Fuel 85 (2006) 1232–1241

www.fuelfirst.com

Chemical characterization of oil-based asphalt release

agents and their emissions
Bing Tang, Ulf Isacsson *
Division of Highway Engineering, Department of Civil and Architectural Engineering, Royal Institute of Technology,
Brinellvägen 34, SE-100 44 Stockholm, Sweden

Received 9 June 2005; received in revised form 10 November 2005; accepted 10 November 2005
Available online 5 December 2005

Abstract
Four commercial asphalt release agents were chemically characterized using different analytical methods. Functional groups and molecular
weight distributions were determined by fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR), gel permeation
chromatography (GPC) and mass spectrometry (MS). General compositions of the agents were obtained as petroleum hydrocarbons, fatty acid
methyl esters (FAMEs), fatty acids and glycerides using gas chromatography–mass spectrometry (GC–MS) and MS probe inlet method. The
contents of health related analytes, such as aromatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs), were determined. Asphalt
release agents emission was investigated using thermogravimetric analysis (TGA) and headspace solid-phase microextraction (HS-SPME). The
emission proneness as well as emission level of aromatic hydrocarbons from these agents were compared. The results obtained were used for
ranking the agents with regard to health hazards.
q 2005 Published by Elsevier Ltd.

Keywords: Asphalt release agents; Petroleum oil; Vegetable oil; Solid-phase microextraction; Aromatic hydrocarbons; PAHs

1. Introduction considerably. The emission generated during application of

Asphalt release agents are widely used in road constructions to
solve the problems of bituminous materials sticking to the metal
surface of truck beds, paving machines or simple paving tools like
shovels during road construction [1]. Most of the commercially
available asphalt release agents can be categorized into three
groups according to main active ingredient: petroleum oil, fatty
oil and non-oil based agents. Traditionally, petroleum oils, such
as diesel oil and kerosene, have been used as asphalt release
agents. However, such products have been criticized from
environmental as well as binder integrity reasons, and therefore,
the interest in other products like fatty oil based agents (mostly,
natural or modified vegetable oils), claimed to be biodegradable
and environmental-friendly, has increased. Non-oil based asphalt
release agents vary with regard to active component(s) and are
often emulsified in water for ease of application.
An asphalt release agent, especially petroleum oil based
one, is a complex mixture, the composition of which can vary
* Corresponding author. Tel.: C46 8 7908700; fax: C46 8 4118432.
E-mail address: ulf.isacsson@byv.kth.se (U. Isacsson).
0016-2361/$ - see front matter q 2005 Published by Elsevier Ltd.
doi:10.1016/j.fuel.2005.11.002
this type of agents, especially when used in hot-mix asphalt
production, may contain a large number of organic compounds,
some of which are hazardous chemicals, e.g. aromatic
hydrocarbons (benzene and alkylated benzenes) and polycyclic
aromatic hydrocarbons (PAHs). Consequently, the health
concern of workers’ exposure to asphalt release agents has
been discussed. Although literature information with regard to
environmental and health aspects of petroleum oils is available
[2,3], however, in terms of asphalt release agents, there is lack
of such information by far in the literature and authority
regulations. Research topics in this connection are demanded.
Evaluation of the health risks of asphalt release agents can
be carried out either in laboratory or in-situ. However, in-situ
measurement of workers’ exposure to the asphalt release
agents may be time-consuming and costly, furthermore, the
other pollution sources (e.g. asphalt fumes and vehicle
emissions) may also contribute to the exposure measurement.
Consequently, laboratory testing could provide such an
alternative of screening and ranking different asphalt release
agents with regard to health aspects.
In the present work, various analytical tools were used for
chemical characterization of four commercial asphalt release
agents and their emissions at different temperatures. Functional
 B. Tang, U. Isacsson / Fuel 85 (2006) 1232–1241
groups and molecular weight distributions were determined
using fourier transform infrared spectroscopy-attenuated total
reflectance (FTIR-ATR), gel permeation chromatography
(GPC) and probe inlet method of mass spectrometry (MS),
respectively. General composition of the agents and the content
of certain hazardous chemicals, such as aromatic hydrocarbons
and PAHs, were obtained using gas chromatography–mass
spectrometry (GC–MS). The proneness of emission (fuming
tendency) of asphalt release agents was characterized using
thermogravimetric analysis (TGA). To obtain the emission
profiles at different temperatures, headspace solid-phase
microextraction (HS-SPME) was applied. SPME, which was
developed since the beginning of the 1990’s [4,5], represents a
solvent-free, quick, sensitive and economical approach and has
been successful for various applications during the last decade
[6–9]. This paper showed that SPME technique is a promising
tool for asphalt release agent emission characterization. The
analytical procedures described provide information for select-
ing suitable asphalt release agents in industrial applications.
2. Experimental
2.1. Chemicals and samples
A standard mixture (revised PVOC/GRO mix, Supelco,
Sweden), containing 10 compounds (methyl tert-butyl ether,
benzene, toluene, ethylbenzene, m-, p-, o-xylene, 1,2,4-
trimethylbenzene, 1,3,5-trimethylbenzene, naphthalene), each
at a concentration of 2000 mg/ml in methanol, was used as
calibration standards after dilution in n-hexane (O99% by GC,
Merck, Germany). Ethylbenzene-d10 (Supelco, Sweden) was
chosen as an internal standard. The stock solution of
ethylbenzene-d10 was made in hexane at 2000 mg/ml and
used for preparation of calibration standards. EPA610 PAH
standard (Supelco, Sweden) in 50:50 methanol: dichloro-
methane, was used to prepare PAH calibration standards in
dichloromethane (SDS, France). The four commercial asphalt
release agents studied, abbreviated as DIE, BIO, RME and
AF1, were obtained from a contractor. General information
about these agents is given in Table 1.
2.2. Characterization of asphalt release agents
The FTIR-ATR used was a Mattson Infinity 60 AR
spectrophotometer (resolution 0.125 cmK1) fitted with a
Table 1
General information of asphalt release agents studied
Agents name Product description
DIE 100% petroleum oil based product hydrocarbons:
C9–C20, boiling point distribution: 163–357 8C
RME 100% derivatives of vegetable oil (rapeseed oil), flash
point: 118 8C, solidifying point: –8 8C
BIO 50–100% mixture of petroleum oil and vegetable oil
hydrocarbons: C11–C16, flash point: O77 8C
AF1 100% vegetable oil from rapeseed and other vegetable
plants, flash point: 140 8C, solidifying point: K12 8C
1233
Graseby Specac ATR. The ATR accessory, fitted with a
ZnSe (zinc selenide) crystal prism (4000 and 650 cmK1), can
be heated up to 200 8C. The spectra were measured at 2 cmK1
spectral resolution using 128 scans. The neat samples of
asphalt release agents were measured in order to avoid
interference of solvent bands.
The GPC system used was Waters Styragel columns in the
order of HR2, HR2, HR1, and a refractive index detector
(Waters 410). The mobile phase was tetrahydrofuran (THF) at
a flow rate of 1 ml minK1. Asphalt release agents were
prepared as a 5% solution (by weight) in THF. The injection
volume was 50 ml, and the GPC system was calibrated with
narrow polystyrene standards.
The mass spectrometer (Finnigan SSQ 7000) was operated
at 70 ev EI mode. The source and the manifold temperatures
were 150 and 70 8C, respectively. 1 ml sample solution (asphalt
release agents at 1 mg gK1 in hexane) was introduced into the
MS system using probe inlet method. The heating of the sample
was programmed from 50 8C (0.5 min hold) to 400 8C at a rate
of 100 8C minK1, and then held at 400 8C for 4 min. MS scan
range was 40–1500 m/z at two scans per second. The
computer-based MS spectrum library used was the NIST
mass spectral search program, version 1.7.
Details of the GC–MS system used for different testing
procedures, including instruments and parameters, are given in
Table 2. Qualitative composition analysis was conducted by
injecting 1 ml solution of asphalt release agents in hexane
(1 mg gK1) into the GC–MS system. Calibration standards of
aromatic hydrocarbons and EPA 16 PAHs as well as the MS
library and literature were used for identification of chromato-
graphic peaks. For quantitative analysis of aromatic hydro-
carbons, calibration standards made from the stock solution
were used, and the concentration of each analyte was 10, 5, 2,
1, 0.5, 0.1, 0.05, 0.01, 0.005 and 0.001 mg mlK1, respectively.
Asphalt release agents were dissolved in hexane and internal
standard was added (5 mg mlK1). BIO, RME and AF1 were
prepared at w10 mg mlK1 but DIE at w1 mg mlK1, because
DIE contains much higher amount of aromatic hydrocarbons,
as indicated in the qualitative composition analysis.
For quantification of semi-volatile polycyclic aromatic
compounds (3–7 rings) in DIE, internal standards d10-
phenanthrene and 2,2 0 -binaphthyl were added to 100 ml of
DIE, and the volume was reduced using a gentle stream of
nitrogen. The residue was dissolved in dichloromethane
(DCM), transferred to 100 mg of deactivated silica gel (10%
water), and the DCM was evaporated while heating under a
gentle stream of nitrogen. The silica gel was put on the top of
the silica gel column, and the DIE sample was fractionated
according to polarity, into two fractions before chemical
analysis. These fractions contained fraction I, ‘light’ aliphatic
hydrocarbons (not analyzed further) and fraction II, ‘heavy’
aliphatic hydrocarbons and PAHs. This procedure followed the
one described elsewhere [10], though the solvent elution
volumes were modified to fit the column size used. The PAH
fraction, II, was further fractionated with HPLC to separate
‘heavy aliphatic material’ and PAH [11]. The obtained PAH
fraction was analyzed by GC–MS as described in Table 2.
1234 B. Tang, U. Isacsson / Fuel 85 (2006) 1232–1241

Table 2
GC–MS instruments and parameters in different testing procedures

Testing procedure Instrument Parameters

GC MS

Qualitative composition Varian 3400 GC coupled with a Finnigan SSQ 7000 Column temperature program: MS full scan mode: 45–465 m/z,
analysis MS detector, DB-5MS capillary column (30 m!0. 1 min at 50 8C, and then a ramp to two scans per second.
25 mm!0.25 mm), DB-wax capillary column 250 8C at 3 8C minK1, hold for
(30 m!0.25 mm!0.25 mm), carrier gas was helium 10 min.
at a 1 ml minK1 flow-rate in a constant pressure mode. Injector and transfer line
temperature: 250 8C.
Quantitative analysis of Column temperature program: MS selected ion monitoring (SIM)
aromatic hydrocarbons 3 min at 40 8C, and then a ramp to mode: monitored ion were m/z 78,
80 8C at 5 8C minK1 and finally a 91, 98, 105, 106, 116 and 120,
ramp to 250 8C at 10 8C minK1 and 2 scans per second.
hold for 3 min.
Injector and transfer line tempera-
ture: 250 8C.
Qualitative screening of Column temperature program: MS SIM mode: monitored ions are
EPA 16 PAHs 1 min at 50 8C, and then a ramp to 128, 152, 166, 178, 202, 228, 252,
270 8C at 10 8C minK1 and hold for 276 and 278 m/z, 2 scans per
2 min. second.
Injector and transfer line
temperature: 270 8C.
HS–SPME Column temperature program: MS full scan mode: 40–400 m/z,
1 min at 50 8C, and then a ramp to 2 scans per second.
120 8C at 5 8C minK1, and finally a
ramp to 250 8C at 20 8C minK1 and MS SIM mode: monitored ion were
hold for 3 min. m/z 78, 91, 98, 105, 106, 116 and
Injector and transfer line 120, 2 scans per second.
temperature: 250 8C.
Quantitative analysis of HP 5890 GC coupled with a HP 5971A MS detector, Column temperature program: MS SIM mode: monitored ions are
semi-volatile PACs in HP5-MS capillary column (30 m!0.25 mm!0. 1 min at 120 8C, a ramp to 300 8C at major ions of target PACs, 2 scans
DIE 25 mm), carrier gas was helium at a 1 ml minK1 the rate 7 8C minK1 and hold for per second.
flow-rate in a constant pressure mode. 10 min.
Injector temperature 285 8C and
transfer line temperature 300 8C

A PAH standard mixture with internal standards was used for
retention time determinations and response factor calculations.
The system used in the present study was described in details
elsewhere [12].
2.3. Characterization of asphalt release agents emissions
In TGA analysis, neat asphalt release agents were tested
directly without any sample pretreatment. 40G3 mg of the
sample was weighted into a 70 ml aluminium oxide crucible
with open lid. The test crucible was placed in the equipment
(Mettlet Toledo TGA/SDTA 851) under a shielding gas (N2) at
a flow rate of 50 ml minK1. The sample was heated from
around 30 to 350 8C at 10 8C minK1. The weight of sample was
recorded continuously every 2 s during the heating process.
In the HS-SPME test procedure, a 30 mm polydimethylsi-
loxane (PDMS) coated fiber (Supelco, Sweden) was used for
screening of emission profile at different temperatures (20, 80,
130 and 170 8C, respectively). The apparatus for emissions
generation is shown in Fig. 1. Approximately, 0.5 mg of each
asphalt release agent was introduced into a 25 ml glass vial.
The glass vial was then covered with two layers of aluminum
foil and sealed by a plastic cap with a hole. Vials were kept in a
heating metal block at the selected temperatures for 1 h to
generate emission in the headspace. The heating block was
proved to maintain a stable headspace temperature in the glass
vial within the SPME sampling period. Sampling of emissions
was performed by piercing the SPME needle through the
aluminum foil and exposing the SPME fiber in the headspace
for 5 s. After sampling, the SPME fiber was ready for GC–MS
analysis (c.f. Table 2 for GC–MS conditions). For quantitative
comparison of volatile aromatic hydrocarbons emitted from
different asphalt release agents, a 100 mm PDMS fiber was
used, since this type of fiber can extract more aromatic
hydrocarbons than a 30 mm PDMS fiber. 100 mm PDMS fiber
has been widely used for extraction of aromatic hydrocarbons
in different applications [13–17]. In this study, only the
emission of asphalt release agents generated at 20 8C was
studied as one temperature was considered enough for ranking
of different agents with regard to the emission. The sample
amount is 1 g with 20 ppm ethylbenzene-d10 added as internal
standard. The SPME extraction time of 5 min was chosen
based on experience and literature [5,18]. In all tests described,
the SPME desorption time was 5 min, which was shown
 B. Tang, U. Isacsson / Fuel 85 (2006) 1232–1241
Fig. 1. HS-SPME device for study of asphalt release agent emission.
enough to clean the fiber. Blank injections were performed
routinely to ensure no carry-over from the previous test.
3. Results and discussion
3.1. Characterization of asphalt release agents
Functional groups determined by FTIR-ATR could reveal
the types of compounds in the samples. The spectra of the
investigated asphalt release agents obtained by FTIR-ATR are
shown in Fig. 2. The strong peaks within 2850–3000 cmK1
region are typical C–H stretching vibrations in aliphatic chains.
C–H bending vibrations are observed at 1458 and 1377 cmK1.
The peak absorption at 3012 cmK1 is probably attributed to
alkenyl C–H stretching. The characteristic absorption peak
around 1745–1750 cmK1 is attributed to CaO, and detailed
check of the wavenumbers indicates that CaO comes from the
ester structure (normally in the 1750–1735 cmK1 region).
Fig. 2. Spectra of asphalt release agents obtained using FTIR-ATR.
1235
Besides this normal CaO absorption peak, AF1 also shows a
distinguished peak at 1713 cmK1, which is due to the
absorption of asymmetrical CaO stretching in carboxylic
dimer. The weak peak at w1660 cmK1 is assigned as CaC
stretching in aliphatic chains. In the 950–1330 cmK1 region,
both AF1 and RME show a broad absorption band with several
overlapped peaks, which are probably related to mixed
absorption of methyl rockings in methyl ester at around
1170 cmK1 and C(aO)–O stretching at 1250 cmK1. As
indicated, all asphalt release agents studied contain aliphatic
chains, but DIE seems not to contain the CaO functional
groups like the other three agents. The content of CaO varies
among the three agents in the order of BIO/RME!AF1.
Both RME and AF1 contain CaC double bonds, whereas in
BIO, the content is so low that it could not be detected by the IR
spectrum. It is interesting to observe, that AF1 may contain
dimer of carboxylic acid, while this dimer is not found in RME.
Molecular weight distribution was determined by GPC and
heated probe inlet method of MS, as illustrated in Fig. 3.
Molecular weight averages are summarized in Table 3. GPC
separates the materials based on molecular sizes and MS based
on boiling point. It is interesting to observe that in Fig. 3, in
general, similar peak pattern was obtained by both GPC
(Fig. 3(a)) and MS (Fig. 3(b)), except a slight difference in the
early stage of MS (before 0. 5 min). This difference is due to
the fast heating program of probe inlet, which leads to fast
evaporation of relatively volatile hydrocarbons at the early
Fig. 3. Gel permeation chromatograms (a) and MS analysis using heated probe
inlet (b) of the asphalt release agents studied.
1236 B. Tang, U. Isacsson / Fuel 85 (2006) 1232–1241

Table 3
Molecular weight averages of four asphalt release agents obtained using GPC

Asphalt release agents Mn Mw

DIE 166 211
BIO 166 203
RME 235 311
AF1 474 489

stage of heating. Compared with GPC, MS can also be used to

elucidate the chemical structures of molecules. As illustrated in
Fig. 3, three major groups of compounds are identified as
hydrocarbon mixtures (group 1, petroleum oil type), FAMEs
(group 2) and glycerides (group 3), respectively. DIE consists
solely of hydrocarbons. Besides hydrocarbons, BIO also
contains a small amount of FAMEs. RME is mainly a mixture
of hydrocarbons and FAMEs. Compared with the other three
agents, AF1 contains mainly FAMEs and glycerides. The
chemical characteristics of asphalt release agents as deter-
mined by the procedures described are generally in agreement
with the product information (c.f. Table 1). However, the
results indicate that RME is not totally based on derivatives of
vegetable oils but also contains some petroleum oil.
A more detailed composition profile of the asphalt release
agents studied was obtained by GC–MS analysis. The total ion
gas chromatograms of asphalt release agents are shown in
Fig. 4, and the major components found are listed in Table 4.
DIE contains predominately hydrocarbons (C9–C22 normal and
branched alkanes, cycloalkanes and aromatic hydrocarbons).
BIO and RME contain not only hydrocarbons but also FAMEs
(C13–C25, saturated and unsaturated fatty acid methyl ester
with 1–3 double bonds). As revealed by GC–MS, AF1 contains
very little amount of hydrocarbons (mostly, C12–C16 n-alkanes)
but a large amount of FAMEs and fatty acids (FAs). It should
be noted that the major group, glycerides, described in the
previous section, could not be analyzed by GC–MS under
current experimental conditions. Therefore, it is important to
explore different analytical methods for more comprehensive
characterization of asphalt release agents.
Aromatic hydrocarbons, especially volatile aromatic hydro-
carbons such as BTEX (benzene, toluene, ethylbenzene and
xylenes), are one of the important groups of hazardous
compounds in environment monitoring. In this study, the
concentration level of BTEX and two trimethylbenzenes was
estimated, and the results are shown in Table 5 (benzene was
not determined due to the solvent effects). The ranking of the
content of aromatic hydrocarbons in asphalt release agents is in
the order of DIE (approximately, 100–1000 ppm)[RME
(approximately, 3–150 ppm)OBIO (approximately, 1–
10 ppm)[AF1 (not quantified up to approximately, 3 ppm).
As discussed in the previous section, AF1 contains very little
amount of hydrocarbons, and therefore, it is not surprising to
observe that that target aromatic hydrocarbons are not
quantifiable in this analysis (less than 1 ppm) except 1,2,4-
trimethylbenzene.
PAHs are another important group of hazardous compounds
Fig. 4. Total ion gas chromatograms of four asphalt release agents studied.
in environmental monitoring. In the preliminary test using GC–
MS, no significant chromatographic peak was found, which
 B. Tang, U. Isacsson / Fuel 85 (2006) 1232–1241 1237

Table 4
Components found in the four asphalt release agents studied using GC–MS

Peak no MW Name or type DIE BIO RME AF1

1 106 C2 alkyl benzene C C C K
2 106 C2 alkyl benzene C C C K
3 128 n-Nonane CC C C K
4 126 C3 alkyl cyclohexane CC C C K
5 142 C10 alkane CC C C K
6 120 C3 alkyl benzene C K C K
7 142 C10 alkane CC CC CC K
8 140 C4 alkyl cyclohexane CC CC CC K
9 120 n-Decane CC K K K
10 156 C11 alkane CC CC CC K
11 140 C4 alkyl cyclohexane CC CC CC K
12 138 Decahydronaphthalene CC CC CC K
13 156 C11 alkane CC CC CC K
14 154 C3 alkyl cyclohexanone CC CC CC K
15 156 n-Undecane CCC CCC CC K
16 152 Methyldecahydronaphthalene CC CC CC K
17 152 Methyldecahydronaphthalene CC CC CC K
18 170 C11 alkane CC CC CC K
19 154 C5 alkyl cyclohexanone CC CC CC K
20 170 C12 alkane CC CC CC K
21 170 C12 alkane CC CC CC K
22 170 C12 alkane CC CC CC K
23 166 Dimethyldecahydronaphthalene CC CC CC K
24 168 C6 alkyl cyclohexane CC CC CC K
25 170 n-Dodecane CCC CCC CC C
26 184 C13 alkane CC CC CC K
27 166 Ethyldecahydronaphthalene CC CC CC K
28 168 C6 kyl cyclohexane CC CC CC K
29 184 C13 alkane CC CC CC K
30 184 C13 alkane CC CC CC K
31 184 C13 alkane CC CC CC K
32 198 C14 alkane CC CC CC K
33 166 Bicyclohexyl CC CC CC K
34 184 n-Tridecane CCC CCC CC C
35 182 C7 alkyl cyclohexane CC CC CC K
36 198 C14 alkane CC CC CC K
37 198 C14 alkane CC CC CC K
38 198 C14 alkane CC CC CC K
39 212 C15 alkane CC CC CC K
40 198 n-Tetradecane CCC CC CC C
41 196 C8 alkyl cyclohexane CC CC CC K
42 226 C16 alkane CC CC CC K
43 212 C15 alkane CC CC CC K
44 212 C15 alkane CC CC CC K
45 212 n-Pentadecane CCC CC CC C
46 210 C9 alkyl cyclohexane CC C C K
47 226 C16 alkane CC C C K
48 226 C16 alkane CC C C K
49 226 C16 alkane CC C C K
50 226 n-Hexadecane CCC CC CC C
51 254 C18 alkane CC K C K
52 224 C10 alkyl cyclohexane CC K C K
53 240 C17 alkane CC K K K
54 240 C17 alkane CC K K K
55 240 n-Heptadecane CC C C K
56 268 C19 alkane CC K K K
57 242 Tetradecanoic acid, methyl ester K K C K
58 238 C11 alkyl cyclohexane CC K K K
59 254 n-Octadecane CC K K K
60 282 C20 alkane CC K K K
61 268 n-Nonadecane CC K K K
62 268 Hexadecenoic acid, methyl ester K K C C
(continued on next page)
1238 B. Tang, U. Isacsson / Fuel 85 (2006) 1232–1241

Table 4 (continued)

Peak no MW Name or type DIE BIO RME AF1

63 270 Hexadecanoic acid, methyl ester K CC CC CC
64 278 Dibutyl phthalate CC CC CC CC
65 256 Hexadecanoic acid K K K CC
66 282 Heptadecenoic acid, methyl ester K K C K
67 282 n-Eicosane C K K K
68 284 Heptadecanoic acid, methyl ester K K C K
69 294 Octadecadienoic acid, methyl ester K CC CC CC
70 292 Octadecatrienoic acid, methyl ester K CC CC CC
71 296 Octadecenoic acid, methyl ester K CCC CCC CCC
72 296 n-Heneicosane C K K K
73 298 Octadecanoic acid, methyl ester K CC CC CC
74 282 Octadecenoic acid K K K CCC
75 310 n-Docosane C K K K
76 324 Eicosenoic acid, methyl ester K CC CC CC
77 326 Eicosanoic acid, methyl ester K K CC CC
78 352 Docosenoic acid, methyl ester K K CC CC
79 354 Docosanoic acid, methyl ester K K CC C
80 380 Tetracosenoic acid, methyl ester K K C C

could be attributed to PAHs. This may be due to interference of
background and/or low concentrations of PAHs. To obtain
more detailed information of PAH content, a further
quantitative analysis was performed on DIE solely, because
DIE is mainly composed of petroleum hydrocarbons and thus
assumed to contain higher concentration level of PAHs, and
furthermore, the method used is only established for petroleum
oils [12]. Using this established method, quantitative results of
the concentration of more than 40 PAH compounds were
obtained (c.f. Table 6). Phenanthrene and its alkylated
derivatives showed a much higher concentration level than
other individual PAHs. The PAHs with three rings dominate
the PAH content profile in DIE, while PAHs with four rings
only marginally contribute. The PAHs with more than four
rings, including benzo(a)pyrene, a widely monitored com-
pound as a surrogate of PAHs due to its health aspects, were not
detected (below 0.1 ng mlK1). Due to limitation of the method,
PAHs with two or three rings (e.g. naphthalene, acenaphthy-
lene) were not selected for analysis. In general, the PAHs
content of the DIE used in this study is relatively low compared
to other similar fuel oils used in industry [12].
3.2. Characterization of asphalt release agents emissions
3.2.1. Fuming tendency determined by TGA
TGA examines the mass change of a sample as a function of
temperature or as a function of time at a given temperature
[19]. In this study, TGA was used to estimate the fuming
tendency of asphalt release agents. As indicated in Fig. 5, DIE
and BIO show single-stage TG curves, whereas RME shows a
two-stage curve, assuming the small loss of mass of BIO and
RME at high temperature end is negligible. Since AF1 contains
two major groups of compounds (fatty acid methyl ester and
glycerides), a multi-stage TG curve was expected. However, in
this study, the curve was not completed within the testing
temperature range used (30–350 8C). Fig. 5 also indicates that
mass change starts at approximately 80 8C for the asphalt
release agents except AF1, and finishes at approximately
200 8C for BIO, 220 8C for DIE and 290 8C for RME. For these
agents, based on the results presented in previous sections, the
first stage of each TG curve should be due to evaporation of
hydrocarbons, of which are evaporated up to approximately
220 8C. The overlapped stages in the TG curve of RME

Table 5
Concentration of aromatic hydrocarbons in four asphalt release agents studied

Concentration (ppmw) (nZ3)

Analytes RRFa DIE BIO RME AF1
Mean RSD% Mean RSD% Mean RSD% Mean RSD%
b
Toluene 0.995 127 1.3 8.7 1.4 2.9 3.4 nq nq
Ethylbenzene 1.159 80 2.8 1.9 1.9 2.9 2.7 nq nq
m, p-xylene (total) 1.661 172 1.9 4.0 0.5 5.7 1.9 nq nq
o-xylene 0.816 175 2.2 3.3 1.0 9.5 1.2 nq nq
1,3,5-trimethylbenzene 0.743 255 3.2 1.4 2.3 32.7 1.0 nq nq
1,2,4-trimethylbenzene 0.730 849 3.1 10.9 4.2 136 0.6 3.4 3.8
a
Mean of relative response factor (nZ7).
b
Below quantitation limit.
 B. Tang, U. Isacsson / Fuel 85 (2006) 1232–1241 1239

Table 6
Quantitative determination of PAHs content in DIE

Compound No. of aromatic Molecular Concentration

rings Ion (ng mlK1)
Fluorene 3 166 5.8
2-Methylfluorene 3 180 3.4
Phenanthrene 3 178 12.9
Anthracene 3 178 0.0
3-Methylphenanthrene 3 192 8.0
2-Methylphenanthrene 3 192 10.1
2-Methylanthracene 3 192 0.4
4H-Cyclopenta(def)- 3 190 0.0 Fig. 5. Thermogravimetry analysis of four asphalt release agents studied.
phenanthrene
9-Methylphenanthrene 3 192 10.4 studied as measured by TGA can be ranked as follows:
1-Methylphenanthrene 3 192 9.6
BIOzDIEORME[AF1.
9-Methylanthracene 3 192 0.0
2-Phenylnaphthalene 3 204 1.2
3,6-Dimethylphenan- 3 206 1.0 3.2.2. Emission profiles at different temperatures
threne During road construction, the workers are exposed to
3,9-Dimethylphenan- 3 206 8.9 asphalt release agents at different temperatures, i.e. from
threne
9,10-Dimethylanthra- 3 206 0.0
ambient temperature (e.g. 20 8C) up to a high temperature (e.g.
cene 160 8C). Consequently, it is important to know the emission
Retene 3 219 2.0 profiles of asphalt release agents at different temperatures. In
Fluoranthene 4 202 0.4 our investigation, four temperatures (20, 80, 130, and 170 8C)
1-Methylfluoranthene 4 216 0.2 were chosen to obtain qualitative profiles of emitted
Pyrene 4 202 1.9
Benz(a)fluorine 4 216 0.5
compounds from the asphalt release agents using HS-SPME
Benz(b)fluorine 4 216 0.3 followed by GC–MS analysis. The test results are illustrated in
2-Methylpyrene 4 216 0.9 Fig. 6. At 20 8C, the emitted hydrocarbons are up to C13
4-Methylpyrene 4 216 0.9 alkanes (c.f. Table 4). The hydrocarbons with larger molecular
1-Methylpyrene 4 216 0.5 weight are emitted at increased temperatures: up to C17 alkanes
Benzo(ghi)fluoranthene 4 226 0.0
Benzo(c)phenanthrene 4 228 0.0
at 80 8C, C20 alkanes at 130 8C and C22 at 170 8C. No emitted
Cyclopenta(cd)pyrene 4 226 0.0 FAMEs and FAs are detected at 20 8C, and only negligible
Benzo(a)anthracene 4 228 0.1 amount of these types of compounds are emitted at 80 8C.
Chrysene 4 228 0.4 However, a large amount of these types of compounds were
3-Methylchrysene 4 242 0.1 observed in the emission profiles at higher temperatures,
2-Methylchrysene 4 242 0.1
6-Methylchrysene 4 242 0.0
especially at 170 8C. As expected, the emission profiles of
1-Methylchrysene 4 242 0.1 asphalt release agents are related to the composition profiles as
Benzo(b)fluoranthene 5 252 0.0 described in the previous section. Among these four asphalt
Benzo(k)fluoranthene 5 252 0.0 release agents, AF1 is the one least prone and DIE the one most
Benzo(e)pyrene 5 252 0.0 prone to emissions, while BIO and RME show intermediate
Benzo(a)pyrene 5 252 0.0
Perylene 5 252 0.0
behavior in this connection. The results of emission profiles at
Indeno(1,2,3-cd)fluor- 6 276 0.0 different temperature could be used as a general guidance of
anthe selecting an agent so that the workers’ exposure to hazardous
Indeno(1,2,3-cd)pyrene 6 276 0.0 compounds could be reduced.
Dibenz(a,h)anthracene 5 278 0.0
Benzo(ghi)perylene 6 276 0.0
Coronene 7 300 0.0 3.2.3. Comparison of volatile aromatic hydrocarbons in
Sum PAHs 80.2 emissions
In Section 3.1, the concentrations of health related
compounds, aromatic hydrocarbons and PAHs, have been
estimated. It is of interest to compare the emission level of
indicate that evaporation of FAMEs, which show higher these groups of compounds among the asphalt release agents
boiling points, follows the loss of hydrocarbons. AF1 has a studied, which may provide useful information in health risk
unique TG curve with high onset temperature (approximately assessments. Since aromatic hydrocarbons are more volatile
220 8C), and even at the highest temperature used (350 8C), than PAHs and the content in asphalt release agents much
only about 30% loss of mass is observed. It is obvious that the higher, special attention was paid to the emission level of
first mass loss of AF1 is due to evaporation of FAMEs and FAs, volatile aromatic hydrocarbons in this paper. As shown in
and the majority of nonvolatile glycerides in AF1 could not be Fig. 7, the emission level of selected volatile aromatic
evaporated within the testing temperature range used. In hydrocarbons from DIE was much higher than from the other
conclusion, the fuming tendency of the different release agents three agents studied (in the case of BIO approximately 10–100
1240 B. Tang, U. Isacsson / Fuel 85 (2006) 1232–1241
Fig. 6. Emission profiles of asphalt release agents at different temperatures
obtained using HS-SPME and GC–MS.
times and RME 10–40 times and AF1 100–1000 times). Except
benzene and toluene, the emission of aromatic hydrocarbons
from BIO was less than that from RME. It was not surprising
that AF1 generated the least emission of aromatic hydro-
Fig. 7. Comparison of volatile aromatic hydrocarbons emitted from asphalt
release agents at 20 8C using HS-SPME and GC–MS (relative response is the
ratio of peak area count of analyte to that of the internal standard, ethylbenzene-
d10)
carbons. Furthermore, by comparing the results presented in
Table 5 and Fig. 7, it was observed that the emission level of
aromatic hydrocarbons was qualitatively related to the contents
of the same compounds in the asphalt release agents. This
phenomenon is often observed in applications of SPME to
aqueous and solid samples and has been theoretically explained
and used as principle of quantitative analysis [5]. Our
observation indicated that SPME technique could also be
applicable for quantitative determination of analytes in oil
samples, provided that SPME parameters were further
optimized. The results presented indicated that SPME
technique could be a valuable and fast tool for ranking asphalt
release agents with regard to health aspects.
4. Conclusions
In this study, chemical characterization of four commercial
asphalt release agents and their emissions were carried out.
Based on the results obtained, the following conclusions could
be drawn:
† To obtain a more detailed image of chemical characteristics
of asphalt release agents and their emissions, a combination
of different analytical methods should be used. The results
showed that the composition can be very complex and differ
considerably between different agents.
† Concerning the content of hazardous chemicals (aromatic
hydrocarbons and PAHs), proneness to emission and
emission level from the agents studied, AF1 would be the
best and DIE the worst choice among the four agents
studied.
† HS-SPME was found to be a promising tool for asphalt
release agent emission characterization, especially for fast
screening of emitted hazardous chemicals. However,
regarding quantitative analysis based on SPME, further
research is necessary.
 B. Tang, U. Isacsson / Fuel 85 (2006) 1232–1241
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