5973). The tubes were first condi-
tioned (30 min at 3508C under a helium flow rate of
100 mL/min).
VOC Emission on the Laboratory Scale
The experimental setup was built around the Shell
laboratory rig, which has been described previously
[11]. This rig is generally used for direct fume genera-
tion and prediction of fume emissions (organic partic-
ulate fractions). To mirror the field conditions, an
inert gas was required and nitrogen flow was used as
forced ventilation, and the headspace atmosphere
was passed through an adsorbent tube (Supelco
Orbo 43 or equivalent), which trapped the emissions.
A stirrer was used to homogenize the temperature
and to measure the influence of binder movement on
the emissions. The binders used in this laboratory
study were sampled from the tanks during the field
experiments: 400 g of sample preheated to 1208C in
the reaction vessel. The measurements were con-
ducted at a temperature close to the storage tempera-
ture in the field (around 190–2008C). The stirrer was
set at 60 rpm, the N2 flow rate at 1.2 L/min, the head-
space sampling rate at 1.0 L/min, and a sampling
time of 60 min was chosen for each sampling. The
randomly sequenced sampling time was set up from
1 h (first sample) to about 1 week for the final one
with a stop at the end of each testing day. Because of
the regular stops, the time to renew the air volume
above the bitumen was not regarded as influential.
The front and back sorbent sections were desorbed
with 1.0 mL of methylene chloride for at least 30 min,
and GC-FID analysis was conducted on the collected
VOCs.
The retention times were tabulated from a calibra-
tion standard blend (n-paraffins in methylene chlo-
ride) versus their respective boiling points for the
determination of the C4–C14 window. The injection
104 April 2011 Environmental Progress & Sustainable Energy (Vol.30, No.1) DOI 10.1002/ep
of calibration standard blends at three concentrations
enables determination of the FID response (n-paraf-
fins have a response similar to that of VOC) for quan-
tification (peak surface integration). Probably due to
the stirring speed used to homogenize the tempera-
ture (60 rpm) compared to the small vessel volumes,
the laboratory emissions were sometimes a little
larger than the common C4–C14 window for
NMVOCs emitted in the field (entrained heavier com-
pounds such as coarser organic particulates). In that
case, quantification (peak integration) was done up
to the C14 limit, whatever the tail of the emission
profile was. GC-MS characterization was also con-
ducted on the samples collected from the laboratory
rig test.
CALCULATIONS
Yearly Emitted VOCs in the Air
Since the studied bitumen tanks were steam blan-
keted, the steam pumped volume was used for the
VOC content calculation in the emissions (steam flow
rate of 30 m3/h). The specific volume of steam is
1.8 m3/kg or 1.8 L/g. Therefore, it is possible to cal-
culate the steam pumped volume:
Steam pumped vol. 5 (steam mass) 3 1.8. The
steam, nitrogen, and oxygen contents in the tank
headspace can be calculated as follows:
Vol % steam ¼ ½ðcalculated steam vol:Þ=
ðdry pumped vol: þ steam vol:Þ
3 100
Vol % O2 ¼ ½ðdry pumped vol:Þ 3 0:19=
ðdry pumped vol: þ steam vol:Þ
3 100
where 0.19 is the common oxygen level in the air
and has been verified experimentally.
Vol % N2 ¼ ½ðdry pumped vol:Þ 3 0:81=
ðdry pumped vol: þ steam vol:Þ
3 100
where 0.81 is the common nitrogen level in the air.
From the total NMVOC content determined with
the FID analyzer, ‘‘dry’’ VOC concentration (after
steam condensation) is measured online at the ppm
level in dry atmosphere. The ppm value is first con-
verted into mg/m3. For a given compound, the equiv-
alences are: (ppm) 5 (mg/m3) 3 V/Mw, where Mw is
the molecular weight of the compound and V is its
molar volume at the given pressure. The molar vol-
ume calculation follows the ideal gas law in which R
is the gas constant. For a given compound at two dif-
ferent temperatures, the number of moles, n, is the
same. If we assume that the atmospheric pressure is
constant, we have: V1/V2 5 T1/T2 with V1 5 22.4 L at
273 K (08C). Consequently, the volume at the sam-
pling temperature (258C) is 24.45 L. A key factor is
the mean value for Mw because the gas is a blend of
hydrocarbons, and an average value is required. The
Table 1. Carbon number distribution of the NMVOC emissions.

C number C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 Average

Mw (g) 58 72 86 100 114 128 142 156 170 184 198
OB 0% 1% 3% 9% 26% 28% 25% 7% 1% 0% 0% 125
CR 0% 7% 6% 8% 16% 20% 28% 15% 0% 0% 0% 125
SR 0% 3% 1% 12% 30% 20% 19% 12% 1% 1% 1% 126

OB, Oxidized bitumen; CR, visbreaker-cracked residue; SR, straight-run bitumen.

Table 2. Calculated steam, nitrogen, and oxygen concentrations in blanketed tanks.

Oxygen
Tank Pumped Mass of content Calculated Calc. Calc. Calc.
Storage Tank vol. dry condensed in dry steam steam nitrogen oxygen
Binder temp. volume used vol. steam gas volume content content content
type (8C) (m3) (m3) (L) (g) (vol %) (L) (vol %) (vol %) (vol %)
OB 195 1090 900 25.5 139 19.5 250 91 7 2
CR 205 285 210 40 51 20 92 70 25 5
SR 191 6000 5100 37 150 19.5 270 88 10 2

carbon number distribution was determined using

gas chromatography with a mass detector (GC-MS).
This technique enables calculations of the molar mass
of the compounds and their relative contents in the
headspace. The results are presented in Table 1 for
the three studied binders showing molecular masses
around 125 g/mol. With the help of these average
molecular masses, the NMVOC concentrations were
given in mg/m3 and the yearly emissions were calcu-
lated.

API and AP-42 Breathing Loss Calculations

As previously discussed, the Owens Corning addi-
tions (estimates of the vapor pressure and the bitu-
men surface temperature) were used in the present
work when comparing the established measurement-
based method with the EPA and API calculations. The
previously determined molecular mass was used in
the calculations (125 g/mol). Calculation details are
given in Appendices A and B for a straight-run resi-
due stored at 1918C.
RESULTS
The calculated steam, nitrogen, and oxygen con-
centrations are given in Table 2. Figure 2 shows the
carbon number distributions in the headspace for the
three bitumen types. The carbon number range is C5
to C14. There are no large differences in carbon
ranges between the binder types. The NMVOC con-
centrations in mg/m3 are given in Table 3. Significant
lower VOC emission values were determined for SR
having several months of hot storage (results not
shown, down to 10 g/h). Since the VOCs are resid-
uals, it was supposed that there was depletion in the
emissions. The conducted set of laboratory experi-
ments was able to mirror the VOC depletion over
Figure 2. Carbon number repartition in the headspace
(mass %).
time. Figure 3 shows the overall depletion obtained
for SR at 1808C with a sequenced sampling (four
sequences from 0 to 25 h), and Figure 4 shows the
quantified levels of emissions over time. The highest
measured concentrations in this study were found for
binders having the shortest storage time. The values
reported here in Table 3 were measured from ‘‘fresh’’
binders, i.e., having short storage times after the dis-
tillation process (i.e., a few days).
The GC-MS analyses identified about 100 different
compounds present in bitumen and coming from
crude oil. Table 4 shows the relative contents of sev-
eral current categories of compounds known to be
NMVOCs. Only about half of these residual com-
pounds were firmly determined due to the large

Environmental Progress & Sustainable Energy (Vol.30, No.1) DOI 10.1002/ep April 2011 105
Table 3. Calculated NMVOC concentrations and emissions.
Binder type Dry VOCs (ppm) Wet VOCs (mg/m3)
OB 279 1428
CR 1103 5630
SR 1133 5792
Figure 3. Four sequences from 0 to 25 h VOC
emissions chromatograms showing the depletion
over time (SR at 1808C).
number of individual compounds present in the
headspace (significant level of background). Alkanes
and, to a lesser extent, alkenes represent the main
part of the emissions. The percentage of sulfur-based
compounds can vary depending on the binder:
repeated analysis on several SRs showed average
contents from 0.1 to 5 mass %. Lighter aromatic com-
pounds with BTEX (benzene, toluene, ethylbenzene,
and xylene) can represent up to about 6% of the
emitted vapor phase concentrations. The resulting
emissions calculated from the API and AP-42 equa-
tions are given in Table 5 for several storage tempera-
ture ranges. They are compared with the figures
obtained from the measurements.
DISCUSSION
As defined in EC Directive 1999/13/EC, VOC is
any organic compound having a vapor pressure of
0.01 kPa or more at 293.15 K, or having a corre-
sponding volatility under the particular conditions of
use. The present carbon number range is C5–C14,
which is in agreement with the NMVOC definitions.
Similar tendency was observed in a study where bitu-
men fumes were generated on the laboratory scale
[12]. NMVOCs were found to be essentially aliphatics
(from C7 to C17, 27% of fumes) and monoaromatic
derivatives (4% of fumes). Owens Corning deter-
mined an average molecular mass value of the vapor
of 84 g/mol, which is very close to n-hexane [6]. The
present C5–C14 fraction corresponds more to a resid-
ual fuel cut such as gasoline with an average molar
mass of about 125 g (close to n-nonane). The vola-
tiles that make up the VOC fraction are residuals after
the distillation process, since the physical separation
106 April 2011 Environmental Progress & Sustainable Energy (Vol.30, No.1) DOI 10.1002/ep
Emitted VOCs (g/h) Emitted VOCs (kg/yr)
42.8 375
168.9 1480
173.8 1522
Figure 4. Quantitative depletion over time (SR at
1808C).
process is not perfect under common operational
conditions. Owens Corning included in their calcula-
tions a partition of the organic emissions in organic
particulates and VOCs [6]. The carbon distribution
determined in the present work only refers to vola-
tiles.
The profiles obtained were analogous for both the
laboratory rig test and field samples. No diaromatic
(e.g., naphthalene) or polyaromatic compounds were
determined in the tank headspaces, since it can be
one of the main aromatic volatile compounds found
during asphalt worker monitoring [13]. However, the
presence of naphthalene was noted on the laboratory
scale in the volatiles at 1608C, but only with a
doubled stirring speed of 120 rpm (about 5 mass %).
Thus, a segregation phenomenon can explain the
absence of polyaromatic emissions via the atmos-
pheric events. The volatile compounds can be segre-
gated by their molecular mass/vapor pressure. Naph-
thalene and more generally diaromatics are in the
upper range of the VOC definition (vapor pressure
below 0.01 kPa). In an attempt to collect fume con-
densates from tank storage that were fully representa-
tive of actual field fumes, condensates were first col-
lected in the vapor space above a heated storage
tank approximately half-filled [14]. Comparison of the
polyaromatic contents and the boiling point distribu-
tion showed considerable differences with workplace
samples. It was necessary to set up a specific sam-
pling pipe 10 cm above the bitumen surface to finally
get representative condensates. In addition, a study
showed that compounds having a Henry’s Law con-
stant, H, in a lower range (i.e., <0.1), which is the
case for naphthalene (H 5 0.017), were subject to
external influences in their volatilization rates, which
are usually governed by the mass transfer coefficient
Table 4. Main identified NMVOC categories (mass %).

Binder Thiophenes Other Other

type H2S/SO2 and disulfides BTEX monoaromatics Alkanes Alkenes compounds
OB 2 7.1 6.1 1.2 59.2 20.7 3.7
CR 0.1 13.5 13.9 2.8 45.6 14.8 9.3
SR 0.8 7.9 12.5 1 51.3 23.8 2.7

BTEX, benzene, toluene, ethylbenzene, and xylene.

Table 5. Emitted NMVOC estimations from the present, the API and AP-42 methods.

Present calculations for

free venting or
blanketed tank with 30 API calculations*,** AP-42 calculations*,**
NMVOC m3/h steam (nonsize for free-venting for free-venting tank
emissions (kg/yr) relative) tank (V 5 6000 m3) (V 5 6000 m3)
Temperature
range SR/CR OB SR OB SR OB
170–1908C 1500 400 1500–2650 1550–2550 600–1200 600–1100
150–1708C 1500 400 825–1500 900–1550 250–600 300–600
130–1508C 1500 400 425–825 500–900 100–250 150–300
Average 1125 1200 400 400

*108C of daily temperature difference.

**Modified with some additions from Owens Corning (vapour pressure calculations).

and the compound concentration in the bulk liquid:
for instance, the gas resistance/air turbulence or the
affinity of the considered compound with the liquid
phase [15]. This demonstrates that the headspace
composition is not homogeneous and can explain the
absence of known volatile compounds in the emis-
sion directly blown in the atmosphere via the vents.
In investigating emissions of polycyclic aromatic
compounds from batch hot mix asphalt plants [16],
naphthalene was determined at a level of 300 lg/m3,
which is significantly higher than the concentrations
usually measured during paving operations (<20 lg/
m3) [13]. This reinforces the tendency of observed re-
sidual volatile compounds contained in fresh bitumen
and progressively emitted during the handling opera-
tions of the asphalt mixture. Then the storage dura-
tion of the binder appears to be one of the predomi-
nant factors acting on VOC emission levels. The
depletion of the laboratory emissions is not usually
observed for the organic particulates generally col-
lected with the help of a filter cassette (these coarser
particulates and VOCs make up the organic part of
bitumen fumes). Usually, the rig testing shows contin-
uous matter collection on the filter over time, with
the depletion being specifically VOC-related.
The temperature that governs the particulate emis-
sions in the field [11] was not noted to impact the
VOC emissions. The set of laboratory experiments
showed that the rotational speed of the stirrer acted
more as a facilitator for NMVOC emissions (binder
movement) than does temperature in the studied
temperature range (up to 1808C). Comparative
experiments showed 50% higher emissions when
doubling the rotational speed (60–120 rpm). It was
not possible to verify the influence of an additional
factor described in the literature (e.g., EPA): the sur-
face area of bitumen in contact with the headspace,
which can have a significant influence on emissions
for large tanks.
Oxidized bitumen shows lower emissions. As
such, Owens Corning describes lower VOC contents
in the gaseous emissions of oxidized bitumens [6].
The blowing operation strips the binder, even though
some new compounds can be produced during this
operation, resulting in lower VOC contents. Two
additional binders were laboratory tested to mirror
and quantify the blowing effect on the volatile emis-
sions (bitumen feed and resulting 100/40 oxidized
bitumen). The average measured laboratory emis-
sions were found to be 130 and 43 mg/m3 for the
feed and the resulting 100/40 oxidized binder, respec-
tively. These laboratory experiments confirmed the
VOC decrease after blowing. This observed decrease
(about 66%) was greater than that determined by
Owens Corning with the help of a combustion meter-
based method (on average 52% less VOC for OB [6]).
The AP-42 and API calculation methods are tem-
perature-related, because there is a high impact of
the vapor pressure with regard to the temperature for
liquid petroleum streams stored at ambient tempera-
ture. For the current temperature range used for hot
bitumen (currently up to 2308C), API average esti-

Environmental Progress & Sustainable Energy (Vol.30, No.1) DOI 10.1002/ep April 2011 107
mates were found to be in the same range as the
highest field values determined on blanketed, stored
straight-run, and cracked residues for a 6000 m3 tank
(around 1200 kg/yr). On the other hand, AP-42 aver-
age estimates were similar to field values for oxidized
bitumen (400 kg/yr). The two calculation methods
framed the actual determinations in the field only
when using average temperature values for storage.
Overall, the API calculation method overestimates the
emissions compared to AP-42. API is less detailed.
For instance, the molecular weight of the vapor is not
tackled. On the other hand, AP-42 tends to underesti-
mate the actual emissions at a given temperature.
For both methods, the nature of the binder and the
storage duration are not tackled. At the recorded field
temperature (around 1908C), API significantly overesti-
mates the emission by a factor of 6 for OB and almost
2 for the two other bitumens. At that temperature, the
AP-42 estimations are more accurate and are similar to
the measurements for SR and CR. Owens Corning
found an overall overestimate by using AP-42, but the
bitumen nature is not specified for the reported esti-
mates [6]. Also, AP-42 calculations highly depend on
the tank vapor space volume (stock liquid height). For
instance, at 1908C the emissions pass from 1200 to
2900 kg/year if the tank holds on average 5100 m3 and
1000 m3, respectively. The article does not sufficiently
describe the features and conditions for further com-
parison. In conclusion, the measurement-based esti-
mates have to be considered as more reliable for hot
stored bitumen than those based on average emission
factors only. In any case, AP-42 could be used as a sur-
rogate for SR and CR.
The present experiments also demonstrated that
volatile emissions are more bitumen-related than tem-
perature-dependent in the studied temperature range.
Consequently, the determined emission values will
be kept for lower temperature ranges. As such, 5000
mg/m3 will be regarded as a reference value for
straight-run and cracked residues in a temperature
range around 130–1908C. For oxidized bitumen, this
value will first be decreased by the ratio of 3
observed during the laboratory experiments (about
1670 mg/m3). Then, when compared with the actual
measurement (1428 mg/m3), an average value of
1500 mg/m3 can be chosen as representative. It can
be assumed that this concentration could be a maxi-
mum value for free-venting tanks or tanks with active
ventilation based on the maximum concentrations
measured on freshly processed bitumens.
In conclusion, the VOC concentration reference
values for each monitored blanketed tank with the
setup steam flow rate are 1500 kg/yr for straight-run
and cracked residues and 400 kg/yr for oxidized bitu-
mens. These estimates can be used to calculate the
overall emissions from some facilities independently
of the storage temperature.
The estimated emissions attributable to hot bitu-
men storage were found to be around 5% of the
overall NMVOC emissions for the fully integrated re-
finery complex studied here. This contribution is sig-
nificantly lower than that usually attributable to other
refinery material storage (can exceed 40% [1]), which
108 April 2011 Environmental Progress & Sustainable Energy (Vol.30, No.1) DOI 10.1002/ep
means that hot bitumen storage is not a priority for
the VOC emission abatement policy. The contribution
of fugitive emissions at the site level can vary, but
these seem to have a constant impact in the energy
sector. For instance, the European Environment
Agency estimated the contribution of either the pro-
duction processes or the distribution of refinery prod-
ucts to be 8% of the overall NMVOC emissions [17].
CONCLUSION
With the help of laboratory experiments that con-
firmed the observed field tendencies, the atmospheric
NMVOC emissions from hot stored bitumen were
shown to be made of residual petroleum compounds
depleting over time during storage. An alternative
method using both actual field measurements and
emission calculations was preferred to estimate the
yearly emissions into the environment. More accurate
emission factors were determined for such hot stored
petroleum streams than those usually used for much
more volatile products stored at ambient temperature
such as fuels. Finally, it is shown that hot bitumen
storage tanks make a low contribution to the overall
fugitive VOC emissions in a refinery process.
APPENDIX A: BREATHING LOSS API CALCULATIONS FOR PASSIVE
FIXED ROOF TANK (WITH SOME ADDITIONS FROM OWENS CORNING)
Purpose
To determine the emission rate of the total product
mixture for a chemical mixture stored in a vertical
dome roof tank. The chemical mixture is a straight-
run residue bitumen.
Main Features
The tank is 22.5 m in diameter (73.80 ft), 15 m
high (49.20 ft), holds about 12.75 m of product (41.83
ft), and its dome roof is made of fugitive aluminum.
The tank working volume is 6000 m3 (holds 5100 m3
of bitumen). The storage temperature is 1918C. The
daily temperature variations are assumed to be about
108C (188F).
Calculations of the Standing Storage Loss
The net breathing loss can be estimated by apply-
ing the following API equation:
Lbreathing ¼ 0:0226 3 Mv 3 ½PV =ðPA  PV Þ
0:68
3 D1:73 3 HV0:51 3 DT 0:5 3 Fp 3 C 3 Kc
where Lb is the daily breathing loss (lb); Mv, stock
vapor molecular weight (lb/lb-mole); Mv 5 0.264 lb;
PV, vapor pressure of stored liquid at bulk liquid con-
ditions (psia); PA, average atmospheric pressure at
tank location (psia); PA 5 14.7 psia; D, tank diameter
(ft); D 5 73.80 ft; HV, average vapor space height,
including roof volume correction (ft); DT, average
ambient diurnal temperature change (8F); DT 5 188F;
Fp, paint factor, dimensionless; Fp 5 1.39 for fugitive
aluminum; C, adjustment factor for small diameter
tanks, D < 30 ft, dimensionless; Kc, product factor,
dimensionless (for all organic liquids, the product fac-
tor default is 1.0; 0.75 for crude oils).
Vapor Pressure Calculation, PV
Because the exact composition of the bitumen
mixture is unknown, Owens Corning assessed the
vapor pressure of three basic classes of bitumen ma-
terial [6]: flux bitumen, paving bitumen, and oxidized
bitumen. Regressions were calculated for each binder
type using the Clausius Clapeyron equation:
Ln P V ¼ a  b=T
where PVA is the equilibrium vapor pressure (in mm
Hg); T, the absolute temperature (8R); a and b, con-
stants (depending on the pressure and temperature
units): Flux: a 5 18.2891, b 5 12725.60. Paving: a 5
20.7962, b 5 15032.54. Oxidized: a 5 18.8642, b 5
13458.56. In our case (paving bitumen): Ln PV 5
20.7962–15032.54/836; PV 5 16.62 mm Hg 5 0.321 psi.
Vapor Space Height HV Calculation for a Cone Roof
For a cone roof, the vapor space, HV, is calculated
by:
HV ¼ HS  HL þ HRO
HS 5 tank shell height, 49.20 ft (given); HL 5 stock
liquid height, 41.83 ft (given); HRO 5 roof outage;
HRO 5 1/3; HR 5 1/3(SR)(RS); SR 5 tank cone roof
slope, 0.0625 ft/ft (given); RS 5 tank shell radius 5
½; D 5 36.9 ft; HRO 5 1/3(0.0625)(36.90) 5 0.769 ft.
Then, to calculate HV: HV 5 49.20 – 41.83 1 0.769
5 8.139 ft.
Vapor Space Height HV Calculation for a Dome Roof
 2
HRO ¼ HR ð1=2Þ þ ð1=6ÞðHR =RS Þ

1=2
HR ¼ RR  RR2  Rs2
where RR is the tank dome roof radius. Section 3.10.6
of API Standard 650 indicates that the tank dome roof
radius, RR, varies between a minimum of 0.8D and a
maximum of 1.2D. If the tank dome roof radius is not
known, a typical value of 1.0D may be assumed. In
this case, the equations are simplified:
HR ¼ 0:268; Rs ¼ 9:89 ft; HRO ¼ 0:137; RS ¼ 5:06 ft
HV ¼ 49:20  41:83 þ 5:06 ¼ 12:43 ft
Net Breathing Loss Lbreathing Calculation for a Dome Roof
Lbreathing ¼ 0:0226 3 0:264 3 ½0:321=ð14:7  0:321Þ
0:68
3 73:81:73 3 12:430:51
3 180:5 3 1:39 3 1 3 1
Lbreathing ¼ 16:35 lb=day or 2712 kg=yr
Environmental Progress & Sustainable Energy (Vol.30, No.1) DOI 10.1002/ep
APPENDIX B: CALCULATIONS USING THE AP-42 METHOD FOR
CHEMICAL MIXTURES IN A FIXED ROOF TANK (WITH SOME ADDITIONS
FROM OWENS CORNING)
Note: The equation numbers refer to the AP-42
final report issued in 2006; see http://www.epa.
gov/ttn/chief/ap42/ch07/final/c07s01.pdf.
Purpose
To determine the emission rate of the total product
mixture for a chemical mixture stored in a vertical
dome roof tank. The chemical mixture is a straight-
run residue bitumen.
Main Features
The tank is 22.5 m in diameter (73.80 ft), 15 m
high (49.20 ft), holds about 12.75 m of product (41.83
ft), and its dome roof is made of aluminum. The tank
working volume is 6000 m3 (holds 5100 m3 of bitu-
men). The storage temperature is 1918C (3768F or 836
8R). The number of turnovers per year for the tank
can also be used to calculate the working loss.
Calculations of the Standing Storage Loss
The product is made up of organic liquids, all of
which are miscible in each other, which makes for a
homogenous mixture if the material is well mixed.
The tank emission rate will be based on the proper-
ties of the mixture. Raoult’s law is assumed to apply
to the mixture and will be used to determine the
properties of the mixture.
For a vertical, fixed roof storage tank, the follow-
ing equations apply:
LT ¼ LS þ LW (3-1)
LS ¼ 365WV  VV  KE  KS (3-2)
LW ¼ 0:0010 MV  PVA  Q  KN  KP (1-29)
where LT is the daily total loss (lb); LS, daily standing
storage loss (lb); LW, daily working loss (lb); and VV,
tank vapor space volume (ft3).
VV ¼ p=4D2 HVO (3-3)
WV 5 vapor density (lb/ft3).
WV ¼ ðMV  PVA Þ=ðR  TLA Þ (3-21)
KE 5 vapor space expansion factor, dimensionless
KE ¼ ðDTV =TLA Þ þ ððDPV  DPB Þ=ðPA  PVA ÞÞ (3-7)
KS 5 vented vapor space saturation factor, dimen-
sionless
KS ¼ ð1 þ 0:053 PVA HVO Þ1 (3-20)
where D is the diameter (ft); HVO, vapor space out-
age (ft); MV, molecular weight of vapor (lb/lb-mole);
PVA, vapor pressure at the average liquid surface
temperature (psi); R, ideal gas constant 5 10.731 psi
ft3/lb mole 8R; TLA, average liquid surface tempera-
ture (8R); DTV, vapor temperature range (8R); DPV,
vapor pressure range (psi); DPB, breather vent pres-
April 2011 109
sure setting range (psi); PA, atmospheric pressure,
psi (given, 14.7); Q, annual net throughput (given);
tank capacity in ‘‘barrels of oil’’ times annual turn-
over rate (bbl/yr); conversion factor: 1 US gal 5
0.02381 bbl; KN, working loss turnover factor,
dimensionless; given: 1 for turnovers < 37, for
turnovers > 36; KN 5 (180 1 N)/6N; N, number of
turnovers per year, dimensionless; N 5 5.614 Q/
VLX; VLX, tank maximum liquid volume (ft3)
(given); KP, working loss product factor, dimen-
sionless; given: 1 for volatile organic liquids, 0.75
for crude oils.
Tank Vapor Space Volume, VV from (3-3)
D 5 73.80 ft (given)
For a cone roof, the vapor space outage, HVO, is
calculated by:
HVO ¼ HS  HL þ HRO (3-15)
where HS 5 tank shell height, 49.20 ft (given); HL 5
stock liquid height, 41.83 ft (given); HRO 5 roof out-
age.
HRO ¼ 1=3HR ¼ 1=3ðSR ÞðRS Þ (3-16)
SR 5 tank cone roof slope, 0.0625 ft/ft (given by
default); RS 5 tank shell radius 5 36.9 ft.
HRO ¼ 1=3ð0:0625Þð36:9Þ ¼ 0:769 ft
Then, use Eq. 3-15 to calculate HVO, HVO 5 49.20 –
41.83 1 0.769 5 8.139 ft.
Therefore, VV 5 p/4 (73.80)2 (8.139) 5 34816 ft3.
For a dome roof (the present case), the vapor
space outage, HVO, is calculated by:
 
HRO ¼ HR ð1=2Þ þ ð1=6ÞðHR =RS Þ2 (3-18)
HR ¼ RR  ðRR2  RS2 Þ1=2 (3-19)
where RR is the tank dome roof radius. Section 3.10.6
of API Standard 650 indicates that the tank dome roof
radius, RR, varies between a minimum of 0.8D and a
maximum of 1.2D. If the tank dome roof radius is not
known, a typical value of 1.0D may be assumed. In
this case, the equations are simplified: HR 5 0.268, RS
5 9.89 ft; HRO 5 0.137, RS 5 5.06 ft; HVO 5 49.20 –
41.83 1 5.06 5 12.43 ft. Therefore, VV 5 p/4 (73.80)2
(12.43) 5 53171 ft3.
Vapor Density, WV from (3-21)
MV is the stock vapor molecular weight (lb/lb-
mole). First, calculate TLA using Eq. (3-26).
TLA ¼ 0:44 TAA þ 0:56 TB þ 0:0079a:I (3  26)
where TAA is the average ambient temperature (8R);
TB, liquid bulk temperature (8R); I, daily total solar
insolation, Btu/ft2; and a 5 tank paint solar absorp-
tance.
110 April 2011 Environmental Progress & Sustainable Energy (Vol.30, No.1) DOI 10.1002/ep
In AP-42 for tanks, the correct temperature to use
in the equations is the bitumen surface temperature.
Owens Corning concluded that the bulk temperature
should be used as the bitumen surface temperature
[6]. Consequently, TLA 5 8368R.
Second, calculate PVA. Regressions are calculated
for each binder type using the Clausius Clapeyron
equation (see Appendix A also cited in the report as
Eq. 3.24):
PVA ¼ 16:62 mm Hg ¼ 0:321psi
Third, calculate the molecular weight of the vapor,
MV. The GC-MS characterization assessed the bitumen
vapor molecular weight by determining the organic
species in the vapor spaces of tanks storing different
types of bitumens. The result is a molecular weight of
125. Since all variables have been solved, the vapor
density, WV, can be calculated from (3-21):
WV ¼ ð125Þð0:321Þ=ðð10:731Þð836ÞÞ ¼ 0:0044 lb=ft3
Vapor Space Expansion Factor, KE from (3-7)
PA, PVA, and TLA are known. First, calculate the
vapor temperature range, DTV, from Eq. (3-8):
DTV ¼ 0:72DTA þ 0:028 a:I ð3-8Þ
where DTA is the ambient temperature range 5 TAX
– TAN; I 5 daily total solar insolation, Btu/ft2; a
mean value of 1500 is used; a 5 tank paint solar
absorptance (given for aluminum in good condition:
0.39).
Ideally, bitumen stored at hot temperature should
not be sensitive to external temperature variation.
However, it has been noted during the field experi-
ments that a 108C variation maximum could occur at
constant heat consumption to keep the bitumen hot.
This range has also been accepted as representative
of the temperature variation due to movement (filling
and discharging). Consequently:
TAX ¼ 191 C ¼ 376 F ¼ 836 R
½deg K ¼ ðdeg C 3 9=5Þ þ 32

TAN ¼ 181 C ¼ 818 R
½deg R ¼ ðdeg C 3 1:8Þ þ 492

DTA ¼ 18 R
Therefore, DTV 5 0.72(18) 1 0.028 (0.39) (1500) 5
29.348R.
Second, calculate the vapor pressure range, DPV,
using Eq. (3-9):
DPV ¼ PVX  PVN ð3-9Þ
where PVX, PVN 5 vapor pressures at the daily maxi-
mum, and minimum liquid temperatures can be cal-
culated in a manner similar to the PVA calculation
shown earlier:
TLX ¼ maximum liquid temperature
¼ TLA þ 0:25 DTV ¼ 836 þ 0:25ð29:34Þ ¼ 843 R
TLN ¼ minimum liquid temperature
¼ TLA  0:25DTV ¼ 836  0:25ð29:34Þ ¼ 829 R
LnPVX ¼ 20:7962  15032:54=843
PVX ¼ 19:38 mm Hg ¼ 0:376 psi
LnPVN ¼ 20:7962  15032:54=829
PVN ¼ 14:34 mm Hg ¼ 0:274 psi
Therefore, from (3–7) DPV 5 0.375 – 0.277 5 0.102
psi.
Next, calculate the breather vent pressure, DPB,
from Eq. (3-11):
DPB ¼ PBP  PBV ð3-11Þ
where PBP is the breather vent pressure setting 5
0.03 psi (given); PBV, breather vent vacuum setting 5
20.03 psi (given); these typical values are given for
tanks having bolted or riveted construction in which
the roof is vapor-tight:
DPB ¼ 0:03  ð0:03Þ ¼ 0:06 psi
Finally, KE can be calculated by substituting values
into Eq. (3-7).
KE ¼ ð29:34=836Þ þ ðð0:102  0:06Þ=ð14:7  0:321ÞÞ
¼ 0:038
Vented Vapor Space Saturation Factor, KS from (3-20)
KS ¼ ð1 þ ð0:053Þð0:321Þð12:43ÞÞ1 ¼ 0:825
Calculate Standing Storage Losses from (3-2)
LS ¼ 365ð0:0044Þð53203Þð0:038Þð0:825Þ
¼ 2620 lb=yr ¼ 1190 kg=yr
Since these calculations are based on temperature
variations on passively vented hot asphalt tanks, the
previously determined LS value has to be applied for
each 108C variation. AP-42 estimates this assumption
on a daily scale.
Calculations of the Working Loss Functions
and Total Losses
The amount of VOCs emitted as a result of filling
operations can be calculated from Eq. (3-29) when all
Environmental Progress & Sustainable Energy (Vol.30, No.1) DOI 10.1002/ep
the elements are known (MV, PVA, KP) or can be cal-
culated from given data (Q, KN). Total losses are then
calculated using Eq. (3-1).
ACKNOWLEDGMENTS
The author is grateful to the study participants,
especially Patricia Le Coutaller, SHELL Bitumen, for
her analytical support and Burgard Koenders, SHELL
Bitumen, for reviewing the technical data. Mike
Southern, Technical Director of Eurobitume and for-
merly of SHELL Bitumen, is also thanked for his
insightful discussions, his support and coordination at
the start of the study.
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