A Forensic Approach for Discerning Hydrocarbon

Sources during Vapor Intrusion Pathway Investigations

Gina M. Plantz, Kevin McCarthy, Stephen Emsbo-Mattingly and Allen D. Uhler, Ph.D.
NewFields Environmental Forensics Practice, LLC
100 Ledgewood Place, Suite 302
Rockland, MA 02370
gplantz@newfields.com

ABSTRACT
Determining the sources of hydrocarbons in soil gas and indoor and ambient air is an
issue at many vapor intrusion sites. Vapor and air samples collected for chemical
characterization at vapor intrusion sites are typically analyzed following EPA Method
TO-15. The BTEX (benzene, toluene, ethylbenzene and xylenes) compounds, among the
few petroleum- or tar-derived hydrocarbons included as target analytes in the standard
TO-15 method, are commonly used by investigators to determine if hydrocarbons are
present in subsurface soils, and to infer the source(s) of such hydrocarbons.
Unfortunately, using only BTEX chemicals for identifying specific hydrocarbon sources
in soil gas is problematic because BTEX is present in virtually every type of hydrocarbon
product commonly encountered in the subsurface.
Owners of former MGP sites, gasoline stations and refineries are particularly vulnerable
to mistaken liability assignments, because the vapor phase of these petroleum and MGP
residues are easily confused with background sources. Conventional analytical
techniques (e.g. EPA TO-15) for soil gas and indoor air analysis include a limited number
of hydrocarbons with little or no ability to differentiate petroleum and MGP residues
from background influences. Although these methods are applicable for quantitative
assessments to very low risk levels, these methods were primarily designed for
chlorinated solvent analyses. They lack the analyte list and sensitivity for accurate
hydrocarbon source identification.
In order to accurately characterize the nature and type or types of hydrocarbons sources
in soil gas, indoor and ambient air, these environmental samples must be analyzed using a
descriptive method of analysis that employs a more robust target analyte list. This paper
presents a forensic air method (Forensic TO-15) specifically developed to differentiate
tar, gasoline, and background sources during VI investigations. The robust target analyte
list includes many Paraffin, Isoparaffin, Aromatic, Naphthene, and Olefin (PIANO)
compounds. Forensic TO-15 can be a critical tool for site characterization by producing
distinct fingerprints for source determination. The importance and advantages of being
able to fingerprint hydrocarbons in the subsurface and indoor air will be discussed and
case study data will be presented.

INTRODUCTION
Over the past several years, the vapor intrusion (VI) pathway has gained significant
attention from the regulatory, risk assessment, real property management, and legal
communities because of concerns for potential indoor human exposure to volatile organic
chemicals (VOCs) via this transport mechanism. Numerous guidance documents have
been developed to assist site investigators in assessing whether or not the pathway poses
a significant health risk to potentially-exposed individuals in both residential and
industrial settings.
A significant challenge for assessing the VI pathway is defensibly determining the
source(s) of the VOCs detected in indoor air samples. Many of the compounds present in
contaminated soil and groundwater are also present in consumer products, building
materials and even in the outdoor air
Conclusively linking any VOCs found in indoor air to a particular subsurface
contaminant versus VOCs associated with a background source(s) - poses a significant
environmental forensic challenge. This challenge is best met through a combination of
detailed analytical chemistry and a thorough evaluation of the site-specific conditions.
Analysis of air samples by the Standard EPA Method TO-15 yields characterization data
lacking the specificity and sensitivity to distinguish among most sources of VOCs.
However, this method of analysis can be modified for chemical fingerprinting by (1)
quantifying the absolute concentrations of a larger number of VOCs than Standard TO-15
using GC/MS and (2) simultaneously acquiring conventional GC/FID fingerprints that
permit discrimination among different VOC sources, particularly hydrocarbon-rich
sources such as petroleum fuels, solvents, and MGP wastes. Forensic TO-15 analytical
data provides a unique and powerful tool to profile indoor air contamination and confirm
or refute the existence of a complete VI pathway through careful comparison of the
indoor air chemical profile with that of suspected sources.

DISCUSSION
The most common contaminants of potential concern for VI investigations are VOCs.
While this paper focuses on VOCs, it is important to note that other compounds may be a
driver at a VI pathway assessment.
In addition to ambient background sources, a number of potential subsurface sources of
VOCs such as natural oil/gas seeps, leaks from oil or gas production wells, natural gas or
other pipelines, landfills, and hydrocarbon-contaminated soil and groundwater. It is
extremely important to understand the source of hydrocarbon vapors for mitigation and
liability management. Some VOC sources, such as methane, offer little molecular basis
to distinguish one source from another (e.g., natural/thermogenic gas versus biogenic gas)
and therefore rely upon stable isotopic parameters (13C/12C; Lundegard, 2006). Other
VOC sources, such as petroleum fuels (e.g., gasoline) or MGP tars can yield a complex
molecular fingerprint that after considering the effects of partitioning - can be used to

differentiate these sources from one another and other sources (Stout et al. 2002).
Therefore, the collection of sufficiently specific molecular data is critical in
distinguishing different VOC sources and should be considered in any VI evaluation. In
the following sections, the Standard and Forensic methods for molecular
characterization of VOC in soil gas and air samples are described and compared.

Standard TO-15
The EPA has promulgated a series of Toxic Organics (TO) methods for measuring the
concentrations of contaminants in ambient air. EPA Method TO-15 is a recommended
method for collection and analysis of soil gas and indoor and ambient air samples in
many of the VI guidance documents. Method TO-15 was first published in 1997 and
updated in 1999 under the U.S. EPAs Compendium of Methods for the Determination of
Toxic Organic Compounds in Ambient Air (USEPA, 1999).
The standard TO-15 target analyte list includes an extensive list of halogenated VOCs
(Table 1), which renders the standard method appropriate for evaluating chlorinated
solvent indoor air issues. However, only a handful of the standard target analytes are
petroleum-type hydrocarbons or gasoline additives that would be useful in
fingerprinting hydrocarbon-rich sources (e.g., gasoline or tars). This list includes
methyl tert-butyl ether (MTBE), pentane, hexane, heptane, benzene, ethylene dichloride,
toluene, ethylene dibromide, ethylbenzene, styrene, p-xylene, m-xylene, o-xylene, and
1,3,5-trimethylbenzene. Given that there potentially are hundreds of VOCs in gasoline or
the volatile range of other important hydrocarbon sources (e.g. MGP tars or creosotes),
the few hydrocarbons among the standard TO-15 target analytes (Table 1) are of limited
forensic benefit because they lack the specificity to distinguish one hydrocarbon source
from another, including background sources.

Table 1. Standard TO-15 Analyte List.

1,1,1-trichloroethane
1,1,2,2-tetrachloroethane
1,1,2-trichloroethane
1,1-dichloroethane
1,1-dichloroethene
1,2,4-trichlorobenzene
1,2,4-trimethylbenzene
1,2-dibromoethane
1,2-dichlorobenzene
1,2-dichloroethane
1,2-dichloropropane
1,3,5-trimethylbenzene
1,3-butadiene
1,3-dichlorobenzene
1,4-dichlorobenzene
1,4-dioxane
2-butanone
2-hexanone
3-chloropropene
4-Ethyltoluene
acetone
benzene
benzyl chloride
bromodichloromethane
bromoform
bromomethane
carbon disulfide
carbon tetrachloride
chlorobenzene
chloroethane
chloroform
chloromethane

cis-1,2-dichloroethene
cis-1,3-dichloropropene
cyclohexane
dibromochloromethane
dichlorodifluoromethane
ethanol
ethyl acetate
ethylbenzene
Freon-113
Freon-114
heptane
hexachlorobutadiene
hexane
isopropyl alcohol
methylene chloride
MIBK
MTBE
m+p-xylene
o-xylene
pentane
propylene
styrene
tetrachloroethene
tetrahydrofuran
toluene
trans-1,2-dichloroethene
trans-1,3-dichloropropene
trichloroethene
trichlorofluoromethane
vinyl acetate
vinyl bromide
vinyl chloride

Forensic TO-15
The standard TO-15 method can be modified for hydrocarbon VI studies by developing a
more appropriate target analyte list that provides the specificity necessary to distinguish
different hydrocarbon sources. A comparable modification was previously applied to the
standard EPA Method 8260 for the characterization of hydrocarbon sources in water, soil,
and oils (Uhler et al., 2000). The Forensic TO-15 method presented in this paper has an
extensive target analyte list that includes various PIANO compounds, as well as tarspecific (e.g., styrene) or gasoline-specific compounds (e.g., oxygenate additives) and
various thiophenes (Table 2). These compounds provide far more specificity than

standard TO-15 analytes (Table 1) and thereby provide a much more powerful means for
distinguishing the source of gas phase constituents in vapor or air samples that cannot be
achieved using the standard methods smaller analyte list.
Table 2. Forensic TO-15 Analyte List.
Class

Abbrev.

Analyte

Class

Abbrev.

Analyte

O
I
O
O
P
O
O
OX
N
I
I
OX
I
O
P
OX
OX
I
N
I
ADD
N
I
A
I
S
I
OX
O
I
P
N
I
I
I
I
I
I
I
I
A
S
S
O
N

13B
IP
1P
2M1B
C5
T2P
C2P
TBA
CYP
23DMB
2MP
MTBE
3MP
1HEX
C6
DIPE
ETBE
22DMP
MCYP
24DMP
12DCA
CH
2MH
B
23DMP
THIO
3MH
TAME
1H
ISO
C7
MCYH
25DMH
223TMP
234TMP
233TMP
23DMH
3EH
2MHEP
3MHEP
T
2MTHIO
3MTHIO
1O
1E1MCP

1,3-Butadiene
Isopentane
1-Pentene
2-Methyl-1-butene
Pentane
2-Pentene (trans)
2-Pentene (cis)
Tertiary butanol
Cyclopentane
2,3-Dimethylbutane
2-Methylpentane
MTBE
3-Methylpentane
1-Hexene
Hexane
Diisopropyl Ether (DIPE)
Ethyl Tertiary Butyl Ether (ETBE)
2,2-Dimethylpentane
Methylcyclopentane
2,4-Dimethylpentane
1,2-Dichloroethane
Cyclohexane
2-Methylhexane
Benzene
2,3-Dimethylpentane
Thiophene
3-Methylhexane
TAME
1-Heptene
Isooctane
Heptane
Methylcyclohexane
2,5-Dimethylhexane
2,4-Dimethyhexane / 2,2,3-TMP
2,3,4-Trimethylpentane
2,3,3-Trimethylpentane
2,3-Dimethylhexane
3-Ethylhexane
2-Methylheptane
3-Methylheptane
Toluene
2-Methylthiophene
3-Methylthiophene
1-Octene
1-Ethyl-1-methylcyclopentane

P
ADD
A
S
A
O
P
A
A
A
A
A
A
A
O
A
P
A
A
A
A
A
A
A
A
A
A
A
A
A
A
P
A
A
A
A
A
A
P
A
S
ADD
P
A
A

C8
12DBE
EB
2ETHIO
MPX
1N
C9
STY
OX
IPB
PROPB
1M3EB
1M4EB
135TMB
1D
1M2EB
C10
124TMB
SECBUT
1M3IPB
1M4IPB
1M2IPB
IN
INE
1M3PB
1M4PB
BUTB
12DM4EB
12DEB
1M2PB
14DM2EB
C11
13DM4EB
13DM5EB
13DM2EB
12DM3EB
1245TMP
PENTB
C12
N
BT0
MMT
C13
2MN
1MN

Octane
1,2-Dibromoethane
Ethylbenzene
2-Ethylthiophene
p/m-Xylene
1-Nonene
Nonane
Styrene
o-Xylene
Isopropylbenzene
n-Propylbenzene
1-Methyl-3-ethylbenzene
1-Methyl-4-ethylbenzene
1,3,5-Trimethylbenzene
1-Decene
1-Methyl-2-ethylbenzene
Decane
1,2,4-Trimethylbenzene
sec-Butylbenzene
1-Methyl-3-isopropylbenzene
1-Methyl-4-isopropylbenzene
1-Methyl-2-isopropylbenzene
Indan
Indene
1-Methyl-3-propylbenzene
1-Methyl-4-propylbenzene
n-Butylbenzene
1,2-Dimethyl-4-ethylbenzene
1,2-Diethylbenzene
1-Methyl-2-propylbenzene
1,4-Dimethyl-2-ethylbenzene
Undecane
1,3-Dimethyl-4-ethylbenzene
1,3-Dimethyl-5-ethylbenzene
1,3-Dimethyl-2-ethylbenzene
1,2-Dimethyl-3-ethylbenzene
1,2,4,5-Tetramethylbenzene
Pentylbenzene
Dodecane
Naphthalene
Benzothiophene
MMT
Tridecane
2-Methylnaphthalene
1-Methylnaphthalene

Class
P
I
A
N
O
S
ADD

Paraffin
Isoparaffin
Aromatic
Naphthene
Olefin
Sulfur
Additive

Another modification to the standard TO-15 method involves the simultaneous analysis
of the VOCs by both GC/MS and gas chromatography/flame ionization detection
(GC/FID). The GC/MS is used to quantitatively measure the target VOCs (Table 2)
using a conventional calibration curve and individual response factor for each target
analyte. The MS data are acquired simultaneously using both full scan and SIM modes,
the former allowing for the identification of unknown (non-target) VOCs and the latter
allowing for sub-ppbv RLs for targeted analytes (Table 2). The GC/FID is used to
simultaneously collect a conventional fingerprint spanning the C3-C13 carbon range.
The GC/FID analysis provides additional chemical fingerprinting information useful for
product type identification, a necessary and important element in differentiating and
identifying chemical source signatures at contaminated sites. Examples of the GC/FID
fingerprints obtained using this method for the vapor phase of unweathered automotive
gasoline, diesel fuel #2, and coal tar are shown in Figure 1.
Figure 1. GC/FID chromatograms for vapor phases of (A) unweathered automotive
gasoline, (B) diesel fuel #2, and (C) coal tar.

Tiered Approach
As with any investigation, it is not always necessary to utilize the most sophisticated
analytical methodologies for the first tier of the forensic investigation. Many regulatory
agencies will require the use of standard TO-15 for the initial investigation and reporting
of site conditions. The data from the standard TO-15 can be a useful screening tool to
help in deciding whether it is necessary to continue to a more detailed forensic analysis.
Standard TO-15 can:
Quantitate many VOCs of concern to below the risk based
concentrations; if there are no VOCs of concern above the screening
criteria, there may be no reason to continue with forensic TO-15
Discern basic hydrocarbon signatures
Provide qualitative assessment of hydrocarbon TICs
If after reviewing the TO-15 data, there is a need for Forensic TO-15, the analysis can be
conducted from the same canister as was used for TO-15.
An example of the advantage of the expanded target analytes is shown in Figure 2 and
Figure 3, which compares the VOC histograms for the same soil gas and indoor air
samples collected near a former MGP and analyzed using the Standard and Forensic TO15 methods. The comparison of these histograms resolves a significantly higher degree
of source signature information for the soil gas samples analyzed using the Forensic TO15 method.
The quantitative data from TO-15 (Figure 2) shows Benzene, Toluene and m/p-Xylene in
both the soil gas and indoor air, which may lead the investigator to believe that there is a
VI impact occurring in the building. With further analysis and review of the Forensic
TO-15 histograms (Figure 3), it is clear that the soil gas signature is uniquely different
then the indoor air signature. Utilizing Forensic TO-15 for this investigation revealed
two key factors:
1. The VOCs present in the soil gas outside of the building did not contain chemical
characteristics of coal tar vapor (see Figure 4 for an example histogram);
2. The indoor air was impacted by a source - or sources - which did not emanate
from the soil gas which was analyzed.

0.00
13B
IP
1P
2M1B
C5
T2P
C2P
TBA
CYP
23DMB
2MP
MTBE
3MP
1HEX
C6
DIPE
ETBE
22DMP
MCYP
24DMP
12DCA
CH
2MH
B
23DMP
THIO
3MH
TAME
1H
ISO
C7
MCYH
25DMH
DMH/TMP
234TMP
233TMP
23DMH
3EH
2MHEP
3MHEP
T
2MTHIO
3MTHIO
1O
1E1MCP
C8
12DBE
EB
2ETHIO
MPX
1N
C9
STY
OX
IPB
PROPB
1M3EB
1M4EB
135TMB
1D
1M2EB
C10
124TMB
SECBUT
1M3IPB
1M4IPB
1M2IPB
IN
INE
1M3PB
1M4PB
BUTB
12DM4EB
12DEB
1M2PB
14DM2EB
C11
13DM4EB
13DM5EB
13DM2EB
12DM3EB
1245TMP
PENTB
C12
N
BT0
MMT
C13
2MN
1MN

0.00

13B
IP
1P
2M1B
C5
T2P
C2P
TBA
CYP
23DMB
2MP
MTBE
3MP
1HEX
C6
DIPE
ETBE
22DMP
MCYP
24DMP
12DCA
CH
2MH
B
23DMP
THIO
3MH
TAME
1H
ISO
C7
MCYH
25DMH
DMH/TMP
234TMP
233TMP
23DMH
3EH
2MHEP
3MHEP
T
2MTHIO
3MTHIO
1O
1E1MCP
C8
12DBE
EB
2ETHIO
MPX
1N
C9
STY
OX
IPB
PROPB
1M3EB
1M4EB
135TMB
1D
1M2EB
C10
124TMB
SECBUT
1M3IPB
1M4IPB
1M2IPB
IN
INE
1M3PB
1M4PB
BUTB
12DM4EB
12DEB
1M2PB
14DM2EB
C11
13DM4EB
13DM5EB
13DM2EB
12DM3EB
1245TMP
PENTB
C12
N
BT0
MMT
C13
2MN
1MN

Concentration ppbv

Concentration ppbv

Figure 2. Standard TO-15 Histogram (see Table 2 for identification of abbreviations).

TO-15 Histogram
Indoor Air

0.20

0.16

0.12

0.08

0.04

Analytes

TO-15 Profile Histogram

Soil Gas

4.00

3.50

3.00

2.50

2.00

1.50

1.00

0.50

Analytes

0.00
13B
IP
1P
2M1B
C5
T2P
C2P
TBA
CYP
23DMB
2MP
MTBE
3MP
1HEX
C6
DIPE
ETBE
22DMP
MCYP
24DMP
12DCA
CH
2MH
B
23DMP
THIO
3MH
TAME
1H
ISO
C7
MCYH
25DMH
DMH/TMP
234TMP
233TMP
23DMH
3EH
2MHEP
3MHEP
T
2MTHIO
3MTHIO
1O
1E1MCP
C8
12DBE
EB
2ETHIO
MPX
1N
C9
STY
OX
IPB
PROPB
1M3EB
1M4EB
135TMB
1D
1M2EB
C10
124TMB
SECBUT
1M3IPB
1M4IPB
1M2IPB
IN
INE
1M3PB
1M4PB
BUTB
12DM4EB
12DEB
1M2PB
14DM2EB
C11
13DM4EB
13DM5EB
13DM2EB
12DM3EB
1245TMP
PENTB
C12
N
BT0
MMT
C13
2MN
1MN

0.00

13B
IP
1P
2M1B
C5
T2P
C2P
TBA
CYP
23DMB
2MP
MTBE
3MP
1HEX
C6
DIPE
ETBE
22DMP
MCYP
24DMP
12DCA
CH
2MH
B
23DMP
THIO
3MH
TAME
1H
ISO
C7
MCYH
25DMH
DMH/TMP
234TMP
233TMP
23DMH
3EH
2MHEP
3MHEP
T
2MTHIO
3MTHIO
1O
1E1MCP
C8
12DBE
EB
2ETHIO
MPX
1N
C9
STY
OX
IPB
PROPB
1M3EB
1M4EB
135TMB
1D
1M2EB
C10
124TMB
SECBUT
1M3IPB
1M4IPB
1M2IPB
IN
INE
1M3PB
1M4PB
BUTB
12DM4EB
12DEB
1M2PB
14DM2EB
C11
13DM4EB
13DM5EB
13DM2EB
12DM3EB
1245TMP
PENTB
C12
N
BT0
MMT
C13
2MN
1MN

Concentration ppbv

Concentration ppbv

Figure 3. Forensic TO-15 Histogram (see Table 2 for identification of abbreviations).

Forensic TO-15 Histogram
Indoor Air

1.40

1.20

1.00

0.80

0.60

0.40

0.20

Analytes

Forensic TO-15 Histogram

Soil Gas

25.00

20.00

15.00

10.00

5.00

Analytes

Figure 4. Forensic TO-15 Histogram of a MGP tar vapor.

MGP Tar Vapor

35000.00

30000.00

Concentration ppbv

25000.00

20000.00

15000.00

10000.00

0.00

13B
IP
1P
2M1B
C5
T2P
C2P
TBA
CYP
23DMB
2MP
MTBE
3MP
1HEX
C6
DIPE
ETBE
22DMP
MCYP
24DMP
12DCA
CH
2MH
B
23DMP
THIO
3MH
TAME
1H
ISO
C7
MCYH
25DMH
DMH/TMP
234TMP
233TMP
23DMH
3EH
2MHEP
3MHEP
T
2MTHIO
3MTHIO
1O
1E1MCP
C8
12DBE
EB
2ETHIO
MPX
1N
C9
STY
OX
IPB
PROPB
1M3EB
1M4EB
135TMB
1D
1M2EB
C10
124TMB
SECBUT
1M3IPB
1M4IPB
1M2IPB
IN
INE
1M3PB
1M4PB
BUTB
12DM4EB
12DEB
1M2PB
14DM2EB
C11
13DM4EB
13DM5EB
13DM2EB
12DM3EB
1245TMP
PENTB
C12
N
BT0
MMT
C13
2MN
1MN

5000.00

Analytes

CONCLUSIONS
Due to increasing regulatory scrutiny and the potential liability associated with civil cost
recovery litigation, it is becoming critical for the regulated community to assess whether
or not a vapor VI pathway exists at sites currently, or even historically, under
investigation for subsurface contamination. However, because the assessment of VI is a
relatively new and evolving science, there are many challenges with assessing this
pathway. The key to successful VI evaluations include:

The selection of appropriate tools to substantiate the existence of a VI pathway,

The differentiation of VI impacts from confounding sources (including
background),
The credible protection of human health, and
The satisfaction of regulatory compliance criteria.
This sounds straightforward, but in the midst of rapidly developing technical standards
and regulatory guidance, it is important for investigators to understand the air chemistry,
soil gas assessment options, ambient air quality, conventional analytical method
limitations (Standard Method TO-15), and emerging strategies for risk and source
identification (Forensic TO-15). As with any environmental forensic investigation it is

necessary to utilize multiple lines of scientific data and site-specific information to

address the typical forensic questions:
What is the chemical nature of the contaminants?
What is the source(s) of the contamination?
The ability of Forensic TO-15 to define and track the source signature(s) of the vapor
borne contamination greatly improves the capability of the forensic investigator to
confirm or refute the presence of a completed VI pathway.

REFERENCES
1. Compendium of Methods for the Determination of Toxic Organic Compounds in
Ambient Air: Method TO-15, Second Edition, U.S. Environmental Protection
Agency: Research Triangle Park, NC January 1999; EPA 600/625/R-96/010b.
2. Lundegard, P.D. (2006) Methane. In: Environmental Forensics: A Contaminant
Specific Approach, B. Murphy and R. Morrison, Eds.,. Elsevier Publishing Co.,
San Francisco, CA. pp. 97-110.
3. Stout, S.A., Uhler, A.D., McCarthy, K.J. and Emsbo-Mattingly, S.D. (2002)
Chemical Fingerprinting of Hydrocarbons. In: Introduction to Environmental
Forensics, (B. Murphy and R. Morrison, Eds.), Academic Press, New York, p.
135-260.
4. Uhler, R.M., Healey, E.M., McCarthy, K.J., Uhler, A.D., and Stout, S.A. 2003.
Molecular Fingerprinting of Gasoline by a Modified EPA 8260 Gas
Chromatography/Mass Spectrometry Method. Int. J. Environ. Anal. Chem. 83(1):
1-20

KEY WORDS
BTEX
Forensic Air Analysis
Fingerprinting Soil Gas
Forensic TO-15
Indoor Air Background
MGP
Soil Gas
Soil Vapor
TO-15
Vapor Intrusion