Laboratory Forensic Investigations For

Asphalt Paving Issues

Joe Rovani
Jenny Loveridge

P3 Symposium
Laramie, WY
July 15, 2010
 Response
p 101

• Y Axis: Response
• X Axis: Time

100

90

80

70

Response: 60

detector signal 50

% full scale 40

30

20

10

0
1 2 3 4 5 6 7 8 9 10

Time: minutes 2
 Example
p 1

• Y Axis: Response
• X Axis: Time

100

90

80

70

Response: 60

% of audience 50

that is awake 40

30

20

10

0
1 2 3 4 5 6 7 8 9 10

Time: duration of Joe’s presentation 3

 Example
p 2

• Y Axis: Response
• X Axis: Time

100

90

80

70

Response: 60

% of audience 50

that is awake 40

30

20

10

0
1 2 3 4 5 6 7 8 9 10

Time: duration of Joe’s presentation 4

 Petroleum Product Types
yp

C4 C6 C8 C10 C12 C14 C16 C18 C20 C22 C24 C26 C28 C30 >C30
VV.M.&P. Naphtha 
M &P Naphtha "Solvent
Solvent, Light
Light"
Mineral Spirits
Gasoline
,
Commercial Jet A‐1, USAF JP‐8
#1 Diesel
#2 Diesel
Heavy Diesel
#2 Fuel Oil  "Heating Oil"
#6 Fuel Oil  "Bunker C"
Lubricating Oil
Residuum and Asphalt
Residuum and Asphalt
B. P. of n‐Paraffin, 760 mm Hg, °C ‐0.5 69 126 174 216 253 287 316 343 369 391 412 431 450
─ Drews, A.W., Ed., Manual on Hydrocarbon Analysis, ASTM, 1989 .
─ PRO-ACT Fact Sheet: Petroleum Fuels: Basic Composition and Properties
Properties,
www.p2pays.org/ref/07/06026.htm, NC Dept. of Env. & Nat. Resources, 1999.
5
Note: Carbon Number Ranges Vary In References
 GC/MS: Gasoline and Asphalt
p
Abundance

TIC: FHWA017.D\data.ms
6500000
TIC: Sinclair072.D\data.ms (*)

Gas Chromatography /Mass Spectrometry Parameters

6000000

5500000 GC Inlet: 5:1 split, 280 ºC, 1 µL injection

GC Column: DB-5, 25 m x 0.2 mm ID x 0.11 µm
5000000
GC Oven: 30 ºC (3 min) – 10 ºC/min – 275 ºC (12.5 min)
4500000
MS Parameters: EI 70 eV, Scan 35 – 350 amu

4000000

Gasoline Range Organics (GRO)

3500000

3000000
Includes BTEX
2500000

2000000

Asphalt Binder
1500000

1000000

500000

5.00 10.00 15.00 20.00 25.00 30.00 35.00

Time-->

6
 Sample
p Prep
p
• Weigh 10 – 20 g of pavement sample into 40 mL glass vial
• Pipette 10 – 20 mL of dichloromethane (methylene chloride) into vial
• Shake vigorously and sonicate in ultrasonic bath; allow to settle overnight
• Inject supernatant sample extract into GC/MS

7
 Was The Prime Coat Applied?
pp
Abundance

n-C12 2 Control Pavement Samples

1100000

1000000

900000

Diesel Range
800000
Organics (DRO)
700000

600000

500000

400000

300000

200000

100000

0
5.00 10.00 15.00 20.00 25.00 30.00 35.00
Time-->

8
 Was The Prime Coat Applied?
pp
Abundance

3 Pavement Locations With DRO

1300000

1200000

1100000

1000000

900000

800000

700000

600000

500000

400000

300000

200000

100000
Primer
0
5.00 10.00 15.00 20.00 25.00 30.00 35.00
Time-->
9
 Was The Prime Coat Applied?
pp
Abundance

3 Pavement Locations With No DRO

1100000

1000000

900000

800000

700000

600000

500000

400000

300000

200000

100000

0
5.00 10.00 15.00 20.00 25.00 30.00 35.00
Time-->
10
 Was Diesel Fuel Spilled?
p
Abundance
• Central Federal Lands Highway
400000
Division
380000

360000 • Project: Grand Canyon Road Failure

340000

320000

n-C17
300000

280000

260000

Diesel Fuel Reference

240000

220000

200000 S
Standard
d d
180000

160000

140000

120000

100000

80000

60000

40000

20000

5.00 10.00 15.00 20.00 25.00 30.00

Time-->
11
 Petroleum Product Types
yp

C4 C6 C8 C10 C12 C14 C16 C18 C20 C22 C24 C26 C28 C30 >C30
VV.M.&P. Naphtha 
M &P Naphtha "Solvent
Solvent, Light
Light"
Mineral Spirits
Gasoline
,
Commercial Jet A‐1, USAF JP‐8
#1 Diesel
#2 Diesel
Heavy Diesel
#2 Fuel Oil  "Heating Oil"
#6 Fuel Oil  "Bunker C"
Lubricating Oil
Residuum and Asphalt
Residuum and Asphalt
B. P. of n‐Paraffin, 760 mm Hg, °C ‐0.5 69 126 174 216 253 287 316 343 369 391 412 431 450
─ Drews, A.W., Ed., Manual on Hydrocarbon Analysis, ASTM, 1989 .
─ PRO-ACT Fact Sheet: Petroleum Fuels: Basic Composition and Properties
Properties,
www.p2pays.org/ref/07/06026.htm, NC Dept. of Env. & Nat. Resources, 1999.
12
Note: Carbon Number Ranges Vary In References
 Was Diesel Fuel Spilled?
p
Abundance

450000 n-C17
Diesel Fuel at 0.1% Concentration
400000

350000

300000

250000

200000

150000

100000

50000

0
11.00 12.00 13.00 14.00 15.00 16.00 17.00 18.00 19.00 20.00 21.00
13
Time-->
 What Is Causing The Petroleum
Odor?
• Central Federal Lands Highway Division
• Project:
P j t Saddle
S ddl Road,
R d Big
Bi Island
I l d off Hawai’i
H i’i
190000

180000

170000

160000
• Road Base Material Under Existing Road
150000 p
• Asphalt Cutback Suspected
p (Naphtha,
p ,
140000
Kerosene?)
130000

120000

110000

100000

90000

80000

70000

60000

50000

40000

30000

20000

5.00 10.00 15.00 20.00 25.00 30.00

Time-->

14
 Selected Hydrocarbon Ions Within
TIC
Ion 57.00 (56.70 to 57.70):4.D
FHWA19
\data.ms
Ion 71.00 (70.70 to 71.70): FHWA194.D
\data.ms
Ion 85.00 (84.70 to 85.70): FHWA194.D
\data.ms
10.999
Ion 99.00 (98.70 to 99.70): FHWA194.D
\data.ms 18.906
Ion 113.00 (112.70 to 113.70): FHWA194.D
\data.ms
Ion 127.0
0 (126.70 to 127.70): FHWA194.D
\data.ms

23.709

14.993 18.276

Total Ion Chromatogram

5.00 10.00 15.00 20.00 25.00 30.00
16.081
20.004

Ion 57: CH3CH2CH2CH2

15.00 15.50 16.00 16.50 17.00 17.50 18.00 18.50 19.00 19.50 20.00 15
 Road (Top) vs. Diesel Reference
dance Std.
Std
Ion 57.00 (56.70 to 57.70): FHWA174.D\data.ms
Ion 71.00 (70.70 to 71.70): FHWA174.D\data.ms 18.902
2600 Ion 85.00 (84.70 to 85.70): FHWA174.D\data.ms
Ion 99.00 (98.70 to 99.70): FHWA174.D\data.ms 19.999
Ion 113.00 (112.70 to 113.70): FHWA174.D\data.ms
2400 Ion 127.00 (126.70 to 127.70): FHWA174.D\data.ms
18.282
2200

2000

1800

1600
16.088

1400 14.995

1200

1000

800

600

400

200

ndance 0
15.00 15.50 16.00 16.50 17.00 17.50 18.00 18.50 19.00 19.50 20.00
-> Ion 57.00 (56.70 to 57.70): FHWA194.D\data.ms
Ion 71.00
1 00 ((70.70
0 0 to 71.70):
1 0) FHWA194.D\data.ms
19 \
45000 Ion 85.00 (84.70 to 85.70): FHWA194.D\data.ms
Ion 99.00 (98.70 to 99.70): FHWA194.D\data.ms 18.906
Ion 113.00 (112.70 to 113.70): FHWA194.D\data.ms
Ion 127.00 (126.70 to 127.70): FHWA194.D\data.ms
40000

14.993 18.276
35000
16.081
20.004
30000

25000

20000

15000

10000

5000

0
15.00 15.50 16.00 16.50 17.00 17.50 18.00 18.50 19.00 19.50 20.00 16
e-->
 n-Alkanes Are Missing
But Isoprenoids Are Present

14.99 minutes:
2,6,10-trimethyldodecane, C15H32
Farnesane

18.90 minutes:
, , , yp , C19H40
2,6,10,14-tetramethylpentadecane,
Pristane

19.99 minutes:
2,6,10,14-tetramethylhexadecane, C20H42
Phytane
17
 DRO Biodegradation
g

• Middle distillates such as diesels are weathered mainly by biodegradation,

biodegradation
however, isoprenoids degrade very slowly compared to n-alkanes1.
• The rate of biodegradation is dependent on environmental conditions2.
• Th
The age off spilled
ill d diesel
di l may be b calculated
l l t d if,if for
f instance,
i t th soil
the il
samples have been collected from a zone that is beneath a paved area3.

1“Ageing
g g Diesel Spills”,
p , Jones Environmental Laboratory,
y,
http://jones-forensics.com/technical-information/ageing-diesel-spills.aspx
2“Can Diesel Fuel, #2 Fuel Oil or Home Heating Oil Be Age-dated?”,
Trillium’s Two Scents, Vol 2, Issue 1, Winter 1998, http://trilliuminc.com/V2N1.html
3 “Method for Determining the Age of Diesel Oil Spills in the Soil”,
Christensen, L.B. and T.H. Larsen, GWMR, Fall 1993, pp 142-149.
18
 Was The Polymer Modifier Added?
• Central Federal Lands Highway Division
• Project: Glacier Point Road, Yosemite
• Out-Of-Specification Grading…..Sample
Misrepresentation?
• Compare Loose Mix Sample and PG 64-28
64 28 Binder

Standard Method of Test for

Polymer Content of Polymer-Modified
Emulsified Asphalt Residue and Asphalt Binders

AASHTO Designation:
D i ti T 302-05
302 05
1. SCOPE
1.1. This test method is used to determine the percent concentration of a Styrene-Butadiene-
R bb (SBR),
Rubber (SBR) Styrene-Butadiene
S B di (SB),
(SB) or Styrene-Butadiene-Styrene
S B di S (SBS) polymer
l iin a
polymer modified asphalt binder or emulsified asphalt residue. By using the infrared spectrum
and the principles of Beer’s Law, the polymer content of the asphalt material can be determined. 19
 FTIR Technique
q 1
3.96
3.8
KBr Technique FTIR
3.6
3.4

3.2 Blue Trace: Control

3.0

2.8

2.6
Green Trace: Loose Mix
2.4

2.2
A
2.0
Polymer Absorbance Peaks
1.8

1.6
1.4

1.2

1.0

0.8

0.6 Magenta Trace: PG 64-28 Binder

0.4
0.29
990.1 985 980 975 970 965 960 955 950 945 942.9
cm-1

20
 FTIR Technique
q 2

ATR Technique FTIR

Blue Trace: PG 64-28 Binder

0.0370
0.034

0.032

0.030

0.028 Red Trace: Control

0.026

A
0.024

0 022
0.022
Polymer
y Absorbance Peaks
0.020

0.018

0.016

0.014
Black Trace: Loose Mix
0.012

0.010

0.0090991.0 985 980 975 970 960 955 950 945 940 935 930 925 920 914.0
965 cm-1

21
 FTIR Technique
q 3
0.746

0.70
Liquid Cell Technique FTIR
0.65

0.60

0.55
Polymer Absorbance Peaks
0 50
0.50

0.45

0.40

A 0.35

0.30

0.25

0.20

0.15

0.10

0.05

0.004
0 004
1037.1 1030 1020 1010 1000 990 980 970 960 950 940 930 920 910 900 891.7
cm-1
22
 Estimation Of Polymer
Content

Sample Peak Height 967 cm-1 Peak Height 1376 cm-1 Ratio
PG 64-28 Binder 0.0337 0.1247 0.27
Loose Mix 0.0449 0.1361 0.33

─The
The analysis shows that consistent
amounts of polymer modifier are present in
both the binder and loose mix samples that
were submitted to WRI.WRI The polymer
modifier content is estimated to be
approximately greater than or equal to 5 %
in the submitted samples.
23
 Is Fuel Oil Contaminating The Mix?
• Central Federal Lands Highway Division
• Project: Beartooth Highway, Park County, WY
• Concern That Fuel Oil Is Not Completely Combusted By Hot Mix
Plant
1600000

1400000

1200000

1000000
Fuel Oil: DRO + Higher Range
Used Motor Oil?
800000

600000

400000
Pavement Extract

200000

0
5.00 10.00 15.00 20.00 25.00 30.00 35.00 24
Time-->
 Is Fuel Oil Contaminating The Mix?

Abundance

1500000

1400000
Used Motor Oil
1300000

1200000

1100000

1000000
Second-Source
900000
Asphalt Binder
800000
For Comparison
700000
Purposes
600000

500000

400000

300000

200000
Pavement Extract
100000

0
5.00 10.00 15.00 20.00 25.00 30.00 35.00
Time--> 25
 Is Fuel Oil Contaminating The Mix?
Abundance

3500000

3000000 Fuel Oil Spiked

Into Pavement
2500000 Extract At Three
Concentrations
2000000

1500000

1000000

500000
Pavement Extract
0
5 00
5.00 10 00
10.00 15 00
15.00 20 00
20.00 25 00
25.00 30 00
30.00 35 00
35.00
Time-->
26
 Petroleum Product Types
yp

C4 C6 C8 C10 C12 C14 C16 C18 C20 C22 C24 C26 C28 C30 >C30
VV.M.&P. Naphtha 
M &P Naphtha "Solvent
Solvent, Light
Light"
Mineral Spirits
Gasoline
,
Commercial Jet A‐1, USAF JP‐8
#1 Diesel
#2 Diesel
Heavy Diesel
#2 Fuel Oil  "Heating Oil"
#6 Fuel Oil  "Bunker C"
Lubricating Oil
Residuum and Asphalt
Residuum and Asphalt
B. P. of n‐Paraffin, 760 mm Hg, °C ‐0.5 69 126 174 216 253 287 316 343 369 391 412 431 450
─ Drews, A.W., Ed., Manual on Hydrocarbon Analysis, ASTM, 1989 .
─ PRO-ACT Fact Sheet: Petroleum Fuels: Basic Composition and Properties
Properties,
www.p2pays.org/ref/07/06026.htm, NC Dept. of Env. & Nat. Resources, 1999.
27
Note: Carbon Number Ranges Vary In References
 Future Needs
• Overcome the GC Volatility Obstacle for Heavier
Petrochemicals
─ High Temperature GC
─ Liquid Chromatography (LC)
─ Gel
G l Permeation
P ti Chromatography
Ch t h (GPC)
• Overcome the Common Hydrocarbon Obstacle for Spills in
Asphalt
─ SARA or Solid Phase Extraction (SPE) as Pre-
separation?
p
─ Signature Elements, Compounds, Functional Groups?
p
• Perform Method Development Using:
─ Heavy Fuel Oil
─ Lubricating
L b i ti Oil
Oils ((motor
t oil,
il gear oil)
il)
─ Hydraulic Fluids (brake fluid) 28

─ Coolants (glycols) ?
 High
g Temperature
p GC

Injection
j Port: 20:1 split,
p , 375°C
Column: 15m x 0.32mm x 0.1µm DB-1HT
201°C → 385°C
Detector: FID, 395°C

29
 LC and GPC
Analysis of High Boiling Components in Petroleum Products by LC/MS
Jennifer Huang, Ray Chen, and Chris Loran, Thermo Fisher Scientific, San Jose, CA USA

Application Note: 371

Goal: To develop a robust LC/MS method for the complete analysis of petroleum products,
particularly for non-volatile or semi-volatile components not amenable to separation by
GC or GC/MS.
-------------------------------------------------------
30.0

GPC Analysis
25.0

Asphalt
p Binder

M illivv olts
20 0
20.0

15.0

Polymer 10.0
6 8 10 12 14 16

Time, Minutes
30
 Future Needs
• Overcome the GC Volatility Obstacle for Heavier
Petrochemicals
─ High Temperature GC
─ Liquid Chromatography (LC)
─ Gel
G l Permeation
P ti Chromatography
Ch t h (GPC)
• Overcome the Common Hydrocarbon Obstacle for Spills in
Asphalt
─ SARA or Solid Phase Extraction (SPE) as Pre-
separation?
p
─ Signature Elements, Compounds, Functional Groups?
p
• Perform Method Development Using:
─ Heavy Fuel Oil
─ Lubricating
L b i ti Oil
Oils ((motor
t oil,
il gear oil)
il)
─ Hydraulic Fluids (brake fluid) 31

─ Coolants (glycols) ?
 Acknowledgment
g

Our Sincere Thanks To:

Federal Highway Administration

Mike Peabody, Central Federal Lands Materials
Engineer
Denver Federal Center

32