Kriech, Osborn, Prowell, Redman, West 1

Comparison of worker breathing zone exposures between hot mix asphalt and
warm mix asphalt applications

Anthony J. Kriech1, Linda V. Osborn1, Brian D. Prowell2, Adam P. Redman1, and Randy
C. West3
1
Heritage Research Group, 7901 West Morris Street, Indianapolis, Indiana 46231 USA
(317-390-3137) tony.kriech@hrglab.com, linda.osborn@hrglab.com
2
Advanced Materials Services, LLC, 2515 E. Glenn Avenue Suite 107, Auburn,
Alabama 36830 USA (334-246-4428) Brian.AMSLLC@charterinternet.com
3
Auburn University, 277 Technology Parkway, Auburn, Alabama 36830 USA (334-844-
6228) westran@auburn.edu

Original Submission date: May 19, 2011

Resubmission date: September 9, 2011

Abstract Word Count: 464

Text - Word Count: 3,356

Corresponding author:
Linda V. Osborn
7901 W. Morris St.
Indianapolis, Indian 46231
Phone: (317) 390-3188 Fax: (317) 486-2985
Email: linda.osborn@hrglab.com

Keywords: asphalt (bitumen); breathing zone exposure; total organic matter (TOM),
polycyclic aromatic compounds (PACs)
Kriech, Osborn, Prowell, Redman, West 2

ABSTRACT
The primary objective of this study was to determine if reducing asphalt temperature
using warm mix asphalt (WMA) reduced worker exposure to total organic matter (TOM)
as compared to hot mix asphalt (HMA) applications.
Eight workers were recruited from two asphalt paving crews and were monitored
for four consecutive days. One of the four days of sampling was conducted under normal
working conditions using HMA. The other three days of sampling were conducted under
similar conditions, but using different warm mix technologies each day. All days
excluded the use of diesel oil as a release/cleaning agent to focus the assessment on
asphalt emissions. The two sites included one in Indiana and one in New York. Within a
given site, controlled variables included use of the same asphalt source, the same
aggregate and amount of recycled asphalt pavement, the same type of plant and mixer,
the same crew, and similar traffic patterns with the paving occurring in congruent
locations. Measured in the freshly paved mat directly behind the paver, the two sites
were different in terms of the HMA temperatures; Indiana HMA temperatures averaged
only 121oC, whereas the New York site averaged 161oC. For Indiana, the WMA
temperatures averaged 106oC (sd=4.3) and the New York WMA temperatures averaged
117oC (sd=10.8). WMA technologies included BituTech PER, Cecabase RT,
Evotherm DAT, SonneWarmix, Ultrafoam GX2 and Wax. Although these
technologies are not identified with results, the deviation within the six WMA
technologies is smaller than the deviation between HMA and WMA within a given
asphalt source.
Sampling strategy included collection of TOM using a sorbent tube comprised of
XAD-2 resin and charcoal followed by extraction and analysis by Gas Chromatography
(GC) with Flame Ionization Detection and GC/ Time of Flight Mass Spectrometry
(GC/TOF/MS). Use of this approach compared to the more traditional NIOSH Method
5042 was based on internal data included here where the benzene soluble fraction of the
total particulates was below the limit of detection (LOD). Collection of the more volatile
compounds using a sorbent tube resulted in detectable results for all samples allowing
quantification of reductions. Extracts containing the highest level of TOM from each
experiment were also tested for 40 individual polycyclic aromatic compounds (PACs)
using GC/TOFMS.
WMA compared to the corresponding HMA resulted in a minimum of 33%
reduction in TOM exposures with the exception of one WMA technology. (Individual
reductions for the six WMA technologies tested were -8.4%, 33.1%, 36.8%, 46.9%,
54.0%, and 60.9%). Within a given asphalt source, an increase in temperature generally
resulted in an increase in TOM. Overall, these six WMA technologies resulted in lower
TOM exposures within the paving worker breathing zones. Only one 4-6 ring PAC
(pyrene) was detected in the 8 highest samples analyzed. Of the 2-3 ring PACs,
naphthalene was detected at the highest concentration.

INTRODUCTION
Based on volume, asphalts primary use has been in paving, as a binder for mineral
aggregates in asphalt mixes to globally build roadway infrastructures. It is indirectly
estimated that there are over 870,000 asphalt paving workers as of 2007 (1). Asphalt is
the non-distillable fraction of crude oil. Small amounts of volatile and semi-volatile
Kriech, Osborn, Prowell, Redman, West 3

organic compounds are trapped in this highly viscous material (2). Heating asphalt above
the softening point and agitation facilitates the release of these emissions constituting the
potential for worker exposure.
A large nested case control epidemiology study by Olsson et al., (3) showed no
consistent evidence of an association between indicators of either inhalation or dermal
exposure to asphalt and lung cancer risk and attributed increased incidence in cancer to
confounding issues like smoking, exposure to coal tar etc.
A recent 2-year skin painting study by Clark et al., (2) confirmed the absence of
tumorigenic effects in paving asphalt fume condensate treated skin regions. Fuhst et al.,
(4) conducted an inhalation study involving exposure of Wistar (WU) rats to asphalt
fume for 2 years. Results showed that asphalt fume is not considered to be tumorigenic
to rats via the inhalation route. Asphalt-related irritant effects were, however, observed
in the nasal passages and in the lungs.
Other studies have also shown an association with various irritation health
endpoints. A recent German human study by Raulf-Heimsoth et al. (5) detected
potentially (sub-) chronic irritative inflammatory effects in the lower airways of bitumen
exposed workers. Tepper et al. (6) reported throat symptoms that were statistically
significant compared to a control group. Similar symptoms are discussed in the Norseth
et al. studies (7) evaluating self-reported symptoms that included fatigue, reduced
appetite, eye irritation, and laryngeal-pharyngeal irritation reported more frequently
among workers exposed to asphalt fumes than among unexposed workers in a statistically
significant manner.
These studies emphasize the need for reducing worker exposure to asphalt
emissions. The National Institute for Occupational Safety and Health (NIOSH) has
recommended use of engineering controls and good work practices to minimize worker
exposure to asphalt fumes (8), including reduction of the asphalt mix temperature. First
developed in Europe in the late 1990s, warm-mix asphalt (WMA) mixtures are produced
at lower temperatures as compared to those typically associated with hot-mix asphalt
(HMA); produced and applied at temperatures typically 20 55 C lower than HMA (9).
WMA is generally laid and compacted at temperatures between 100-140oC compared
with traditional hot mix (150-180oC) (9). Recent studies (10) show that reduced asphalt
application temperature is predictive of reduced inhalation exposures (11) and the total
absorbed dose of PAC and PAC metabolites (12).
WMA products fall into one of three general classifications; those that add water,
those that add some form of organic additive or wax, or those that include chemical
additives or surfactants (13). Information in the public domain regarding worker
reduction of WMA technologies is often based on marketing or in the format of
presentations, conference proceedings, or government reports. Few peer reviewed
publications specifically document this promoted benefit of WMA. DAngelo et al., (9)
for asphalt aerosols/fumes and polycyclic aromatic hydrocarbons (PAHs), indicated
significant reductions compared to HMA, showing a 30-50% reduction. Measurements
by von Devivere et al., (14) showed a reduction in fume emissions of 75% where zeolite
had been added with an application temperature reduction of 26oC. In a study of WAM-
Foam, exposure values were shown to be in the lower range when compared to exposure
measurements conducted on paving HMA (15). The Minnesota Asphalt Pavement
Association showed that WMA reduced emissions by 35-65% (16, 17). Shifa et al., (18)
Kriech, Osborn, Prowell, Redman, West 4

claimed a 90.2% reduction of asphalt fume for emulsion warm mix asphalt in a long
tunnel pavement study.
This present study was designed to compare warm-mix technologies versus
traditional HMA applications under similar conditions, controlling many variables in the
field (albeit not all) to allow a side-by-side comparison of the worker breathing zone
exposures. Three different WMA technologies are compared to one HMA at each of two
sites.
METHODS

Study Population
During each sampling event, four workers per crew were studied; the paver operator, two
screed operators (Indiana site foreman), and the raker. Of the entire crew, these four
workers had the greatest potential for asphalt emission exposure.

Study Design
These eight workers (one crew in Indiana (IN) and one in New York (NY)) were
monitored for four consecutive days; one conducted under normal working conditions
using HMA and the other three conducted under similar conditions, but using different
warm mix technologies each day. No diesel oil was used as a release/cleaning agent to
focus assessment on asphalt emissions. Within a given site, controlled variables included
asphalt source, aggregate, amount of recycled asphalt pavement from same batch, plant,
mixer, crew, with similar traffic patterns (paved in congruent locations). Paving
machines were equipped with properly functioning engineering controls.
Whereas many classify mixture temperature at the production facility, for this
study application temperatures were monitored at the back of the screed area six times
throughout the workday using a HMA Lab Supply 8" Stainless Steel Dial Stem
thermometer, with a -18 to 204 C range in the newly placed mat.
For the IN crew, diesel oil normally used as a release agent and to clean tools and
equipment was removed from the site and replaced with B-100, (biodiesel) (19) (CAS
Number: 67784-80-9). Biodiesel contains no straight chain hydrocarbons or PACs.
Workers in NY did not use diesel oil; instead they use a water-based product called FO
Release II (Fine Organics Corp), also free of straight chain hydrocarbons or PACs.

Collection and Analysis of Breathing Zone Samples

Each worker wore two sorbent tube samplers containing XAD-2 and charcoal (150 mg
XAD-2 followed by 50 mg activated charcoal; FIGURE 1). A 1-inch piece of Tygon
tubing (dichloromethane rinsed) was added to the end of tube, once broken, to protect the
workers. Care was taken to break the inlet end of the tube to 4-mm to equal the NIOSH
sampler. Set to a flow rate of 2.0 + 0.2 L/min, pumps were calibrated pre-shift and re-
measured post-shift. One background sample was collected each day/experiment,
positioned upwind of the paving operation. A field blank was collected on each
day/experiment for each crew. Sorbent tubes were eluted with 5 mL dichloromethane;
charcoal end up.
Kriech, Osborn, Prowell, Redman, West 5

FIGURE 1 Photograph of a worker at the Indiana site, who wore two XAD-
2/charcoal sorbent tubes for collection of breathing zone exposures.

Sampler Selection Justification

Internal data is provided in TABLE 1 showing results of previous studies conducted by
Heritage Research Group that included breathing zone monitoring of workers during
three different WMA applications. Each worker was monitored in a similar manner as
described above. However, the breathing zone air entered a membrane filter first,
followed by the sorbent tube; allowing determination of total particulates (TP), benzene
soluble fraction (BSF) and total organic matter (TOM) using NIOSH Method 5042 (20).
BSF levels were all below the LOD; hindering quantitative comparisons to HMA. Since
all samples contained detectable levels of TOM, this was selected as the primary tool for
evaluating differences in exposure between HMA and WMA.

TABLE 1 Summary of Existing Internal Data

mg/m3
Technology Worker Total Benzene Total Organic
Particulates Soluble Fraction Matter
WMA-1 Raker Left 0.69 bdl 0.73
WMA-1 Raker Right 0.54 bdl 0.97
WMA-1 Screed Area 1.11 bdl 0.66
WMA-1 Screed Area 0.78 bdl 1.03
WMA-1 Operator Left 0.91 bdl 0.91
WMA-1 Operator Right 0.70 bdl 0.93
WMA-1 Operator Area 0.55 bdl 1.67
WMA-1 Screed Area 0.81 bdl 1.00
WMA-2 Screedman 0.13 bdl 0.56
WMA-2 Screedman 0.16 bdl 0.55
WMA-2 Operator 0.20 bdl 0.42
WMA-2 Raker 0.17 bdl 0.59
WMA-2 Raker 0.18 bdl 0.57
WMA-3 Screedman 0.76 bdl 0.99
Average 0.52 <0.04 0.81
bdl = below detection limit
Kriech, Osborn, Prowell, Redman, West 6

Total Organic Matter

TOM (21) included hydrocarbons ranging from C6 to C42 as determined by gas
chromatography/flame ionization detection (GC/FID). A Varian model 3400 GC with a
1077 split/splitless injector (set at 250C) was used, with a 5% phenyl /95% methyl-
polysiloxane column (30 m x 0.33 mm ID, 0.25 m film thickness; Restek RTX-5);
hydrogen carrier gas was set at 2 mL/min. With detector at 310oC, the oven temperature
program was 40C held for 3 minutes, increased to 120oC at 9oC/min, held for 0.5 min,
then ramped to 305oC at 11oC/min, and held for 10.89 min. Calibration included
kerosene standards for quantification of the TOM.

Polycyclic Aromatic Compounds

Forty PACs (see TABLE 2) were determined using gas chromatography/time-of-flight
mass spectrometry (GC/TOFMS) following a modified version of a published procedure
(Kriech et al.) (22). Using a Leco Pegasus II GC/TOFMS, source temperature was
275C, transfer line: 300C, mass range: 35-400, 5 spectra/sec with split/splitless injector
(splitless mode, set at 300C). A Varian Select PAH column was used
(30 m x 0.25 mm ID, 0.15 m film thickness; Varian CP 7462). Helium carrier gas was
2.0 mL/min. Oven temperature program was 50oC for 0.7 min.; ramped to 180oC at
85C/min for 0 min; ramped to 230 at 3oC/min for 7 min; ramped to 280oC for 10 min at
28oC/min and finally taken to 350oC at 14oC/min and held for 5 min. Four standards
supplied by AccuStandard Inc. and three from Sigma Aldrich were used. AccuStandard
Inc. standards included a mix of 24 PACs, a custom order standard of nine PACs,
dibenzo[a,e]fluoranthene, and thianaphthene. Sigma-Aldrich standards included
dibenz[c,h]acridine, benz[a]acridine and dibenz[c,h]acridine. Prior to injection, an
internal standard mix was added to each calibration standard and sample (10 L to each
100 L aliquot). Only the samples with the highest TOM values per experiment were
analyzed by GC/TOFMS.
This includes 9 of 13 PACs recently listed by the International Agency for
Research on Cancer (IARC) Volume 103 as their preliminary list of agents to be
reviewed for asphalt and asphalt fumes, and some heterocyclic PACs. Four 6-ring
PACs are also on the IARC list but were not tested due to lack of available standards.
Supplier and catalogue number information for products described above are
provided in TABLE 3.
Kriech, Osborn, Prowell, Redman, West 7

TABLE 2 List of Polycyclic Aromatic Compounds Investigated in Eight Worker Breathing Zone Samples

Benzene Polycyclic Polycyclic

CAS NO CAS NO
Rings Aromatic Compound Aromatic Compound
1 1+ 95-15-8 Benzothiophene 21 5522-43-0 1-Nitropyrene
2 2 91-20-3 Naphthalene 22 27208-37-3 Cyclopenta[cd]pyrene
3 2+ 83-32-9 Acenaphthene 23 205-99-2 Benzo[b]fluoranthene
4 2+ 208-96-8 Acenaphthylene 24 205-82-3 Benzo[j]fluoranthene
5 2+ 225-11-6 Benz[a]acridine 25 207-08-9 Benzo[k]fluoranthene
6 2+ 225-51-4 Benz[c]acridine 26 194-59-2 7H-Dibenzo[c,g]carbazole
7 2+ 86-74-8 Carbazole 27 56-49-5 3-Methylcholanthrene
8 2+ 132-65-0 Dibenzothiophene 28 50-32-8 Benzo[a]pyrene
9 2+ 86-73-7 Fluorene 29 192-97-2 Benzo[e]pyrene
10 3 120-12-7 Anthracene 30 53-70-3 Dibenz[a,h]anthracene
11 3 85-01-8 Phenanthrene 31 226-36-8 Dibenz[a,h]acridine
12 3+ 239-35-0 Benzo[b]naphtho[2,1-d]thiophene 32 224-42-0 Dibenz[a,j]acridine
13 3+ 206-44-0 Fluoranthene 33 224-53-3 Dibenz[c,h]acridine
14 3+ 243-46-9 Benzo[b]naphtho[2,3-d]thiophene 34 2997-45-7 Dibenzo[a,e]fluoranthene
15 4 56-55-3 Benz[a]anthracene 35 193-39-5 Indeno[1,2,3-cd]pyrene
16 4 3697-24-3 5-Methylchrysene 36 191-24-2 Benzo[ghi]perylene
17 4 218-01-9 Chrysene 37 192-65-4 Dibenzo[a,e]pyrene
18 4 129-00-0 Pyrene 38 189-55-9 Benzo[rst]pentaphene
19 4 57-97-6 7,12-Dimethylbenz[a]anthracene 39 189-64-0 Dibenzo[a,h]pyrene
20 4 217-59-4 Triphenylene 40 191-30-0 Dibenzo[a,l]pyrene

Note: The grayed compounds represent 9 of 13 Polycyclic Aromatic Compounds (PACs) recently listed by the International Agency
for Research on Cancer as their preliminary list of agents to be reviewed for asphalt and asphalt fumes. Benzene rings=no. of 6-
membered aromatic rings in the structure, + indicates one additional four or five sided ring within the structure.
Kriech, Osborn, Prowell, Redman, West 8

TABLE 3 Supply Information with Catalogue Numbers

Supplier Description CAT. NO. City State

HMA Lab Supply, Inc. Stainless Steel Dial Stem thermometer, with a - TM-4500 Richmond VA
18 to 204 C range
SKC, Inc. 150 mg XAD-2 followed by 50 mg activated CPM032509-001 Eighty Four PA
charcoal
Fisher Scientific Tygon tubing 14-176-272 Pittsburg PA
EMD Dichloromethane HPLC Grade OmniSolv DX0831-1 Gibbstown NJ
High Purity
AccuStandard, Inc. Kerosene standards FU-005N Neat New Haven CT
AccuStandard, Inc. Custom mix of 24 PACs H-QME-01 New Haven CT
AccuStandard, Inc. Custom mix of 9 PACs S-13911-R1 New Haven CT
AccuStandard, Inc. dibenzo[a,e]fluoranthene Cat. No. H-247S New Haven CT
AccuStandard, Inc. thianaphthene Cat. No. H-238N New Haven CT
Sigma-Aldrich dibenz[c,h]acridine BCR 156R St. Louis MO
Sigma-Aldrich benz[a]acridine R308714 St. Louis MO
Sigma-Aldrich dibenz[c,h]acridine BCR 156R St. Louis MO
Supelco Internal standard mix 4 8902 St. Louis MO

RESULTS
Average HMA temperatures for each experiment are presented in TABLE 4. NY HMA
temperatures were an average of 35oC higher than the IN site. Differences between the
HMA and WMA experiments in IN were only 15oC or less, whereas the NY mat
temperatures were >44oC lower for the WMA as compared to the corresponding HMA.
In fact, the HMA, IN was within the normal temperature range for WMA (100-140oC).
HMA, NY had an average mat temperature of 161oC, well within the typical HMA range
(150-180oC).

TABLE 4 Average Temperature of the Asphalt Mat Directly Behind the Screed for
each Experiment. Temperature Differences were Significant for the New York Site,
while Differences at the Indiana Site were Minimal

Mix Temperature behind

Screed Difference oC
o
C
Hot Mix Asphalt, Indiana 126 IN Reference
Warm Mix Asphalt-A 114 12
Warm Mix Asphalt-B 111 15
Warm Mix Asphalt-C 116 10
Hot Mix Asphalt, New York 161 NY Reference
Warm Mix Asphalt-D 106 55
Warm Mix Asphalt-E 109 52
Warm Mix Asphalt-F 117 44
Kriech, Osborn, Prowell, Redman, West 9

Both sites used PG 64-22 asphalt for the HMA and in their WMA formulations.
The source of asphalt was different between IN and NY, but the same within each
location.
The paver machines were very different for the two sites. At the NY site, one
paver was used the first 2 days of sampling; then experienced mechanical problems. Day
3, after 3-4 hours trying to fix the paver; they switched to a different paver.
TOM results are listed in TABLE 5 (IN) and TABLE 6 (NY), with summary
statistics shown in TABLE 7. Average data are also shown graphically (FIGURE 2).
Background and blank data were all below the LOD of ~0.04 mg/m3. Breathing zone
results show that TOM concentrations for the NY site were substantially higher than
those for the IN site. WMA arithmetic mean data compared to the corresponding HMA
arithmetic mean data resulted in a minimum of 33 % reduction in TOM exposures with
the exception of one WMA technology that was 8.4% higher. The NY TOM data
showed a statistically significant difference between the HMA reference and the WMA
technologies D, E and F (95% confidence intervals (CI95%) were 1.90-2.52 mg/m3 and
1.29-1.54 mg/m3 respectively). For the IN data, there was not a statistically significant
difference between the HMA and the aggregate WMA technologies A, B and C (CI95%
were 0.23-0.41 mg/m3 and 0.16-0.25 mg/m3 respectively). Since the HMA was applied
at WMA temperatures, this was not surprising. Evaluation of the CI95% for each
individual WMA showed that all except WMA-B were lower than their corresponding
HMA as displayed graphically in FIGURE 3.
Kriech, Osborn, Prowell, Redman, West 10

TABLE 5 Indiana Site Information and Total Organic Matter (TOM) Data for all
Samples

Experiment
Lab L TOM
Product Date Tonnage Description Minutes Average TOM
ID air (mg/m3)
(mg/m3)
51 Operator 350 721 0.30 0.32
52 Operator 285 581 0.17
HOT-MIX, IN

53 Raker 429 875 0.25

9/14/2010

1200
54 Raker 430 854 0.24
55 Screedman 430 851 0.52
56 Screedman 430 858 0.53
57 Foreman 430 894 0.21
58 Foreman 430 882 0.33
61 Operator 425 871 0.05 0.12
62 Operator 425 876 0.05
63 Screedman 424 837 0.13
WMA - A

9/15/2010

1187

64 Screedman 424 854 0.09

65 Raker 419 848 0.12
66 Raker 422 850 0.11
67 Foreman 432 886 0.19
68 Foreman 432 873 0.25
71 Operator 262 542 0.27 0.34
72 Operator 262 542 0.30
73 Screedman 268 531 0.45
WMA - B

9/16/2010

74 Screedman 268 547 0.58

881

75 Raker 267 545 0.27

76 Raker 267 542 0.31
77 Foreman 264 546 0.29
78 Foreman 264 539 0.30
81 Operator 225 464 0.04 0.15
82 Operator 225 467 0.05
83 Screedman 227 452 0.24
WMA - C

9/16/2010

84 Screedman 227 462 0.30

890

85 Raker 228 463 0.12

86 Raker 228 462 0.12
87 Foreman 230 475 0.12
88 Foreman 230 470 0.18
Kriech, Osborn, Prowell, Redman, West 11

TABLE 6 New York Site Information and Total Organic Matter (TOM) Data for
all Samples

Experiment
Lab L TOM
Product Date Tonnage Description Minutes Average TOM
ID air (mg/m3)
(mg/m3)
49 Operator 430 837 2.78 2.21
50 Operator 430 834 2.97
Hot Mix, NY

10/20/2010

51 Screedman 436 859 2.15

1100
52 Screedman 436 857 1.62
53 Raker 447 871 1.84
54 Raker 447 896 1.91
55 Laborer 434 862 2.21
56 Laborer 434 860 2.20
41 Operator 377 744 1.46 1.17
40 Operator 377 752 1.78
10/19/2010

42 Screedman 370 738 1.02

WMA-D

38 Screedman 370 733 1.31

800

44 Raker 373 724 1.11

43 Raker 376 759 1.25
39 Laborer 387 777 0.58
37 Laborer 387 778 0.87
61 Operator 345 695 1.79 1.40
62 Operator 345 667 1.57
10/21/2010

63 Screedman 352 683 1.37

WMA - E

64 Screedman 352 681 1.46

780

65 Raker 362 723 1.29

66 Raker 362 721 0.78
67 Laborer 385 765 1.41
68 Laborer 385 759 1.51
73 Operator 346 696 2.14 1.48
74 Operator 347 700 1.81
10/22/2010

75 Screedman 382 764 1.60

WMA-F

76 Screedman 382 745 1.58

798

77 Raker 342 691 1.77

78 Raker 343 680 1.73
79 Laborer 388 770 1.48
80 Laborer 387 766 1.33

TABLE 7 Summary Statistics for Total Organic Matter (TOM) Data

mg/m3 WMA, NY HMA, NY WMA, IN HMA, IN

Average 1.42 2.21 0.21 0.32
minimum 0.58 1.62 0.04 0.17
maximum 2.14 2.97 0.58 0.53
Standard Deviation 0.36 0.46 0.13 0.14
Number 24 8 24 8

WMA=Warm Mix Asphalt, HMA=Hot Mix Asphalt, NY=New York, IN=Indiana

Kriech, Osborn, Prowell, Redman, West 12

3
Total Organic Matter mg/m

3.0

2.21
2.5

2.0

1.40 1.48
1.17
1.5

1.0

0.32 0.34
0.5 0.15
0.12

0.0
HMA WMA-A WMA-B WMA-C HMA WMA-D WMA-E WMA-F
Indiana New York

FIGURE 2 Average site results comparing hot mix asphalt worker exposures to the
corresponding worker breathing zone exposures while using three different warm
mix technologies formulated with the same base asphalt per site (Indiana and New
York).

Overall, use of these six WMA technologies resulted in lower application

temperatures that subsequently resulted in lower TOM exposures within the paving
worker breathing zones.
PAC results are shown in TABLE 8 for the eight samples with the highest TOM
concentrations per experiment. Only one 4-6 ring PAC (pyrene) was detected in these 8
samples. Of the 2-3 ring PACs, naphthalene was detected at the highest concentration.
Since only the highest samples were tested, comparisons between HMA and WMA were
not made.
Kriech, Osborn, Prowell, Redman, West 13

TABLE 8 Polycyclic Aromatic Compound Results for the Eight Samples with the Highest Total Organic Matter
concentrations per Experiment

INDIANA SITE NEW YORK SITE

HMA, HMA,
HMA, IN WMA-A WMA-B WMA-C HMA,
Ring IN IN WMA-D WMA-E WMA-F
Size
g/m3 Back- Field
Screed- Fore- Screed- Screed- NY Operator Operator Operator
man man man man Operator
ground Blank
1+ Benzothiophene 0.06 bdl 0.22 0.07 0.23 0.13 0.10 bdl bdl bdl
2 Naphthalene 0.15 bdl 3.60 2.16 5.42 2.74 2.46 2.13 1.91 4.13
2+ Acenaphthene bdl bdl 0.28 0.10 0.16 0.15 0.06 bdl bdl bdl
2+ Acenaphthylene bdl bdl bdl bdl bdl bdl bdl bdl bdl 0.31
2+ Dibenzothiophene bdl bdl 0.25 0.12 0.15 0.19 0.07 bdl bdl bdl
2+ Fluorene bdl bdl 0.35 0.13 0.19 0.18 0.10 bdl bdl 0.10
3 Anthracene bdl bdl 0.06 bdl bdl bdl bdl bdl bdl bdl
3 Phenanthrene bdl bdl 0.75 0.27 0.38 0.39 0.11 bdl bdl 0.13
3+ Fluoranthene bdl bdl 0.14 0.06 bdl bdl bdl bdl bdl bdl
4 Pyrene bdl bdl 0.11 bdl bdl bdl bdl bdl bdl bdl
Sum of Detectable PACs* 0.45 0.40 5.80 3.04 6.80 4.09 3.07 2.56 2.32 4.97
Detection Limits 0.049 0.061 0.058 0.057 0.091 0.11 0.060 0.066 0.072 0.072
*Polycyclic Aromatic Compounds. Within this data set, when bdl (below detection limit), the detection limit divided by the square
root of 2 was used for the summation.
Kriech, Osborn, Prowell, Redman, West 14

WMA-F

WMA-E

WMA-D

HMA, NY
WMA-C

WMA-B

WMA-A

HMA, IN

-0.30 0.20 0.70 1.20 1.70 2.20 2.70

Total Organic Matter (TOM) mg/m3

FIGURE 3 Total Organic Matter - 95% confidence intervals. HMA=Hot Mix

Asphalt; WMA=Warm Mix Asphalt. Within the New York site, WMA- D, E and F
were significantly different than the corresponding HMA, NY. At the Indiana site,
WMA-A and WMA-C were significantly different than HMA, IN. WMA-B was
not; however the reference HMA was applied at WMA temperatures.

DISCUSSION
Average TOM data from previous HMA studies (1.69 mg/m3) (21) showed lower results
than seen at the NY site (2.21 mg/m3). Although NY HMA temperatures were
significantly higher than IN, the warm mix temperatures were similar, yet the TOM
concentrations were seven times higher in NY. Although the asphalt grades were all PG
64-22, the source of the asphalt was different and likely the most prominent factor
contributing to differences. To confirm that source was the cause, a sample of each
HMA obtained during the study was soxhlet extracted to separate the binder from filler
materials. After evaporation of the dichloromethane solvent, each binder was tested
using Thermal Gravimetric Analysis (TGA).
TGA is performed on samples to determine changes in weight in relation to
changes in temperature. Previous studies have used this technique to evaluate various
roofing asphalts (23). Overlays are shown in FIGURE 4 for the two asphalts. An
expanded view of the region from 100oC to 250oC shows that at application temperatures
used in this study, the NY binder is indeed more volatile than the IN binder.
Kriech, Osborn, Prowell, Redman, West 15

FIGURE 4 Thermal gravimetric analysis (TGA) on the two PG 64-22 asphalt

binders used in this study: expanded view of the temperature region that
corresponds to the actual application temperatures. It is evident that the NY binder
is more volatile than the IN binder until the crossover at ~236oC, which is well above
the application temperatures employed.

It is difficult to directly compare these results with other published data. For
example, Shifa et al., (18) reported 21.1 mg/m3 bitumen fume for HMA versus 2.06
mg/m3 for WMA (a 90.2% reduction), but methods used and location of sampling are not
provided. Shifa et al., also reported results for benzopyrene (HMA = 0.094 mg/m3 versus
WMA = 0.019 mg/m3) whereas we did not detect any benzo[a]pyrene in either HMA or
WMA on worker samples; average LOD = 0.07 g/m3).
Lecomte et al., (15) concluded that the volatile fraction was higher for HMA (up
to 6 times more) and represented almost all the organic emissions (up to 99%). This is
consistent with our internal studies in that the BSF fractions were also below the LOD.
Also consistent with our internal data, a report by the Virginia Transportation Research
Counsel (24) showed all worker results below the LOD of 0.08 mg/m3 for BSF.
It is interesting to note that the highest TOM concentrations occurred for the
screedman/foreman in IN. However, in NY, the paver operator consistently received the
highest exposure levels. This may be due to design differences between the types of
paver machines or may be related to landscape differences i.e., with 2 and 3-story
buildings connected in NY creating an almost tunnel effect versus the open, more rural
IN.
All TOM results were above the LOD demonstrating that it is a useful measure
for assessing reductions in worker breathing zone exposures with the use of WMA.
Results for these two sites appeared to bracket the high and low ends of the spectrum of
asphalt paving worker breathing zone exposures.
Kriech, Osborn, Prowell, Redman, West 16

CONCLUSIONS
Overall, use of these six WMA technologies resulted in lower application
temperatures as compared to their corresponding HMA; yielding a 36% reduction
in TOM exposures within the paving worker breathing zones.
Exposures using WMA are not the same across technologies.
Twenty-two of the 40 individual PACs tested were below the LOD for the eight
samples tested.
o Naphthalene was detected at the highest concentration.
o Only one 4-6 ring PAC (pyrene) was detected in any of these worker
breathing zone samples and it was in a HMA sample.
o The nine PACs tested that are part of the compounds recently listed by
IARC as their preliminary list of agents to be reviewed for asphalt, asphalt
fumes, and some heterocyclic PACs were all below the LOD.
o Since only one 4-ring PAC was detected, it is unlikely that the 6-ring
compounds not included in this study were present.
Not all asphalts are the same; here the source resulted in significantly different BZ
exposure levels.

ACKNOWLEDGEMENTS
Financial support was based on a grant between the National Center for Asphalt
Technology (NCAT) and the National Cooperative Highway Research Program
(NCHRP) TRANSPORTATION RESEARCH BOARD (TRB) National Research
Council (NCHRP 09-47A).

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