Science of the Total Environment 832 (2022) 155037

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Science of the Total Environment

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Research Paper

Recycled plastic modified bitumen: Evaluation of VOCs and PAHs from

laboratory generated fumes
Yeong Jia Boom, Marie Enfrin, Stephen Grist, Filippo Giustozzi
⁎
Civil and Infrastructure Engineering, Royal Melbourne Institute of Technology (RMIT) University, 376392 Swanston St, VIC, 3000 Melbourne, Australia

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• The use of recycled plastics in bitumen

can reduce total VOC and PAH concentra-
tions.
• TGA showed the enhanced thermal resis-
tance of recycled plastics modified bitu-
men.
• The inhibition rate of emissions is depen-
dent on the type/content of plastics used.
• Increase in working temperature resulted
in higher levels of emissions (up to 248%).

A R T I C L E I N F O A B S T R A C T

Editor: Damia Barcelo A key aspect when investigating the use of recycled plastics in bitumen relates considerably to the issues relating to
occupational, health and safety for humans and the environment from a fuming and emissions perspective. This re-
Keywords: search investigates laboratory-generated fumes in the forms of volatile organic compounds (VOCs), and polycyclic ar-
Fuming omatic hydrocarbons (PAHs) generated from producing polymer modified bitumen using five different types of
Emissions
recycled plastics. A comparative analysis of recycled plastic modified bitumen fumes was conducted based on a series
Recycled plastics
Polycyclic aromatic hydrocarbons
of optimized parameters, including working temperatures (160 °C, 180 °C and 200 °C) and polymer contents (1%, 2%,
Volatile organic compounds 4% and 6% by weight of bitumen) against neat bitumen and polymer-modified bitumen. Forty-eight volatile organic
Bitumen compounds (VOCs) and sixteen polycyclic aromatic hydrocarbons (PAHs) were quantified using gas chromatography–
Asphalt mass spectrometry (GC–MS). The results from the comparative analysis revealed that the incorporation of recycled
plastics could reduce overall emissions from both VOCs and PAHs perspectives. The reduction in emissions can be at-
tributed to the enhancement in thermal stability of the bitumen blend when recycled plastics are added. The reduction
rate is heavily dependent on the type and source of recycled plastics used in the blending process. Furthermore, a spe-
cific compound concentration analysis of the top-four weighted compounds emitted reveals that the total concentra-
tion of emissions can be deceiving as specific compounds can spike when adding recycled plastics in bitumen
despite a reduction trend for the overall concentration.

1. Introduction solvents such as petroleum distillate so that bitumen is easier to manage

(Robertus et al., 2016). Although the chemical composition of bitumen is
Bitumen is a product derived from crude oil and is the result of refinery complex, it is generally categorized into four groups referred to as aromatic
products made of hydrocarbon molecules that are commonly mixed with hydrocarbons (40–53%), asphaltenes (10–12%), resins (23–35%) and

⁎ Corresponding author.
E-mail address: filippo.giustozzi@rmit.edu.au (F. Giustozzi).

http://dx.doi.org/10.1016/j.scitotenv.2022.155037
Received 30 January 2022; Received in revised form 26 March 2022; Accepted 31 March 2022
Available online 5 April 2022
Y.J. Boom et al.
saturates (12–16%) (Liang et al., 2019). The relative content of each frac-
tion depends on the bitumen's country of origin and its refinery process
(Liang et al., 2019). Due to its versatile properties, bitumen has been used
in various industrial applications, including waterproofing, preserving,
sealing, adhering and most commonly as a construction material in road
and airport pavements (Lu et al., 1999). A report suggested that 85% of
the total consumption of bitumen is used to build asphalt pavements
(Asphalt Institute, 2015). However neat bitumen is still facing challenges
due to the lack of suitable mechanical properties in specific environments
and loading conditions (Moghadas Nejad et al., 2015). The polymer modi-
fication of neat bitumen significantly improves a wide range of properties
such as its thermal susceptivity, rutting, moisture damage, adhesion to ag-
gregates and fatigue life, therefore, enhancing the demand for polymer-
modified bitumen (Nizamuddin et al., 2021; Santos et al., 2021). The
most commonly used types of polymers for modifying bitumen include ap-
proximately 75% of elastomers, 15% of plastomers and 10% of shredded
vehicle tire rubber and other types of materials (Pérez-Lepe et al., 2003).
While considered the most suitable material worldwide for road pave-
ments construction, bitumen also poses environmental health risks if
mishandled. The emissions produced during bitumen production, such as
reactive organic gases (ROGs) and particulate matter (PM), have raised sev-
eral health and environmental concerns (Heikkilä et al., 2003; Kalagaeva,
2014). ROGs consist of several volatile organic compounds (VOCs), such
as toluene, 4-ethyl toluene, xylene, 1,3,5-trimethyl benzene, ethylbenzene,
benzene, 1,2-dibromoethane, and semi-volatile organic compounds
(SVOCs), including all polycyclic aromatic hydrocarbons (PAHs) and al-
kanes (Chong et al., 2014; Gasthauer et al., 2008).
When volatilized and emitted during the life cycle of asphalt pavements
(production, hauling, paving, usage, demolition, and recovery), VOCs can
have a significant impact on human health and the environment (Cui
et al., 2019; Li et al., 2020). Typical asphalt applications are conducted at
high temperatures (up to 170–180 °C); in this conditions, a complex mix-
tures of organic compounds with a wide volatility range can be released
(Long-Sheng, 2018). While such working temperatures are known to con-
tribute to VOC emissions during asphalt production, a recent study showed
that the environmental temperature also affects the total VOC emission fac-
tor, with increments of up to 70% recorded during summer at a tempera-
ture of 35 °C to 45 °C (Khare et al., 2020).
Furthermore, asphalt plants can release significant quantities of asphalt
vapours containing VOCs, hence potentially posing potential health risks to
onsite workers. According to a 2010 study commissioned by Environment
and Climate Change Canada, 1301 kilotons (kt) of bitumen were used in
Canada in 2009, producing 88 kt of VOC emissions (Government of
Canada, 2017).
VOCs account for thousands of compounds. While there are no clear
standards for total permissible threshold values outside of some industrial
settings, some VOC limits such as benzene and formaldehyde have been
identified to potentially generate health risks such as damage to kidney,
liver, nervous system as well as cancer (Smith, 2020). For asphalt/bitumen
production, the maximum permissible threshold limit value is 0.5 mg/m3
over an 8-hour weighted average or 5 mg/m3 for a 15-minute short-term
period as recommended by ACGIH and NIOSH, respectively (Moo et al.,
2019).
As bitumen comprise over 50% of aromatic hydrocarbons, PAHs are
produced when bitumen is heated to high working temperatures. Studies
have shown that temperature plays a significant role in the emission of
PAHs during asphalt production (Xia et al., 2019). Bitumen and asphalt va-
pours produced at higher temperatures (i.e. 160 °C to 180 °C) emit more
dangerous levels of PAHs in comparison to low production and laying tem-
peratures (130 °C to 160 °C) (Motta et al., 2012). The effect of temperature
suggests that other methods such as warm-mix asphalt (WMA) can poten-
tially help reduce emissions of alkanes and PAHs while simultaneously sav-
ing energy (CPWR, 2018).
Working temperature is a critical factor impacting fumes emission. In-
creasing working temperature by 20 °C can lead to a total emitted
2
Science of the Total Environment 832 (2022) 155037
particulate concentration of 3 to 7 times higher than when exposed to a
lower temperature (Mo et al., 2019; Yang et al., 2019). Aging of materials
can also affect the concentration of emissions produced during working pe-
riods; this includes oxidised asphalt content (Bolliet et al., 2013; Jamshidi
et al., 2012b; Mo et al., 2020), binder (Jamshidi et al., 2012a) and additives
(Gong et al., 2016). Emission tests conducted on thermal, ultra-violet (UV),
and naturally aged, reclaimed asphalt pavement (RAP) showed that more
particulates were generated than fresh asphalt mixtures using virgin mate-
rials.
Some studies have shown that road paver operators - under the specific
conditions of the study - are exposed to emissions that exceed the maximum
permissible levels set for PAHs in the air of 10 mg/m3 and in some cases
even in short-term exposure of 25 ppm (Breuer et al., 2011; Burstyn et al.,
2002). With a growing number of studies investigating PAH carcinogenic-
ity (Abdel-Shafy and Mansour, 2016; Gehle, 2009), the maximum permissi-
ble exposure levels to PAHs for workers are applied to only five analytes of
interest, namely; naphthalene, phenanthrene, anthracene, chrysene and
benzo[a]pyrene (NIOSH, 1994). While other PAHs do not have threshold
limits, toxicology studies on PAHs reported that occupational exposure to
high concentrations of harmful substances and mixtures containing PAHs
could lead to symptoms such as eye irritation nausea, vomiting, diarrhoea
and confusion (Gehle, 2009; Ramírez et al., 2012), therefore posing a threat
to human health.
Due to the potential health effects of bitumen emissions, there have
been attempts to reduce VOCs and PAHs via the introduction of foreign ma-
terials during production or paving process such as deodorant (Cao et al.,
2021), Ca(OH)2-incorporated zeolite (Zhang et al., 2021), latex
(Rasoulzadeh et al., 2011), activated carbon filler (Xiao et al., 2017),
styrene-butadiene-styrene (SBS) thermoplastic (Cui et al., 2014) and
geopolymer additives (Tang et al., 2020). The addition of deodorants en-
hances the dispersion of waste rubber in the asphalt mix, improving overall
stability that attributes to increased oxidation and aging resistance. This im-
provement directly correlates to the release of sulphur-containing groups
(Cao et al., 2021). The use of a self-designed Ca(OH)2-incorporated zeolite
was found to reduce VOC emissions from asphalt due to the nature of its
mesoporous structure, which allowed water molecules to be released
within the cavities and channels, causing the bitumen's viscosity to de-
crease and, therefore, lowering the overall temperature of the asphalt lay-
ing operation (Zhang et al., 2021). If coupled with warm mix asphalt
technology, the addition of Ca(OH)2-incorporated zeolite significantly re-
duced the VOC emissions of bitumen up to 37%.
Similarly, the use of SBS coupled with activated carbon also contributed
to the reduction of VOC emissions from bitumen due to the high porosity
and large internal surface areas of the activated carbon that significantly re-
duce VOC emissions by up to 53% (Xiao et al., 2017). Furthermore, by
adding SBS without activated carbon fillers, the results exhibited a total
VOC reduction of 30% due to the physical cross-linking structure that can
prevent small molecules in the bitumen from escaping to the surface (Cui
et al., 2014).
The reduction of VOC emissions seems to be heavily attributed to mate-
rials that can divert the emissions from one place to another; geopolymer
additives such as a mixture of metakaolin, silica fume and ground granu-
lated blast-furnace slag are another group of materials used to reduce
VOCs and PM emissions from asphalt production. The pore structure of
the geopolymer additive coupled with their adsorption capabilities acts
like an internal “sponge” that suppresses the emissions of VOCs and partic-
ulate matter (PM) in both warm-mix and hot-mix asphalt production. The
total emitted compounds for warm-mix asphalt were reduced by 60% and
65% for hot-mix asphalt emissions (Tang et al., 2020). Additionally, post-
consumer latex is another material shown to reduce PAH emissions during
bitumen production by 50% compared to conventional methods due to the
prevention of maltene oxidation that normally results in an increase of
asphaltene from being emitted (Rasoulzadeh et al., 2011).
Despite the growth in the use of recycled plastics as bitumen modifier in
recent years, there have been no studies to the author's knowledge on
Y.J. Boom et al.
recycled plastics modified bitumen emissions. Therefore, this study aims to
investigate the gaseous emissions from several blends of bitumen modified
by various polyolefin recycled plastics.
2. Materials and methodology
2.1. Experimental design
The research investigated five types of recycled plastic in bitumen
(commingled polyethylene, low-density polyethylene, linear low-density
polyethylene, high-density polyethylene, and polypropylene) at various
temperatures (160 °C, 180 °C and 200 °C) and polymer content (1%, 2%,
4% and 6% by weight of bitumen). Neat bitumen and common industrial
polymer-modified bitumen are used as a reference for result comparisons.
A10E in Fig. 1 is an SBS-modified bitumen commonly used in Australia
on heavy trafficked roads and contains approx. 5.5–6% SBS by weight of
the binder; A35P is an ethylene vinyl acetate (EVA)-modified bitumen
with 5–5.7% EVA content. The structure of the study is based on the exper-
imental design shown in Fig. 1.
2.2. Reagents
The calibration standards of the 48 VOC compounds are from a single
mixture at 1000 mg/l in methanol (40353-U, 48 Component Indoor Air
Standard from Supelco, Bellefonte, USA). The standards of the 16 PAH com-
pounds were also from a single mixture at 1000 mg/l in methylene chloride
(PAH-615-1, EPA 610 from Agilent Technologies, Inc., Santa Clara, USA).
The minimal purity of the calibration standards was 98%. An internal
standard mixture of 1,4‑dichlorobenzene‑d4, chlorobenzene‑d5 and
fluorobenzene from Agilent Technologies, Inc. (STM-520-1, EPA 8000
Series Standards) was used for VOC analysis as internal standards as recom-
mended by Method 8260D (US EPA, 2018). In addition, an internal stan-
dard mixture of 1,4‑dichlorobenzene‑d4, acenaphthene-d10, chrysene-
d12, naphthalene-d8 and phenanthrene-d10 from Sigma-Aldrich was
used to analyze PAHs as recommended Method TO-13A (US EPA, 1999).
Fig. 1. Experimental design of research study.
3
Science of the Total Environment 832 (2022) 155037
2.3. Recycled plastics and reference bitumen
Five sources of recycled plastics were obtained from local plastic recy-
clers. The recycled plastics were used to produce recycled plastic modified
bitumen in this study. The visual representation of each plastic is shown in
Table A1. The selected plastics include, recycled low-density poly(ethylene)
(rLDPE), commingled polyethylene (cPE), recycled linear-low density poly
(ethylene) (rLLDPE), recycled high-density poly(ethylene) (rHDPE), and re-
cycled poly(propylene) (rPP). The properties of the polymers selected in
this study are tabulated in Table 1. It should be noted that the properties
of recycled plastics can differ from those of their virgin counterparts
(i.e., recycled LDPE from virgin LDPE) due to the addition of several addi-
tives during the recycling process such as UV-resistant agents, antioxidants,
quenchers, and fillers.
Recycled plastics were incorporated into base C170 bitumen, while A10E
and A35P grade polymer-modified bitumen was used as comparison refer-
ences. The physical properties of C170 grade, A10E and A35P bitumen are
tabulated in Table 2. C170 grade bitumen is equivalent to a standard
70/100 penetration grade bitumen, while A10E and A35P are often regarded
as the industry-standard polymer modified bitumen in Australia containing
approximately 5.5–6% SBS and 5–5.5% EVA polymer content, respectively.
2.4. Sample preparation
Bitumen was initially heated to the respective testing temperature (160
°C, 180 °C or 200 °C) in an oven before being transferred to an automatic
temperature-controlled hotplate. Plastic-modified bituminous blends were
produced with a total polymer content of 1%, 2%, 4% and 6% by weight of
base bitumen (C170). The blends were mixed with a mechanical shearing
overhead stirrer at an agitation rate of 2000 rpm and 160 °C, 180 °C, 200
°C for 2 h to ensure a homogenous dispersion of the polymer in the mix.
The temperature was monitored via a temperature probe and adjusted auto-
matically by the hotplate to guarantee constant temperature during the sam-
pling phase. This procedure was replicated for the neat C170 bitumen with no
addition of recycled polymers and polymer-modified bitumen A10E and
A35P for comparison purposes. Each sample was replicated twice for repeat-
ability, totalling the number of samples to 138 for this study.
Y.J. Boom et al. Science of the Total Environment 832 (2022) 155037

Table 1 VOCs, respectively. The sample size of all bitumen blends was 500 ± 5 g.
Physical properties of recycled plastics used in this study. Upon completion, the filter and sorbent tubes were capped and wrapped
Parameters rLDPE rLLDPE cPE rHDPE rPP with aluminum foil and stored in a refrigerant bag for analysis to prevent
Colour Grey Grey Multi-coloured White/clear Multi-coloured
the evaporation of the captured compounds in the sorbent tubes during
Shape configuration Pellet Pellet Flake Flake Granules transport.
Density (g/cm3) 1.01 0.95 0.93 0.95 0.89
2.6. Analytical methods

A total of 48 VOCs and 16 PAHs target compounds were selected based

on their occurrence in past studies (Boczkaj et al., 2014; Brandt and de
Table 2 Groot, 1999; Osborn et al., 2013; Ramírez et al., 2011; Roy et al., 2007)
Physical properties of C170, A35P and A10E used in this study. and their adverse effects on the environment and human health.
Properties Standard C170 A35P A10E After sampling, each sorbent tubes (XAD-2 and charcoal sorbent tube)
Penetration at 25 °C (0.1 mm) AS 2341.12 74 34 84 were scored with a tube cutter (Orbo tube cutter, Supelco). Each sorbent
Softening point (°C) AGPT-T131 48.1 67 88.4 tube's front and back sections were placed in individual 10-ml capped
Dynamic viscosity at 135 °C (Pa.s) AS/NZS 2341.4 0.62 2.43 2.96 vials amounting to two capped vials for each type of sorbent tube. The
Dynamic viscosity at 165 °C (Pa.s) AS/NZS 2341.4 0.10 0.39 0.98
PTFE-laminated membrane filter was opened by cutting through the plastic
wrap, and the membrane filter was placed in a 10-ml capped vial. All sam-
ples were handled with designated forceps for each sampling component
2.5. Fume generation and measurement and rinsed with stock solution in between each sample. In total, a sample
will comprise of five vials (two for VOC and three for PAH) that include
The sampling process was conducted following NIOSH Method 5515 for one vial for the membrane filter, two vials (front and back sorbent section)
PAHs and Method 0031 for VOCs (NIOSH, 1994; US EPA, 1996). The sam- for the XAD-2 sorbent tubes and two vials (front and back sorbent section)
pling was conducted at three constant temperatures of 160 °C, 180 °C and for the charcoal sorbent tubes.
200 °C throughout the entire mixing process. An SKC AirChek XR5000 per- During the extraction process, 1.6 ml of extraction solution (40 mg/l of
sonal sample pump extracted a measured volume of ambient air during the internal standards diluted in carbon disulfide for VOCs, 7.5 mg/l of internal
blending process. The air sampling train was connected to the side necks of standards diluted in methylene chloride for PAHs) was added to each vial
the three-neck vial via a silicone stopper to direct the emissions onto the respective to the compounds of interest. The vials containing sorbent tube
inlet of the sorbent tubes/filter. The modified sampling setup inspired by sections were immediately capped with PTFE caps and sat for 30 min
the Brandt method (Brandt and de Groot, 1999) in a laboratory environ- with occasional swirling. At the same time, the vial with the membrane fil-
ment is shown in Fig. 2. The air was drawn through a XAD-2 sorbent tube ter was placed in an ultrasonic bath for 30 min to extract the particle-based
(8 × 110 mm) attached to a 37 mm diameter PTFE-laminated membrane PAH emissions. Immediately following the extraction process, all sample
filter at a constant flow rate of 2 l/min for PAH collection, while the air solutions were transferred into 1.5 ml GC vials supplied by Agilent Technol-
was captured onto a charcoal sorbent tube at a constant flow rate of ogies, Inc., via single-use syringes attached to 0.45 μm filters.
0.5 l/min for VOC collection. All bitumen blends were sampled for All sample vials were analyzed by using GC/MS via direct injection. The
120 min to obtain 240 l and 60 l of air volume captured for PAHs and GC/MS conditions for each category compound of interest (VOC and PAH)
were conducted separately according to modified standards.
VOC samples were analyzed using an Agilent 5977B series gas
chromatography–mass spectrometry equipped with a single quadrupole.
The separation column used was 30 m × 250 μm with a 1.4 μm film thick-
ness coated with 6% cyanopropylphenyl/94% dimethylpolysiloxane
(DB-624). The GC/MS was programmed from 35 °C to 100 °C (6 °C/min),
100 °C to 180 °C (12 °C/min), and 180 °C to 200 °C (20 °C/min). The tem-
perature of the injector was 225 °C (30:1 split ratio with an injection
volume of 1 μl). Helium was used as the carrier gas at 1.3 ml/min to quan-
tify the identified VOCs with the GC/MS. The MS interface was set at
280 °C. The mass spectrometer acquired data in scan mode with an interval
mass spectrum from 35 to 280 m/z, operating at an electron impact energy
of 70 eV. Qualitative identification of the target VOCs was based on the
match of the retention times and the ion ratios of the target quantifier
and qualifier ions. 48 VOCs were analytically quantified using an internal
standard mixture and response factors related to a VOC calibration stan-
dard based on an 8-point calibration curve for each compound. The 48 com-
pounds were grouped and assigned to three corresponding analytes
(internal standards) following USEPA Method 8260D. The retention times
and the quantifier/qualifier ions for 48 VOC compounds and three internal
standards are presented in Table A2. Internal standards are identified by
highlighted cells.
It should be noted that, the use of carbon disulfide must only be used
where specific studies are catered towards the requirement of using carbon
disulfide. Alternative solvents are recommended when investigating less
analytical sensitive compounds. As a strict safety measure, carbon disulfide
must be handled with appropriate personal protective equipment under a
fume hood and according to procedures listed in its safety data sheet.
PAH analysis was conducted on the same GC/MS (Agilent 5977B series)
Fig. 2. Modified Brandt sampling method used in the study. using single ion monitoring (Motta et al.). The separation column used was

4
Y.J. Boom et al.
a 30 m × 250 μm with a 0.25 μm film thickness coated with 5% phenyl-
methyl siloxane phase (HP-5MS). The GC/MS was programmed from 80
°C (1 min) to 325 °C (5 min) at 12.5 °C/min. The temperature of the injector
was 300 °C (0:1 split ratio with an injection volume of 0.5 μl). Helium was
used as the carrier gas at 1 ml/min to quantify the identified PAHs with the
GC/MS. The MS interface was set at 230 °C. The mass spectrometer ac-
quired data in SIM mode with 11 interval time segments for 16 individual
PAHs. Qualitative identification of the target PAHs was based on the
match of the retention times and the ion ratios of the target quantifier
and qualifier ions. Sixteen PAHs were analytically quantified using an isoto-
pically internal standard mixture and the response factors related to a PAH
calibration standard based on a 6-point calibration curve for each com-
pound. The precursor ions and retention time defined the PAH compounds
present in all samples and quantification via internal standards highlighted
in Table A3.
2.7. Statistical analysis
Data presented are reported as the mean ± standard deviation. Depen-
dent (paired) t-tests (two-tailed) were conducted to determine the signifi-
cance of intra-group differences (replicates of samples tested within the
same parameters). To evaluate the differences between emissions from
recycled plastic blends against benchmark reference bitumen blends
(C170, A10E and A35P), an independent (unpaired) t-test (two-tailed)
was conducted for comparison. A p-value below 0.05 was considered to as-
sess thesignificance difference between two mean values.
2.8. Characterization of the recycled plastics
The physical and chemical properties of each of the recycled plastic ma-
terials were assessed via differential scanning calorimetry (DSC), thermal
degradation analysis (TGA) and water contact angle (WCA). Details of
each analytical method can be found in another study of the authors
(Giustozzi et al., 2021).
The DSC analysis was used to identify and determine the polymer com-
position of each plastic source while the TGA showed the onset of thermal
degradation of the materials, i.e., the maximum temperature at which the
material can be used with no structural change. The melting point and hy-
drophobicity of each plastic was determined by DSC and WCA, respec-
tively, a WCA higher than 90° demonstrating a hydrophobic behavior
(Tables 3 and 4).
3. Results and discussion
3.1. Total VOC and PAH concentrations
The selected GC–MS quantification ion chromatograms of the 48 VOCs
and 16 PAHs in a calibration standard mix are shown in Figs. A1 and A2 in
the Appendix. The chromatogram displays excellent sensitivity, separation,
and peak shape of each selected analyte, including its internal standards. In-
ternal standards used for both VOC and PAH emissions are marked in bold
and italicized.
Table 3
Chemical and physical properties of each source of recycled plastics.
Parameters/plastics rLDPE rLLDPE
Composition 68% LDPE 87% LLDPE
32% LLDPE 13% PP
Melting point (°C) a 108 108
122 123
Thermal degradation onset (°C) 429 424
WCA (°) 78b 100
a
Multiple melting points can be observed for each polymer part of a blend.
b
Calcium carbonate, a relatively hydrophilic filler, was detected in rLDPE.
5
Science of the Total Environment 832 (2022) 155037
Table 4
Chemical and physical properties of virgin thermoplastics used as references.
Parameters/plastics Virgin EVA Virgin SBS
Composition 100% EVA 100% SBS
Melting point (°C) 71 Nonea
Thermal degradation onset (°C) 323 433
WCA (°) 80 121
a
SBS is an amorphous material with no true melting point.
The recycled plastic modified bitumen emission results are shown in
Fig. 3 for VOC emissions and Fig. 4 for PAH emissions; both graphs are
sorted by working temperature to obtain three sets of graphs. VOC and
PAH concentrations of neat C170, A10E and A35P are plotted as lines on
the graph as reference values for comparison purposes. According to
Figs. 3 and 4, it is clear that the addition of EVA and SBS into bituminous
blends achieve the lowest VOC and PAH concentration at various working
temperatures.
The effect of temperature on bitumen fumes is relative to the emissions
of VOC and PAH concentrations; as the temperature increases, the higher
the concentration of VOCs and PAHs is emitted. According to Fig. 3, VOC
concentrations are increased significantly by 43% (t-test, p = 0.013) and
163% (p = 0.0003) when temperatures are increased from 160 °C to
180 °C and 200 °C, respectively, for neat C170. Specifically, the emissions
reached 2.96 ± 0.11 mg/m3 at 180 °C and 7.87 ± 0.10 mg/m3 at
200 °C. In A35P grade bitumen, increments of 30% and 25% in VOC con-
centrations are observed for the same temperature increase from 160 °C.
Similarly, A10E grade bitumen exhibited 68% and 52% increments in
VOC concentrations at 180 °C and 200 °C, respectively from 160 °C. This
trend is also seen in the case of recycled plastic modified bitumen at various
temperatures.
Similarly, Fig. 3 also shows the effect of temperature on PAH concentra-
tions. PAH concentrations of C170, A35P and A10E at 160 °C increased by
67%, 24% and 39% when working temperatures were increased to 180 °C.
At 200 °C, the PAH concentrations for all three reference bitumens in-
creased significantly compared to their respective 160 °C blends by 243%
(p = 0.001), 248% (p = 0.002) and 34% (p = 0.032) for C170 (21.4 ±
0.16 μg/m3), A35P (9.36 ± 0.20 μg/m3) and A10E (3.84 ± 0.24 μg/m3),
respectively. The spike in A35P bitumen could be likely due to the EVA
polymers starting to degrade. Although the precise content of vinyl acetate
in the EVA used is not known, EVA with low percentages of vinyl acetate
are known to decompose at a lower temperature compared to higher per-
centages of vinyl acetate (Crawford and Throne, 2002). In recycled plastic
modified bitumen, PAH concentrations were below C170 values but
exceeded both A10E and A35P values at 160 °C. However, when tempera-
tures were increased to 180 °C and 200 °C, PAH concentration levels
exceeded A35P and A10E. This spike could be due to the composition of
plastics in general, as they release PAHs when heated to high temperatures
(Yamashita et al., 2009). All polyolefins would have presumably melted at
180 °C and 200 °C therefore, releasing high PAH concentrations (Yamashita
et al., 2009). Ultimately, the effect of temperature poses a significant contri-
bution to VOC and PAH emissions (up to 163% for VOCs and 248% for
cPE rHDPE rPP
61% PP 100% HDPE 99% PP
23% LLDPE 1% LLDPE
16% LDPE
163 134 164
122 122
112
389 438 383
109 101 101
Y.J. Boom et al.
Fig. 3. VOC concentrations of recycled plastic modified bitumen and neat C170, A10E and A35P bitumen at various temperatures.
PAHs). The results of each emission categorized by plastic-type are shown
in Figs. A3a–e and A4a–e.
VOC and PAH emissions vary greatly in bituminous fumes generated
when different amounts of recycled plastics are used. VOC concentrations
generated from rLDPE blends at all temperatures show that it yielded the
highest VOC reduction at 180 °C compared to other recycled plastic types;
this can be seen throughout all-polymer contents at 1%, 2%, 4% and 6%.
However, at 200 °C, the blend yielded higher VOC concentrations than
cPE at 1% and 4% polymer content. All rLDPE blends exhibited lower
VOC concentration values in comparison to C170 reference values across
all polymer contents. However, compared to A35P and A10E, the reference
polymer modified bitumen blends yielded lower VOC concentrations across
all temperatures. This reduction trend of rLDPE compared to other recycled
plastics can possibly be explained by the exact polymer composition of the
rLDPE found via TG analysis as over 15% of the actual composition was
identified as foreign compounds (i.e., external fillers). This modification oc-
curred during the recycling phase of the waste plastic, and it is common
practice by many recyclers depending on the final application.
6
Science of the Total Environment 832 (2022) 155037
Bituminous blends using cPE yielded the highest VOC concentrations at
temperatures 160 °C and 180 °C in comparison to all other recycled plastic
blends. At both temperatures, 1% cPE blends yielded VOC concentrations
like neat C170, signifying little effect on the reduction of VOC concentra-
tion. However, when the polymer contents were increased to 2%, 4% and
6%, the VOC concentrations decreased although still showing higher values
compared to the other types of plastic. Despite acquiring higher VOC con-
centrations at 160 °C and 180 °C, cPE blends at 200 °C yielded the
second-lowest VOC concentrations compared to other plastic types, the
first being rPP. The spike in VOC concentration could be attributed to the
various plastic blends or possible additives in cPE, as shown in Table 3.
VOC concentrations generated from rLLDPE marked the average level
between all plastic types, not attributing to the highest reduction in VOC
concentration nor the lowest. At 160 °C, rLLDPE blends provided the sec-
ond least VOC reduction at 1%, 2% and 4% polymer content. Despite hav-
ing the least effect on VOC reduction at 6% polymer content in comparison
to other polymer types, the VOC concentrations from 6% rLLDPE (1.02 ±
0.11 mg/m3) were still significantly reduced by over 100% (t-test, p =
Y.J. Boom et al.
Fig. 4. PAH concentrations of all recycled plastic modified bitumen and neat C170, A10E and A35P bitumen at various temperatures.
0.011) and over 45% (p = 0.049) compared to neat C170 and A35P, re-
spectively. At 180 °C, 4% rLLDPE blends (1.59 ± 0.12 mg/m3) attributed
to 47% (p = 0.008) decrease in VOC concentrations, while 6% rLLDPE
blends (1.15 ± 0.13 mg/m3) acquired 61% reduction in VOC concentra-
tions compared to C170 (2.99 ± 0.09 mg/m3). At 200 °C, when tempera-
tures have far exceeded the melting point of rLLDPE, VOC concentrations
are well above A10E and A35P reference values. Despite these concentra-
tion levels, the total VOC concentration is still lower in comparison to con-
ventional C170 blends.
The use of rHDPE in bituminous blends saw the highest VOC reduction
across 160 °C and 180 °C at nearly all polymer contents. Additionally, at
both temperatures, 2%, 4%, and 6% rHDPE blends yielded lower VOC con-
centrations than A35P, while 4% and 6% rHDPE blends yielded VOC con-
centrations below A10E. However, at 200 °C, the VOC concentrations
exceed all other plastic types and above A35P and A10E values. The rising
trend in VOC concentration contributed by rHDPE blends at 200 °C could
7
Science of the Total Environment 832 (2022) 155037
be attributed to the modification of the plastic during its reprocessing/
recycling stage (Alassali et al., 2020).
VOC concentration from rPP blends exhibited VOC reductions at all
temperatures and polymer contents. At 160 °C, 4% and 6% rPP blends
could reduce VOC reductions lower than A10E. VOC concentrations at
200 °C were reduced by over 152% (1% rPP) compared to neat C170. As
the polymer content increases to 6%, VOC reductions continue to increase
and yield values below A10E and A35P, a feat no other plastics could
achieve. The VOC reduction trend at high temperatures is attributed to
the thermal susceptibility of polypropylene as their melting temperature
is significantly higher (ranging from 30 °C to 56 °C) than other polyolefins
such as HDPE and LDPE/LLDPE.
For PAH concentrations, rLDPE blends reduce total PAH concentration
levels at all temperature levels compared to C170 values. Despite yielding
higher values than A10E and A35P at 160 °C and 180 °C, all rLDPE blends
at 200 °C yielded lower PAH concentration levels in comparison to A10E
Y.J. Boom et al.
and C170 reference values across all polymer contents. 6% rLDPE at 160 °C
exhibited PAH levels below all reference values due to the increasing
amount of polymer content. Despite a reduction in PAH concentration
levels, at 180 °C across all polymer contents, rLDPE blends did not dip
below A10E or A35P reference values.
Bituminous blends using cPE saw a PAH reduction at 160 °C, while the
PAH reductions at 1%, 2% and 4% were still above A10E and A35P refer-
ence values, 6% cPE blends reduced PAH concentrations below the two-
reference polymer modified bitumen blends. At 180 °C, all cPE blends
yielded higher PAH concentration values than A10E and A35P values. De-
spite PAH concentration levels dipping below A35P values at 200 °C across
all polymer contents, PAH concentration values were still above A10E ref-
erence values. PAH concentration levels were at their lowest among all
plastic-type at 200 °C across 1%, 2% and 4% cPE. At 6% cPE, PAH concen-
tration levels were slightly above rLDPE blends.
PAH concentration levels of rLLDPE blends exhibited the highest PAH
reduction at 160 °C across 1% and 2% polymer contents. The increasing
trend of PAH reduction was not exponential, as 4% and 6% rLLDPE blends
yielded the second-lowest PAH reduction and the lowest PAH reduction, re-
spectively. All PAH reductions yielded at 160 °C were below neat C170;
however, above A10E and A35P values. At 180 °C, no rLLDPE blends
achieved lower PAH concentrations in comparison to A10E or A35P. The
increment in temperature to 200 °C resulted in a PAH reduction below
C170 and A35P values across all polymer contents. Despite the reduction,
the exhibited values were still above A10E values at 200 °C.
The use of rHDPE in bituminous blends saw a drastic PAH reduction
below all reference values at 6% polymer content when heated to 160 °C
despite yielding the second-highest PAH concentration at 1%, 2% and 4%
rHDPE. At 180 °C, significant PAH reduction from 4% rHDPE blends
(2.30 ± 0.26 μg/m3) attributed to 41% (t-test, p = 0.049), while 6%
rHDPE blends (1.94 ± 0.24 μg/m3) inhibited 60% (p = 0.032) reduction
in PAH concentration against C170 (3.73 ± 0.21 μg/m3). The PAH trend
of rHDPE blends at 200 °C was like the VOC trends, yielding the highest
concentration across all polymer contents. Despite a decreasing trend in
PAH concentration across all polymer contents of rHDPE at 200 °C, all
values were significantly higher (ranging from 35% to 80%) than A35P
and A10E reference values.
Despite yielding the highest PAH level at 160 °C across 1%, 2% and 4%
polymer content, all values were below C170. At 6% rPP, PAH concentra-
tion values dipped below all reference values, including A10E and A35P.
Compared to 160 °C, rPP blends yielded the lowest PAH concentration
values at 180 °C across all polymer contents. Specifically, the emissions
from 4% rPP (3.14 ± 0.18 μg/m3) and 6% rPP (2.62 ± 0.24 μg/m3) attrib-
uted to a decrease in PAH concentration by 50% and 58%, respectively
against C170 (6.24 ± 0.18 μg/m3). While 1%, 2% and 4% polymer content
at 180 °C were above A10E and A35P values, 6% rPP blends yielded lower
values than A10E and A35P values. At 200 °C, rPP blends yielded the
3.5
Mass loss at 200 °C
3
2.5
Mass loss (%)
1.5
0.5
0
1%
rLDPE cPE rLLDPE
Fig. 5. Mass loss in percentage of plastic modified bitumen at 200 °C after 2 h.
Science of the Total Environment 832 (2022) 155037
second-highest PAH concentration across all polymer content. While the
PAH reduction varied from one polymer of rPP content to the other, all ac-
quired values were above A10E and A35P reference values.
3.2. Effect of polymers in bitumen
The effect of recycled plastics in bitumen is further investigated through
thermogravimetric analysis. All samples were held for 1 min at 35 °C then
heated to 200 °C at a heating rate of 10 °C/min in nitrogen, held for 2 h
and subsequently heated to 850 °C in the air at 50 °C/min and held for
5 min to oxidize and burn off remaining residues. TGA tests were replicated
three times to ensure the accuracy and reliability of the obtained results.
Fig. 5 shows the estimation of mass loss results generated from all bitumen
blends in this study.
The plots show the per cent mass as a function of sample temperature
under a nitrogen purge. The TGA results show a unique linear relationship
between increasing polymer content and thermal performance of the bitu-
minous blends whereby, the higher the polymer content, the lower percent-
age in mass loss (i.e. better thermal performance). The enhancement of the
thermal characteristics would also mean that analytes that would typically
burn off at 200 °C have also been strengthened and can resist more heat.
Based on the results above, all cPE and rPP modified blends have emit-
ted lower concentration levels of PAHs and VOCs than rLDPE, rLLDPE and
rHDPE blends; this could be due to their actual content of polypropylene
(approximately 61% and 91% polypropylene for cPE and rPP, respectively).
The higher melting temperature of polypropylene in general compared to
polyethylene was reflected through the mass loss held at 200 °C for 2 h.
When rPP blends were increased to 6% polymer content, the mass loss at
200 °C was identical to A10E blends using SBS polymers. Despite the en-
hancement in thermal degradation using recycled plastics across all poly-
mer contents, no modified blends acquired lower mass loss compared to
A35P blends at 200 °C when held for 2 h. Overall, adding polymers has
changed the compositions of emissions shown above, causing the lesser
weight to be burned off at higher temperatures (200 °C). Individual TGA
graphs can be found in the supplementary document of this article
(Fig. A5a–e).
In general, using polymers in bitumen regardless of its type and source
can ultimately reduce overall emissions from a VOC and PAH perspective.
The results shown via the TGA analysis indicate that adding polymers en-
hances the thermal stability of the modified bitumen blends, resulting in
a lower mass loss than neat C170 when held at 200 °C for 2 h. Additionally,
the increase of polymer contents has also contributed to reducing overall
emissions. Industry-standard polymer modified bitumen A10E and A35P
used as references contain over 5–6% polymer content and exhibit more ro-
bust thermal stability when compared to neat C170. Therefore, with this ra-
tionale, the increase in polymer content contributes to higher reductions in
emissions.
2% 4% 6%
Polymer content (%)
rHDPE rPP C170 A10E A35P
8
Y.J. Boom et al. Science of the Total Environment 832 (2022) 155037

Based on the study, results obtained show that emissions are amplified
by multiple orders when working temperatures are increased regardless of
the blend and type of polymer used. Furthermore, analyzing data through
the total emitted concentration can be misleading; therefore, compound
concentration analysis is necessary to determine the actual effects of
recycled plastics in bitumen. The following section provides an overview
of each group's top-4 heavily weighted compounds to provide insights on
the effects of incorporating recycled plastics into bitumen.
3.3. Compound concentration assessment
Of the 48 VOCs and 16 PAHs that were analyzed in this study, 4 com-
pounds from each group were selected based on their high level of concen-
tration. On average, the selected 4 compounds make up approximately
70–80% of the total emissions of each sample. While the remainder of the
compounds detected must be taken into consideration to study on the ef-
fects of recycled plastics in bitumen, this study will prioritize the emitted
compounds that are significantly affected from the addition of recycled
plastics. The selected compounds for concentration assessment of all sam-
ples based on the total quantity emitted, they include nonane, decane,
undecane and dodecane for VOCs, and naphthalene, acenaphthene,
fluorene and phenanthrene were selected for PAHs. Figs. 6 and 7 depict
the percentage differences of VOCs and PAHs released by the plastic modi-
fied bitumen at 6% polymer content against neat C170 bitumen across all
working temperatures. For reference, the concentration of each respective
compounds from conventional C170 values are denoted by ‘0%’ on the y-
axis. Plastic modified blends that acquired higher values above 0% signified
an increase in concentration for the respective compound while values
below 0% (in the negative region) signified a decrease in concentration of
each respective blend.
The addition of 6% plastics into bitumen decreased all VOC concentra-
tions in comparison to neat C170 across all working temperatures. 6%
rLLDPE blends measured highest concentration levels while rHDPE attrib-
uted to the highest reduction in VOC concentrations at 160 °C. At 180 °C,

VOC compounds assessment at 160 °C

Percentage difference against neat C170

-20

-40
(%)

-60

-80

-100
Nonane Decane Undecane Dodecane
Compounds
VOC compounds assessment at 180 °C
Percentage difference against neat

-20
C170 (%)

-40

-60

-80

-100
Nonane Decane Undecane Dodecane
Compounds

VOC compounds assessment at 200 °C

Percentage difference against neat C170 (%)

-20

-40

-60

-80

-100
Nonane Decane Undecane Dodecane
Compounds
rLDPE cPE rLLDPE rHDPE rPP A10E A35P

Fig. 6. Percentage difference of VOC concentration from 6% polymer content blends against C170 at 160 °C, 180 °C and 200 °C.

9
Y.J. Boom et al. Science of the Total Environment 832 (2022) 155037

PAH compound assessment at 160 °C

20

Percentage difference against neat

0

-20

C170 (%)
-40

-60

-80

-100
Naphthalene Acenaphthene Fluorene Phenanthrene
Compounds

PAH compound assessment at 180 °C

20
Percentage difference against neat

-20
C170 (%)

-40

-60

-80

-100
Naphthalene Acenaphthene Fluorene Phenanthrene
Compounds

PAH compound assessment at 200 °C

Percentage difference against neat C170

200

150

100
(%)

50

-50

-100
Naphthalene Acenaphthene Fluorene Phenanthrene
Compounds

rLDPE cPE rLLDPE rHDPE rPP A35P A10E

Fig. 7. Percentage difference of PAH concentration from 6% polymer content blends against C170 at 160 °C, 180 °C and 200 °C.

rLDPE blends showed the highest reduction in VOC concentrations
followed by rHDPE blends. However, rHDPE blends would ultimately
emit the highest concentration levels at 200 °C. rPP blends on the other
hand attributed to the highest VOC reduction at 200 °C.
The addition of plastics also experienced a decreasing trend in com-
pound concentration across 160 °C and 180 °C. All plastic modified blends
at 6% polymer content yielded lower values compared to neat C170 at
these temperatures. At 200 °C, the addition of 6% rLLDPE, rHDPE and
rPP yielded higher naphthalene values compared to neat C170 by 29%,
200% and 76%, respectively. Despite the spike in naphthalene at these
blends, the concentrations (7 μg/m3) were far from threshold limit values
of naphthalene at 440 μg/m3. Additionally, these values were also lower
compared to conventional C170 bitumen.
According to the USEPA and IARC, none of the selected compounds for
concentration analysis is defined as carcinogenic compound. Naphthalene
was the only compound that yielded a classification code C in 1987, later
deemed “cannot be determined” from a carcinogenicity standpoint (IRIS,
2011). However, further studies involving extreme exposure to naphtha-
lene have shown significant risk to human health (Preuss et al., 2003). Al-
though fluorene and phenanthrene are among the compounds that were
not classifiable as carcinogenic to humans and no cancer risk assessment
was done on acenaphthene, various studies have shown that when exposed
to high levels of these compounds they can potentially harm users
(Alhamdow et al., 2020; Guo et al., 2018; Kadry et al., 1995; Reshetycek
et al., 1970).
From a VOC perspective, nonane, undecane, decane and dodecane are
closely related compounds commonly referred to as n-alkanes typically
found in petroleum-based solvents including gasoline, fuel, and bitumen
(Schmidt et al., n.d.; Speight and El-Gendy, 2018). While these compounds
are not classified as carcinogenic compounds, studies have shown that they
can still potentially cause irritations under high exposure levels (Babu et al.,
2004; Carpenter et al., 1978; Plech et al., 1975). Therefore, considering

10
Y.J. Boom et al.
these discussions, reducing overall emissions from incorporating recycled
plastics is greatly beneficial from human health and environmental per-
spectives.
3.4. Sorption of gases in polymers
To date, there are no similar studies involving the extraction of VOC or
PAH from the use of recycled plastics modified bitumen for result compar-
ison. However, there have been studies focusing on reducing the PAH and
VOC emissions by using SBS thermoplastic. When these studies are com-
pared to the current study, a noticeable trend can be identified whereby in-
corporating similar materials to recycled plastics such as SBS and EVA
promotes a decrease in both VOC and PAH emissions. The decrease in
VOC and PAH concentrations may be due to several reasons, including
the polymer's ability to decrease bitumen's temperature susceptibility, pre-
venting the release of harmful emissions when tested at the same tempera-
ture. Additionally, the adsorption of PAHs onto plastics can be responsible
for the overall emission reduction when introduced in bitumen. Studies in-
vestigating PAHs' absorption rate using plastics suggest that the physical
and chemical properties of the specific plastics, i.e. density (Fries and
Zarfl, 2012), surface area (Teuten et al., 2007), diffusivity (Pascall et al.,
2005; Rusina et al., 2007) and crystallinity (Karapanagioti and Klontza,
2008; Mato et al., 2001) ultimately determine PAH sorption capacity. No-
ticeably, polyethylene is known for its affinity to various organic contami-
nants with varying hydrophobicity and large surface areas compared to
other common plastics such as PP and PVC; therefore, it is commonly
used to trace organic contamination in water as sampling devices
(Lohmann, 2012). Although the importance of particle size and tempera-
ture (Sørensen et al., 2020) must be taken into consideration as they are
major determining factors for the degree of PAH sorption to plastics, the
overall findings suggest that plastics do have the capacity to absorb PAHs
depending on their level of hydrophobicity even at ambient temperature
(Müller et al., 2001; Wang et al., 2021).
While the current study employs high working temperatures (160 °C to
200 °C) instead of low temperatures (5 °C to 30 °C) to investigate the sorp-
tion of PAHs using plastics, the literature presented is sufficient to conclude
on the PAH sorption capabilities of plastics that has contributed to the re-
duction of total emissions when plastics are introduced in bitumen produc-
tion. However, with the use of recycled plastics instead of engineered
polymers, there is a theoretical tipping point of using these plastics at
higher temperatures as exceeding temperatures above the melting point
may cause plastics to deteriorate and break down, leading to an increase
in PAH concentrations (Yamashita et al., 2009). Additionally, the recycling
process of plastics from their source could potentially contribute to the ac-
cumulation of PAHs in the end product; this is attributed to the level of con-
tamination pre-processed (Alassali et al., 2020; Wang et al., 2021).
Ultimately, yielding higher PAH levels when added into the production of
recycled plastic modified bitumen.
4. Conclusion and recommendation for future work
The study investigated the emissions of recycled plastic modified bitu-
men with conventional C170 grade bitumen, A35P and A10E polymer-
modified bitumen as a reference via air sampling according to NIOSH
5515 for PAHs and Method 0031 for VOCs. Analytical methods modified
from Method 8260D for VOC and Method TO-13A for PAH analyses were
employed. This study showcases an extensive overview of the use of differ-
ent polymers obtained from different sources, various polymer content and
blending temperature, and repetitive testing. A total of 138 sample runs
were conducted inclusive of replicates. Based on the test results and discus-
sion, the following conclusions were drawn:
• The effect of temperature on total emissions is evident as emissions are
significantly amplified (up to 248% increase) regardless of polymer con-
tent or type of polymers used.
• The addition of recycled plastics reduces the overall total emissions
11
Science of the Total Environment 832 (2022) 155037
regardless of source and type (recycled or virgin).
• Increasing values of polymer contents contribute to higher reductions (up
to 68% for PAHs and 78% for VOCs) of emissions in general.
• In some instances, higher polymer content blends containing rHDPE and
rPP produced VOC levels below the A10E and A35P reference values at all
working temperatures.
• The reduction rate of VOC and PAH concentration levels from the use of
recycled plastics must consider the contamination levels, source, compo-
sition, and possible modification of plastics occurring during the recycling
process.
• While the overall emitted compounds provide a general understanding on
the effects of adding recycled plastics, individual compound analysis is re-
quired to assess the risks of adding recycled plastics.
Although the inclusion of recycled plastics has resulted in a reduction of
total VOC and PAH emissions, it should also be noted that the laboratory
tests were conducted over a 2-hour period in a closed environment com-
pared to an onsite situation where workers would typically work over
8-hour shifts. In addition, laboratory-generated fumes are severely more
concentrated than onsite testing due to various environmental factors includ-
ing, wind speed and direction, position and activity of workers, temperature,
and altitude, to name a few. Therefore, this study on laboratory-generated
fumes should not be used to develop occupational health and safety guide-
lines or any means of a toxicology report but rather to compare various
types of polymer-modified and neat bitumen in controlled conditions. The
present novel study of laboratory-generated fumes only provides the founda-
tion of incorporating recycled plastics in bitumen. In general, due to the sig-
nificant effect of temperature on emissions, it is recommended to lower as
much as possible the production and laying temperature in the field. In addi-
tion, due to the positive effect of the polymer modification on retaining vola-
tile particles, it is suggested that polymer-modified bitumen can reduce target
compounds up to 80–90% compared to neat bitumen. However, more study
is needed on this latter aspect.
CRediT authorship contribution statement
Yeong Jia Boom: Conceptualization, data curation, formal analysis,
methodology, validation, resource, writing – original draft. Marie Enfrin:
Data curation, formal analysis, investigation, writing – review & editing.
Stephen Grist: Resources, validation, supervision, writing – review.
Filippo Giustozzi: Conceptualization, funding acquisition, project admin-
istration, supervision, writing – review & editing.
Declaration of competing interest
The authors declare the following financial interests/personal relation-
ships which may be considered as potential competing interests: Filippo
Giustozzi reports financial support was provided by Austroads Ltd.
Acknowledgements
This work was supported by Austroads Ltd. under project number
APT6305. The authors are grateful for their financial support. The opinions
expressed therein are of the authors only and any error remains on the sole
responsibility of the authors.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.scitotenv.2022.155037.
References
Abdel-Shafy, H.I., Mansour, M.S.M., 2016. A review on polycyclic aromatic hydrocarbons:
source, environmental impact, effect on human health and remediation. Egypt. J. Pet.
25 (1), 107–123. https://doi.org/10.1016/j.ejpe.2015.03.011.
Y.J. Boom et al.
Alassali, A., Calmano, W., Gidarakos, E., Kuchta, K., 2020. The degree and source of plastic
recyclates contamination with polycyclic aromatic hydrocarbons. RSC Adv. 10 (73),
44989–44996. https://doi.org/10.1039/D0RA08554E.
Alhamdow, A., Essig, Y.J., Krais, A.M., Gustavsson, P., Tinnerberg, H., Lindh, C.H., Hagberg,
J., Graff, P., Albin, M., Broberg, K., 2020. Fluorene exposure among PAH-exposed
workers is associated with epigenetic markers related to lung cancer. Occup. Environ.
Med. 77 (7), 488. https://doi.org/10.1136/oemed-2020-106413.
Babu, R., Chatterjee, A., Ahaghotu, E., Singh, M., 2004. Percutaneous absorption and skin ir-
ritation upon low-level prolonged dermal exposure to nonane, dodecane and tetradecane
in hairless rats. Toxicol. Ind. Health 20 (6–10), 109–118. https://doi.org/10.1191/
0748233704th197oa.
Boczkaj, G., Przyjazny, A., Kamiński, M., 2014. Characteristics of volatile organic compounds
emission profiles from hot road bitumens. Chemosphere 107, 23–30. https://doi.org/10.
1016/j.chemosphere.2014.02.070.
Bolliet, C., Juery, C., Thiebaut, B., 2013. Impact of oxidation process on polycyclic aromatic
hydrocarbon (PAH) content in bitumen. J. Occup. Environ. Hyg. 10 (8), 435–445.
https://doi.org/10.1080/15459624.2013.801820.
Brandt, H.C.A., de Groot, P.C., 1999. A laboratory rig for studying aspects of worker exposure
to bitumen fumes. Am. Ind. Hyg. Assoc. J. 60 (2), 182–190. https://doi.org/10.1080/
00028899908984433.
Breuer, D., Hahn, J.-U., Höber, D., Emmel, C., Musanke, U., Rühl, R., Spickenheuer, A., Raulf-
Heimsoth, M., Bramer, R., Seidel, A., Schilling, B., Heinze, E., Kendzia, B., Marczynski, B.,
Welge, P., Angerer, J., Brüning, T., Pesch, B., 2011. Air sampling and determination of
vapours and aerosols of bitumen and polycyclic aromatic hydrocarbons in the Human
Bitumen Study. Arch. Toxicol. 85 (1), 11–20. https://doi.org/10.1007/s00204-011-
0678-1.
Burstyn, I., Randem, B., Lien, J.E., LangÅRd, S., Kromhout, H., 2002. Bitumen, polycyclic ar-
omatic hydrocarbons and vehicle exhaust: exposure levels and controls among Norwe-
gian asphalt workers. Ann. Occup. Hyg. 46 (1), 79–87. https://doi.org/10.1093/
annhyg/mef023.
Cao, L., Yang, C., Li, A., Wang, P., Zhang, Y., Dong, Z., 2021. Flue gas composition of waste
rubber modified asphalt (WRMA) and effect of deodorants on hazardous constituents
and WRMA. J. Hazard. Mater. 403, 123814. https://doi.org/10.1016/j.jhazmat.2020.
123814.
Carpenter, C.P., Geary, D.L., Myers, R.C., Nachreiner, D.J., Sullivan, L.J., King, J.M., 1978. Pe-
troleum hydrocarbon toxicity studies XVII. Animal response to n-nonane vapor. Toxicol.
Appl. Pharmacol. 44 (1), 53–61. https://doi.org/10.1016/0041-008X(78)90283-1.
Chong, D., Wang, Y., Guo, H., Lu, Y., 2014. Volatile organic compounds generated in asphalt
pavement construction and their health effects on workers. J. Constr. Eng. Manag. 140
(2), 04013051. https://doi.org/10.1061/(ASCE)CO.1943-7862.0000801.
<collab>Asphalt Institute, E.B.A.</collab>, 2015. The bitumen industry: a global perspec-
tive: production, chemistry use, specification and occupational exposure.
<collab>IRIS, E.</collab>, 2011. Integrated Risk Information System (IRIS) US Environmen-
tal Protection Agency. Chemical Assessment Summary National Center for Environmental
Assessment. IRIS Assessments. Browse A to Z List of Chemicals. IRIS Assessments. Browse
A to Z List of Chemicals.
CPWR, 2018. Asphalt in Construction: An Interdisciplinary Annotated Bibliography, Topics in
Construction Safety and Health. The Center for Construction Research and Training, Sil-
ver Spring, Maryland, p. 22.
Crawford, R.J., Throne, J.L., 2002. 2 - rotational molding polymers. In: Crawford, R.J.,
Throne, J.L. (Eds.), Rotational Molding Technology. William Andrew Publishing, Nor-
wich, NY, pp. 19–68 https://doi.org/10.1016/B978-188420785-3.50004-6.
Cui, P., Wu, S., Li, F., Xiao, Y., Zhang, H., 2014. Investigation on using SBS and active carbon
filler to reduce the VOC emission from bituminous materials. Materials 7 (9). https://doi.
org/10.3390/ma7096130.
Cui, P., Cui, Q., Green, H., 2019. Estimating VOC emissions from asphalt pavement. In: El-
Badawy, S., Abd El-Hakim, R. (Eds.), Recent Developments in Pavement Design, Model-
ing and Performance. Springer International Publishing, Cham, pp. 84–93.
Fries, E., Zarfl, C., 2012. Sorption of polycyclic aromatic hydrocarbons (PAHs) to low and high
density polyethylene (PE). Environ. Sci. Pollut. Res. 19 (4), 1296–1304. https://doi.org/
10.1007/s11356-011-0655-5.
Gasthauer, E., Mazé, M., Marchand, J.P., Amouroux, J., 2008. Characterization of asphalt
fume composition by GC/MS and effect of temperature. Fuel 87 (7), 1428–1434.
https://doi.org/10.1016/j.fuel.2007.06.025.
Gehle, K., 2009. Agency for Toxic Substances and Disease Registry (ATSDR) Case Studies in
Environmental Medicine Toxicity of Polycyclic Aromatic Hydrocarbons (PAHs). USA De-
partment of Health and Human Services Agency for Toxic Substances and Disease Regis-
try Division of Toxicology and Environmental Medicine.
Giustozzi, F., Xuan, D., Enfrin, M., Masood, H., Audy, R., Boom, Y., 2021. Use of Road-grade
Recycled Plastics for Sustainable Asphalt Pavements: Towards the Selection of Road-grade
Plastics: An Evaluation Framework and Preliminary Experimental Results. Austroads.
Gong, M., Yang, J., Zhang, J., Zhu, H., Tong, T., 2016. Physical–chemical properties of aged
asphalt rejuvenated by bio-oil derived from biodiesel residue. Constr. Build. Mater.
105, 35–45. https://doi.org/10.1016/j.conbuildmat.2015.12.025.
Government of Canada, 2017. Code of Practice for the Reduction of Volatile Organic Com-
pound (VOC) Emissions From Cutback and Emulsified Asphalt. Environment and Climate
Change Canada, Gatineau, Quebec, p. 15.
Guo, J., Wang, C., Guo, Z., Zuo, Z., 2018. Exposure to environmental level phenanthrene in-
duces a NASH-like phenotype in new born rat. Environ. Pollut. 239, 261–271. https://
doi.org/10.1016/j.envpol.2018.04.030.
Heikkilä, P.R., Väänänen, V., Hämeilä, M., Linnainmaa, K., 2003. Mutagenicity of bitumen
and asphalt fumes. Toxicol. in Vitro 17 (4), 403–412. https://doi.org/10.1016/S0887-
2333(03)00045-6.
Jamshidi, A., Hamzah, M.O., Aman, M.Y., 2012. Effects of Sasobit® content on the rheological
characteristics of unaged and aged asphalt binders at high and intermediate temperatures.
Mater. Res. 15 (4), 628–638. https://doi.org/10.1590/s1516-14392012005000083.
12
Science of the Total Environment 832 (2022) 155037
Jamshidi, A., Hamzah, M.O., Shahadan, Z., 2012. Selection of reclaimed asphalt pavement
sources and contents for asphalt mix production based on asphalt binder rheological
properties, fuel requirements and greenhouse gas emissions. J. Clean. Prod. 23 (1),
20–27. https://doi.org/10.1016/j.jclepro.2011.10.008.
Kadry, A.M., Skowronski, G.A., Turkall, R.M., Abdel-Rahman, M.S., 1995. Comparison be-
tween oral and dermal bioavailability of soil-adsorbed phenanthrene in female rats.
Toxicol. Lett. 78 (2), 153–163. https://doi.org/10.1016/0378-4274(95)03250-O.
Kalagaeva, K., 2014. Bitumen Fumes, Impacts on Human Health and Natural Environment.
Reduction, Prevention and Control of Bitumen Fumes in Road Construction Industry.
Karapanagioti, H.K., Klontza, I., 2008. Testing phenanthrene distribution properties of virgin
plastic pellets and plastic eroded pellets found on Lesvos island beaches (Greece). Mar.
Environ. Res. 65 (4), 283–290. https://doi.org/10.1016/j.marenvres.2007.11.005.
Khare, P., Machesky, J., Soto, R., He, M., Presto Albert, A., Gentner Drew, R., 2020. Asphalt-
related emissions are a major missing nontraditional source of secondary organic aerosol
precursors. Sci.Adv. 6 (36), eabb9785. https://doi.org/10.1126/sciadv.abb9785.
Li, N., Jiang, Q., Wang, F., Xie, J., Li, Y., Li, J., Wu, S., 2020. Emission behavior, environmental
impact and priority-controlled pollutants assessment of volatile organic compounds
(VOCs) during asphalt pavement construction based on laboratory experiment.
J. Hazard. Mater. 398, 122904. https://doi.org/10.1016/j.jhazmat.2020.122904.
Liang, M., Xin, X., Fan, W., Wang, H., Jiang, H., Zhang, J., Yao, Z., 2019. Phase behavior and
hot storage characteristics of asphalt modified with various polyethylene: experimental
and numerical characterizations. Constr. Build. Mater. 203, 608–620. https://doi.org/
10.1016/j.conbuildmat.2019.01.095.
Lohmann, R., 2012. Critical review of low-density polyethylene's partitioning and diffusion
coefficients for trace organic contaminants and implications for its use as a passive sam-
pler. Environ. Sci. Technol. 46 (2), 606–618. https://doi.org/10.1021/es202702y.
Long-Sheng, H., 2018. Effect of cooling efficiency on emissions of volatile organic compounds
from field asphalt pavement mixtures. Sensors Mater. 30 (3), 633–644.
Lu, X., Isacsson, U., Ekblad, J., 1999. Rheological properties of SEBS, EVA and EBA polymer
modified bitumens. Mater. Struct. 32 (2), 131–139. https://doi.org/10.1007/
BF02479440.
Mato, Y., Isobe, T., Takada, H., Kanehiro, H., Ohtake, C., Kaminuma, T., 2001. Plastic resin
pellets as a transport medium for toxic chemicals in the marine environment. Environ.
Sci. Technol. 35 (2), 318–324. https://doi.org/10.1021/es0010498.
Mo, S., Wang, Y., Xiong, F., Ai, C., 2019. Effects of asphalt source and mixing temperature on
the generated asphalt fumes. J. Hazard. Mater. 371, 342–351. https://doi.org/10.1016/j.
jhazmat.2019.03.025.
Mo, S., Wang, Y., Xiong, F., Ai, C., Wang, D., Tan, G.Y.A., 2020. Changes of asphalt fumes in
hot-mix asphalt pavement recycling. J. Clean. Prod. 258, 120586. https://doi.org/10.
1016/j.jclepro.2020.120586.
Moghadas Nejad, F., Gholami, M., Naderi, K., Rahi, M., 2015. Evaluation of rutting properties
of high density polyethylene modified binders. Mater. Struct. 48 (10), 3295–3305.
https://doi.org/10.1617/s11527-014-0399-z.
Moo, A., Bywood, P., Silva, D., McMillan, J., 2019. Bitumen Contents and Fumes.
Motta, R., Vasconcellos, P.C., Bernucci, L., Ávila, S.G., Cornetti, T., 2012. Comparison of the n-
alkanes and polycyclic aromatic hydrocarbons concentrations in the atmosphere during
the preparation of warm and hot mixtures asphalt for pavements. J. Braz. Chem. Soc.
23, 1501–1505.
Müller, J.F., Manomanii, K., Mortimer, M.R., McLachlan, M.S., 2001. Partitioning of polycy-
clic aromatic hydrocarbons in the polyethylene/water system. Fresenius J. Anal. Chem.
371 (6), 816–822. https://doi.org/10.1007/s002160101025.
NIOSH, 1994. Polynuclear Aromatic Hydrocarbons by GC, NIOSH 5515.
Nizamuddin, S., Boom, Y.J., Giustozzi, F., 2021. Sustainable polymers from recycled waste
plastics and their virgin counterparts as bitumen modifiers:a comprehensive review. Poly-
mers 13 (19). https://doi.org/10.3390/polym13193242.
Osborn, L.V., Snawder, J.E., Kriech, A.J., Cavallari, J.M., McClean, M.D., Herrick, R.F.,
Blackburn, G.R., Olsen, L.D., 2013. Personal breathing zone exposures among hot-mix as-
phalt paving workers; preliminary analysis for trends and analysis of work practices that
resulted in the highest exposure concentrations. J. Occup. Environ. Hyg. 10 (12),
663–673. https://doi.org/10.1080/15459624.2013.831981.
Pascall, M.A., Zabik, M.E., Zabik, M.J., Hernandez, R.J., 2005. Uptake of polychlorinated bi-
phenyls (PCBs) from an aqueous medium by polyethylene, polyvinyl chloride, and poly-
styrene films. J. Agric. Food Chem. 53 (1), 164–169. https://doi.org/10.1021/jf048978t.
Pérez-Lepe, A., Gallegos, C., González, O., Martı́nez-Boza, F.J., Muñoz, M.E., Santamarı́a, A.,
2003. Influence of the processing conditions on the rheological behaviour of polymer-
modified bitumen☆. Fuel 82 (11), 1339–1348. https://doi.org/10.1016/S0016-2361
(03)00065-6.
Plech, A., Trzeciak, H.I., Sokola, A., Herman, Z.S., Zawisza, T., 1975. Acute toxicity and the
influence of some undecane, cyclopentylpentane and pyridine alpha- and beta-
carboxylic acid derivatives on the increased hyperlipemia in rats. Pol. J. Pharmacol.
Pharm. 27 (4), 399–404.
Preuss, R., Angerer, J., Drexler, H., 2003. Naphthalene—an environmental and occupational
toxicant. Int. Arch. Occup. Environ. Health 76 (8), 556–576. https://doi.org/10.1007/
s00420-003-0458-1.
Ramírez, N., Marcé, R.M., Borrull, F., 2011. Determination of volatile organic compounds in
industrial wastewater plant air emissions by multi-sorbent adsorption and thermal
desorption-gas chromatography-mass spectrometry. Int. J. Environ. Anal. Chem. 91
(10), 911–928. https://doi.org/10.1080/03067310903584073.
Ramírez, N., Cuadras, A., Rovira, E., Borrull, F., Marcé, R.M., 2012. Chronic risk assessment of
exposure to volatile organic compounds in the atmosphere near the largest Mediterra-
nean industrial site. Environ. Int. 39 (1), 200–209. https://doi.org/10.1016/j.envint.
2011.11.002.
Rasoulzadeh, Y., Mortazavi, S.B., Yousefi, A.A., Khavanin, A., 2011. Decreasing polycyclic ar-
omatic hydrocarbons emission from bitumen using alternative bitumen production pro-
cess. J. Hazard. Mater. 185 (2), 1156–1161. https://doi.org/10.1016/j.jhazmat.2010.
10.026.
Y.J. Boom et al.
Reshetycek, A.L., Talakina, E.I., En'yakova, P.A., 1970. Toxicological evaluation of
acenaphthene and acenaphthylene. Gig Tr Prof Zabol 14 (6), 46–47.
Robertus, C., Thimm, L., Hossain, S., 2016. PAH's in Bitumen: Many Paths - One Destination.
Roy, T.A., Kriech, A.J., Mackerer, C.R., 2007. Percutaneous absorption of polycyclic aromatic
compounds from bitumen fume condensate. J. Occup. Environ. Hyg. 4 (sup1), 137–143.
https://doi.org/10.1080/15459620701334814.
Rusina, T.P., Smedes, F., Klanova, J., Booij, K., Holoubek, I., 2007. Polymer selection for pas-
sive sampling: a comparison of critical properties. Chemosphere 68 (7), 1344–1351.
https://doi.org/10.1016/j.chemosphere.2007.01.025.
Santos, J., Pham, A., Stasinopoulos, P., Giustozzi, F., 2021. Recycling waste plastics in roads: a
life-cycle assessment study using primary data. Sci. Total Environ. 751, 141842. https://
doi.org/10.1016/j.scitotenv.2020.141842.
Schmidt et al., n.d. R. Schmidt K. Griesbaum A. Behr D. Biedenkapp H.-W. Voges D. Garbe C.
Paetz G. Collin D. Mayer H. Höke Hydrocarbons, Ullmann's Encyclopedia of Industrial
Chemistry. pp. 1-74. doi:10.1002/14356007.a13_227.pub3.
Smith, D., 2020. Understanding TVOC: What You Need To Know About Volatile Organic
Compounds. (accessed 6th August 2021) https://bit.ly/3lw9a8W.
Sørensen, L., Rogers, E., Altin, D., Salaberria, I., Booth, A.M., 2020. Sorption of PAHs to
microplastic and their bioavailability and toxicity to marine copepods under co-
exposure conditions. Environ. Pollut. 258, 113844. https://doi.org/10.1016/j.envpol.
2019.113844.
Speight, J.G., El-Gendy, N.S., 2018. Chapter 3 - introduction to petroleum biotechnology. In:
Speight, J.G., El-Gendy, N.S. (Eds.), Introduction to Petroleum Biotechnology. Gulf Pro-
fessional Publishing, Boston, pp. 69–101 https://doi.org/10.1016/B978-0-12-805151-1.
00003-5.
Tang, N., Yang, K.-K., Alrefaei, Y., Dai, J.-G., Wu, L.-M., Wang, Q., 2020. Reduce VOCs and PM
emissions of warm-mix asphalt using geopolymer additives. Constr. Build. Mater. 244,
118338. https://doi.org/10.1016/j.conbuildmat.2020.118338.
13
Science of the Total Environment 832 (2022) 155037
Teuten, E.L., Rowland, S.J., Galloway, T.S., Thompson, R.C., 2007. Potential for plastics to
transport hydrophobic contaminants. Environ. Sci. Technol. 41 (22), 7759–7764.
https://doi.org/10.1021/es071737s.
US EPA, 1996. Sampling Method for Volatile Organic Compounds (SMVOC), Method 0031.
US EPA, 1999. Compendium Method TO 13A—Determination of Polycyclic Aromatic Hydro-
carbons (PAHs) in Ambient Air Using Gas Chromatography/Mass Spectrometry (GC/MS),
Method TO-13A Cincinnati, OH, USA.
US EPA, 2018. Volatile Organic Compounds by Gas Chromatography/Mass Spectrometry
(GC/MS) Revision 4, Method 8260D.
Wang, L.-C., Lin, J.C.-T., Dong, C.-D., Chen, C.-W., Liu, T.-K., 2021. The sorption of persistent
organic pollutants in microplastics from the coastal environment. J. Hazard. Mater. 420,
126658. https://doi.org/10.1016/j.jhazmat.2021.126658.
Xia, W., Xu, T., Wang, H., 2019. Thermal behaviors and harmful volatile constituents released
from asphalt components at high temperature. J. Hazard. Mater. 373, 741–752. https://
doi.org/10.1016/j.jhazmat.2019.04.004.
Xiao, Y., Wan, M., Jenkins, K.J., Wu, S.P., Cui, P.Q., 2017. Using activated carbon to reduce
the volatile organic compounds from bituminous materials. J. Mater. Civ. Eng. 29 (10),
04017166. https://doi.org/10.1061/(ASCE)MT.1943-5533.0002024.
Yamashita, K., Yamamoto, N., Mizukoshi, A., Noguchi, M., Ni, Y., Yanagisawa, Y., 2009. Com-
positions of volatile organic compounds emitted from melted virgin and waste plastic pel-
lets. J. Air Waste Manage. Assoc. 59 (3), 273–278. https://doi.org/10.3155/1047-3289.
59.3.273.
Yang, X., You, Z., Perram, D., Hand, D., Ahmed, Z., Wei, W., Luo, S., 2019. Emission analysis
of recycled tire rubber modified asphalt in hot and warm mix conditions. J. Hazard.
Mater. 365, 942–951. https://doi.org/10.1016/j.jhazmat.2018.11.080.
Zhang, X., Xiao, Y., Long, Y., Chen, Z., Cui, P., Wu, R., Chang, X., 2021. VOCs reduction in bi-
tumen binder with optimally designed Ca(OH)2-incorporated zeolite. Constr. Build.
Mater. 279, 122485. https://doi.org/10.1016/j.conbuildmat.2021.122485.