Journal of Chromatography A 1635 (2021) 461717

Contents lists available at ScienceDirect

Journal of Chromatography A
journal homepage: www.elsevier.com/locate/chroma

Development of retention time indices for comprehensive

multidimensional gas chromatography and application to ignitable
liquid residue mapping in wildfire investigations
Nadin Boegelsack a,b,∗, Court Sandau a,c, Dena W. McMartin b, Jonathan M. Withey d,
Gwen O’Sullivan a
a
Department of Earth and Environmental Sciences, Mount Royal University, 4825 Mount Royal Gate SW, Calgary, AB Canada, T3E 6K6
b
Department of Civil, Geological and Environmental Engineering, University of Saskatchewan, 57 Campus Drive, Saskatoon, SK Canada, S7N 5A9
c
Chemistry Matters Inc., 104-1240 Kensington Rd NW Suite 405, Calgary, AB Canada, T2N 3P7
d
Department of Chemistry and Physics, Mount Royal University, 4825 Mount Royal Gate SW, Calgary, AB Canada, T3E 6K6

a r t i c l e i n f o a b s t r a c t

Article history: In this study, we introduce a simple three-step workflow for a universally applicable RI system, to be
Received 3 August 2020 used in GC×GC analysis of ignitable liquid residue (ILR) for arson investigations. The proposed RI system
Revised 7 November 2020
applies a combination of two well-established GC RI systems: non-isothermal Kovats (K) index in the first
Accepted 9 November 2020
dimension and Lee (L) index in the second dimension. The proposed KLI RI system showed very good
Available online 14 November 2020
correlations when compared with predicted values and existing RI systems (r2 = 0.97 in first dimension,
Keywords: r2 = 0.99 in second dimension) and was valid for a wide range of analyte concentrations and operational
GC×GC settings (coefficient of variance (CV) < 1% in first dimension, < 10% in second dimension). Using the
forensic science KLI RI, an ILR classification contour map was created to assist with the identification of ILR types within
fire debris analysis ASTM E1618. The contour map was successfully applied to neat fuels and a fire scene sample, highlighting
arson investigations the application to wildfire investigation. Standardizing the RI process and establishing acceptable error
margins allows the exploration and comparison of comprehensive data generated from GC×GC analysis
of ILRs regardless of location, time, or system, further enhancing comprehensive and tenable chemometric
analyses of samples. Overall, the KLI workflow was inexpensive, quick to apply, and user-friendly with its
simple 3-step design.
© 2020 The Author(s). Published by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)

1. Introduction ILR analysis is currently regulated in North America by a se-

Wildfires are burning with higher intensity, covering larger ar-
eas and causing unprecedented financial damage [1,2,3]. The main
sources of ignition for wildfires are either natural (e.g., lightning
strikes) or anthropogenic (e.g., intentional acts of arson, unat-
tended campfires, burning of debris, equipment sparks and mal-
functions, discarded cigarettes). Ignitable liquid residues (ILRs)
are the remnants of accelerants, which are substances or mix-
tures used to expedite the development or escalation of fire dur-
ing the act of arson. Laboratory identification of the presence of
ILR, type of accelerant, and source of accelerant used in arson-
ous fires can provide key evidence for conviction in arson cases.
∗
Corresponding author.
E-mail address: nboegelsack@mtroyal.ca (N. Boegelsack).
ries of ASTM International standards (formerly American Society
of Testing and Materials), which prescribe different potential ex-
traction techniques along with analysis using gas chromatogra-
phy coupled with mass spectrometry (GC-MS) [4]. After positive
identification of an ILR, the method requires the detected ILR to
be categorized into defined classes including gasoline, petroleum
distillates, isoparaffinic products, aromatic products, naphthenic-
paraffinic products, normal alkane products, oxygenated solvents,
and other-miscellaneous, where possible. All categories are further
sub-divided into light, medium, and heavy ranges [4]. Light range
is defined by the majority of compounds eluting in the area equiv-
alent to an n-alkane range from C4 to C9 ; Medium is between C8
and C13 ; and Heavy is from C9 to C20 and above [4]. The complex-
ity of the sample matrix and ILR composition, coupled with the
destructive nature of the fire itself [5,6], provides an opportunity
to apply more advanced analytical techniques, with better sensi-

https://doi.org/10.1016/j.chroma.2020.461717
0021-9673/© 2020 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/)
N. Boegelsack, C. Sandau, D.W. McMartin et al.
tivity and selectivity, to improve the detection and prosecution of
arson [7,8]. Particularly for wildfires, where the sample matrix con-
sists of different types of wood and soil, tree bark and other veg-
etation, the background composition has similar physico-chemical
properties to the ILR target compounds and is present at greater
concentrations [9].
Comprehensive multidimensional gas chromatography coupled
with mass spectrometry (GC×GC-MS) is a powerful tool for the
analysis of complex sample mixtures, with a ten-fold or larger in-
crease in separation potential over one-dimensional GC [10]. Appli-
cations of the technique include analysis of petroleum [11,12,13],
and of food and beverages [14,15], and use in medical and diag-
nostic testing [16,17], and in environmental and criminal forensics
[18,19,20]. Initial studies of ILR analysis using GC×GC coupled to a
flame ionization detector [7] and a quadrupole mass spectrometer
[21] highlighted the enhanced potential of the method to improve
resolution, peak detectability, and sensitivity. Analysis of ILR using
GC×GC coupled with time-of-flight mass spectrometry (TOF-MS)
has only recently emerged in the literature [22,23,24,9], and em-
phasizes the accessibility of the large amount of resultant data to
multivariate statistical analysis.
While GC×GC can provide better separation and resolution of
complex mixtures such as ILRs, there remains the challenge of cor-
rectly identifying separated compounds. The most reliable way to
identify a compound is based on co-injection of authentic stan-
dards, which can be both expensive and time consuming, as well
as not always being possible in the absence of existing or compre-
hensive standards. Retention time indices, which convert retention
times of compounds into system-independent unitless constants,
have supported compound identification successfully in conven-
tional GC, as well as GC×GC [14]. For example, the widely used
Kovats Retention Index converts the retention time of compounds
by normalizing the retention time to adjacent eluting n-alkanes.
These derived RI may be used to identify peaks by comparing mea-
sured retention indices with the tabulated published values, re-
ferred to as retention index libraries [25]. The continuous relevance
of this has been demonstrated recently in application to analy-
sis of fragrance, drugs, and environmental pollutants [26,27,28].
An example is the analysis of isomers and diastereomers, which
are indistinguishable based on their mass spectra, but which often
have distinct retention indices (e.g. pentyl- and isopentylbenzene,
xylenes). This highlights the power of RI data to complement mass
spectral data for reliable compound identification [25].
Initial work has begun to develop two-dimensional indices, in-
cluding the use of mathematical (thermodynamic models) [29,30]
and instrumental (isovolatility curves) approaches [14,31,32]. Gard-
ner et al. [33] combined the Kovats index in the first dimen-
sion and the Lee index in the second dimension to profile food-
borne pathogen bacteria using fatty acid methyl esters (FAMES).
And, while those compound groups (n-alkanes and FAME) are rel-
evant to ILR analysis, particularly biodiesels, the complexity (car-
bon number and ring structure) needs to be extended to cover
the range of ILR compound classes. Veenas & Haglund [34] used
n-alkanes and polyethylene glycols (PEGs) in their RI system to
introduce a regular polarity increase in the second dimension. RI
systems in one-dimensional GC can be converted between one an-
other if the correlation for the compound classes of interest is
known [25]. This principle transfers over to the first dimension in
GC×GC as the factors for calculation do not change. A similar study
for the second dimension is yet to be undertaken.
One complication of the second dimension is the process of
defining its ‘zero’ value. This is a straightforward procedure in the
first dimension as it refers to the absolute zero in time. Variabili-
ties exist in determining which data to exclude, e.g. dead time or
first eligible standard, but retention times always relate to the mo-
ment of injection. In the second dimension, wrap-around and va-
2
Journal of Chromatography A 1635 (2021) 461717
riety in compound classes of interest complicate defining its re-
spective zero value. N-alkanes are commonly used as baseline due
to their non-polarity combined with their utility in GC RI [33,34].
One method uses the average n-alkane secondary retention time,
whereas another approach requires a continuous evaluation of the
bracketing n-alkanes for each compound of interest. Meanwhile,
it could be argued that the “true” zero is the modulation period
switch, which is often accompanied by a characteristic peak of sol-
vent.
Defining zero also impacts wrap-around peaks. The aligning of
chromatograms to an arbitrary value in order to minimize or ex-
clude the appearance of wrap-around will result in incongruen-
cies in comparing multiple samples. These initial studies [32,33,34]
highlighting the need to widen the compound class coverage, and
standardize and simplify the RI process, to build comprehensive
databases for identification of unknown compounds.
A standardized RI system would allow for comprehensive anal-
ysis of all the compounds in ILRs, not only the traditional qual-
itative compounds, and facilitate the development of more com-
prehensive ILR databases and libraries. In addition, the RI method
would allow independent data verification by other scientists, and
cross-referencing between applications. An ILR reference library
stemming from retention indices would allow comparison of data
from an arson investigation to a variety of reference samples. These
could originate from different general ILR classes, from locally ac-
quired ILR classes as part of the investigation, and from other po-
tential arson investigations thought to be a result of the same ar-
sonist. The comprehensive analysis of all compounds in ILRs by
GC×GC analysis provides large datasets that may allow the correla-
tion of ILR to a fuel brand. Any reference library standardized to RI
would be comparable and allow the same chemometric approach
for identification of ILRs. In turn, this would facilitate the inclusion
of large amounts of data with minimal logistics, making any statis-
tical deductions more tenable.
In the work described here, an alternate RI system and work-
flow suitable for GC×GC analysis of ILRs is presented. The RI
system is universally applicable, allowing users analyzing simi-
lar chemical mixtures on different systems and analytical condi-
tions to compare results directly, regardless of modulator type.
The benefits of the proposed RI system are that it uses readily
available standards in a single injection, is directly comparable to
one-dimensional GC, and is pertinent to various applications with
petroleum hydrocarbons. The performance and robustness of the
proposed system has been tested by comparison to theoretically
predicted values and other applicable RI systems, and error anal-
ysis has been completed to test the tolerance of the proposed RI
system to instrument changes. Lastly, this work confirms the func-
tionality of the RI system to wildfire arson investigations by apply-
ing it in the analysis of accelerants and ILR in fire debris samples,
in conjunction with the ASTM classification system.
2. Material & Methods
2.1. Standards and reagents
A C7 -C30 saturated alkanes certified reference material (Cat#:
49451-U), C8 -C40 Alkanes Calibration Standard (Cat#: 40147-U),
PAH Mix 3 certified reference material (Cat#:861291), and PAH
Calibration Mix (Cat#: CRM47940) were purchased from Sigma
Aldrich (Supelco, Bellefonte, PA, USA). Benzene (99.9%), carbon
disulfide (CS2 , 99.9%), dichloromethane (DCM, 99.9%), methanol
(99.9%), and toluene (99.9%) were obtained from Fisher Scientific
(Ottawa, ON, Canada). A polyethylene glycol mixture (mono to
deca) was purchased from Chiron AS (Trondheim, Norway).
A 1ppm aromatic standard mixture containing alkanes (49451-
U), benzene, PAHs (861291), and toluene in DCM was prepared for
N. Boegelsack, C. Sandau, D.W. McMartin et al. Journal of Chromatography A 1635 (2021) 461717

the determination of RI values. From this mixture, all n-alkanes, Table 1

First-dimension retention indices and carbon number for each n-alkane calibration
toluene, naphthalene, phenanthrene, chrysene, and benzo(a)pyrene
compound using non-isothermal Kovats indices (KI1 ).
were taken as calibration compounds. The remaining detected
compounds were used as verification compounds in the aromatic n-alkane tR 1 (min) tR 2 (s) tR 2 corr. (s) KI1 Carbon number
calculations. A second 1ppm aromatic standard was prepared with Heptane 5.4 3.2 0.7 700 7
n-alkanes (40147-U), benzene, toluene, and PAHs (CRM47940) in Octane 8.1 3.4 0.9 800 8
methanol, and serially diluted to 62.5ppb to determine linear range Nonane 11.8 3.5 1 900 9
Decane 15.7 3.5 1 1000 10
and variation in response for error analysis.
Undecane 19.7 3.5 1 1100 11
Accelerants were purchased in Calgary, AB, Canada and included Dodecane 23.5 3.5 1 1200 12
a sample of lighter fluid (Ronsonol), and a composite sample of Tridecane 27.1 3.5 1 1300 13
gasoline and diesel. The composite gasoline sample was created Tetradecane 30.5 3.5 1 1400 14
Pentadecane 33.7 3.5 1 1500 15
by combining 21 gasolines of various octane rating 87 (n =6), 89
Hexadecane 36.7 3.5 1 1600 16
(n=7), 91 (n=6), 94 (n=2) collected from seven stations and di- Heptadecane 39.5 3.5 1 1700 17
luted 1/100 with CS2 . The diesel composite was created by com- Octadecane 42.3 3.5 1 1800 18
bining four diesel samples collected from four stations and diluted Nonadecane 44.9 3.5 1 1900 19
1/100 with CS2 . Eicosane 47.3 3.5 1 2000 20
Heneicosane 49.7 3.5 1 2100 21
Docosane 51.9 3.5 1 2200 22
2.2. Calculation of retention indices Tricosane 54.1 3.5 1 2300 23
Tetracosane 56.2 3.5 1 2400 24
Retention indices in the first dimension were calculated using Pentacosane 58.2 3.5 1 2500 25
Eq. (1) according to van den Dool & Kratz [35], also known as non- Hexacosane 60.1 3.5 1 2600 26
Heptacosane 62 3.5 1 2700 27
isothermal Kovats indices:
 t −t  Octacosane 63.8 3.5 1 2800 28
x n Nonacosane 65.5 3.5 1 2900 29
K I1 = 100n + 100 (1)
tn+1 − tn Triacontane 67.2 3.6 1.1 3000 30

Where n is the carbon number of the reference n-alkane eluting

immediately before the compound of interest, tx is the retention
time of the compound of interest, and tn and tn+1 are retention
times of n-alkanes eluting immediately before and after the com-
pound of interest respectively.
In the second dimension, the KLI RI was calculated used
Eq. (2) according to Lee [36]:
 t −t 
x n
LI2 = 100 100z
tn+1 − tn
Where tx is the retention time of the compound of interest, tn and
tn+1 are retention times of aromatics eluting immediately before
and after the compound of interest respectively, and z is the num-
ber of aromatic rings of the aromatic eluting immediately before
the compound of interest. To set the modulation as reference point
0, the secondary retention times were shifted -2.5 seconds prior to
applying Eq. (2), which is denoted as tR 2 corr. in Table 1.
The PEG RI was calculated using Eqs. (3) to (6) according to
Veenas & Haglund [34] in the second dimension. Using n-alkanes
as reference points in their calculations, Veenas & Haglund [34] ex-
trapolated the relative secondary retention time, 2 tR, E , of the PEGs
by applying Eq. (3) & (4).
2
tR, α 2 − 2 tR, α 1
2
tR, alkane (analyte ) = 2 tR, α1 +
R, α 2 − tR, α 1
1t 1
1  (Palo Alto, CA), retrofitted with an Insight flow modulator (Sep-
× tR, analyte − 1 tR, α 1
2t
Where R, alkane (analyte) represents the retention time in the sec-
ond dimension for the individual PEG calibration compound rela-
tive to its n-alkane value in the first dimension. 2 tR,α 1 and 2 tR,α 2
refer to absolute retention times in the second dimension of the
alkane eluting before and after the analyte, respectively, and 1 tR,α 1
and 1 tR,α 2 refer to their absolute retention times in the first di-
mension. 1 tR,analyte represents the absolute retention time in the
first dimension for the individual PEG calibration compound.
These reference values were then transformed into extrapolated
secondary retention times, 2 tR,E (analyte), as follows in Eq. (4):
2
tR,E (analyte ) = 2 t tR (analyte ) − 2 tR,alkane (analyte )
Where 2 tR (analyte) represents the absolute retention time in the
second dimension and 2 tR,alkane (analyte) is the retention time in
the second dimension within the alkane band (“0”).
To calculate reference retention indices of the PEGs in the sec-
ond dimension, PEG-2 I, a linear regression was performed by plot-
ting PEG-2 IPEGs versus 2 tR,E .
P EG−2 IPEG (n ) = O f f set + 10 × nPE (5)
Where ‘Offset’ refers to the number of PEG-2 I
units required to
(2) achieve an intercept of zero, and nPE is the number of polyethy-
lene units of the compound of interest.
Based on this, a calibration graph is plotted as linear regression
of PEG-2 I versus 2 tR,E with an intercept of 0, resulting in Eq. (6),
which was used to calculate retention indices of all compounds of
interest.
P EG−2 I = slope × 2 t tR, E (6)
After the initial calibration, Eqs (3), (4), and (6) were applied to
each compound of interest to calculate their secondary retention
index.
2.3. Instrument parameters
All analyses were performed on a Markes BenchTOF-Select mass
spectrometer (Llantrisant, UK) coupled to an Agilent 7890A GC
(3)
solve, Peterborough, UK) set to 4 s modulation periods. The column
set consisted of a non-polar, 5% diphenyl, column (30 m × 0.18 μm
i.d. × 0.18 μm film thickness) in the first dimension and a semi-
polar, 50% diphenyl, column (5 m × 0.25 μm i.d × 0.18 μm film
thickness) in the second dimension. Helium was used as carrier gas
with an average linear velocity of 4.0 cm s-1 . The injector was op-
erated at 250 °C in split mode with a 10:1 ratio and 1 μl of sample
was injected via Agilent G4567A (Palo Alto, CA) autosampler. The
oven operated with an initial temperature of 40 °C held for 2 min,
followed by a 4 °C/min ramp to a 320 °C and held for 5 min. The
MS transfer line and ion source were held at 250 °C. The electron
energy applied was 70 eV and the scanned mass range was 50-400
(4)
m/z in electron ionization mode.
In order to evaluate the robustness of the KLI system the oven
ramp (2 °C/min, 6 °C/min, and 8 °C/min) and modulation time (3
s) were adjusted one at a time from the above settings.

3
N. Boegelsack, C. Sandau, D.W. McMartin et al.
RI Data Preparation
GC: Step 1: Define data boundaries
KLI: Step 1: Define data boundaries
PEG: Step 1: Define data boundaries
Step 2: Extrapolate t2 PEGs
Step 3: Linear regression PEGs
Fig. 1. Workflow summarizing steps required to generate retention indices using conventional one-dimensional RI systems, the PEG RI system, and the proposed KLI system.
2.4. Data Analysis
Data was acquired and processed using the ChromSpace soft-
ware (V 1.5.1, Sepsolve, Peterborough, UK) and Microsoft Excel (Mi-
crosoft, Redmond, WA). A deconvolution algorithm was used for
integration, with a minimum ion count 300, minimum absolute
area and height of 10 0 0, and peak merging at 10% overlap.
The performance was compared between the proposed KLI
system, the PEG system, and the conventional van den Dool &
Kratz system by evaluating simplicity of use and the total per-
centage of area used. The area covered in both retention spaces
was calculated in accordance with the Cordero method including
wraparound peaks as outlined in Eq.s (7) and (8) [37]:
A=l×w
With l representing the length in minutes (first dimension) and w
representing the width in seconds (second dimension)
Acovered
%Aused = × 100
A potential
With Acovered describing the area pertaining to the RI system and
Apotential as the total area in the chromatogram as calculated by
Eq. (7) respectively.
The KLI system was then evaluated for its overall robustness
by comparing standard deviations associated with a linear range
of analyte concentration and alternative operational settings. For
comparison between units (minutes / seconds for absolute reten-
tion times and retention index units for retention indices), the co-
efficient of variation (CV), expressed as percentage, was calculated
in addition to the standard deviation.
Finally, the KLI system was applied to a variety of ignitable liq-
uids to test the accuracy of tR 2 assumptions and evaluate suit-
ability for classification under ASTM E1618 [4]. In addition, data
from a fire debris sample collected in the 2018 wildfire season
was used to investigate whether a direct comparison was possible
with ILRs analyzed under different conditions. Non-isothermal Ko-
vats (KI1 ) and Lee index (LI2 ) data from analysis of 2018 fire season
were chosen as they had been analyzed with a different secondary
column (smaller i.d. and film thickness), and would simulate the
potential changes in instrumental setup between suspect samples
and ignitable liquid comparison samples.
Journal of Chromatography A 1635 (2021) 461717
RI1 Calculation RI2 Calculation
Step 2: Apply to x values
Step 2: Apply KI1 to x values Step 3: Apply LI2 to y values
Step 4: Apply to x values Step 5: Define 0
(compounds of interest)
Step 6: Extrapolate new t2
Step 7: Apply regression
formula to y values
3. Results & Discussion
3.1. Retention index system workflow
The general workflow for conventional retention index systems
consists of two stages: data preparation, which is where data
boundaries are defined, and RI calculation. Extending this work-
flow to a GC×GC setup requires the additional normalization of
second dimension retention time (Fig. 1). A new workflow for
GC×GC is presented in Fig. 1 and compared with current 1D and
existing GC×GC RIs.
The first stage, data preparation, defines data boundaries re-
quired to ensure that results between different physical systems
will be comparable. Van den Dool and Kratz [35] noted in their
(7) research the importance of keeping a uniform temperature ramp.
They suggest that compounds eluting close to the initial and fi-
nal hold temperatures are affected by pressure changes associated
with the initiation and termination of temperature ramps. For their
RI calculation, any compound impacted by this effect is consid-
ered outside the data boundaries. While the same principles apply
(8) to the first dimension in GC×GC, data processing tools are read-
ily available to correct for these effects and to align data points
to their projected path. Defining data boundaries also requires de-
notation of which data points were acquired outside of the range
bracketed by standard compounds. Any compounds eluting before
the first and after the last calibration compound will require ex-
trapolation to obtain RI results. Table 1, which displays calibration
compounds used for the first dimension, denotes absolute reten-
tion times by tR 1 . The last calibration compound to elute is tria-
contane, and the RI of any compounds with a subsequent tR 1 must
be extrapolated from the temporal relationship of nonacosane and
triacontane. The same principle applies to any compounds exceed-
ing the absolute retention time of the latest calibration compound
in the second dimension, tR 2 (Tables 1 and 2).
An additional component of data preparation for multidimen-
sional RI systems is to define the zero-value in the second dimen-
sion, which is denoted by tR 2 corrected (tR 2 corr.; Tables 1 and
2). The KLI system defines a universal zero across the entire chro-
matogram area, which allows for a single-step data preparation
stage. The PEG system defines a separate zero value for each com-
pound and requires the extrapolation of an intermediate tR 2 cor-
rected relative to the bracketing n-alkane. In addition, a linear re-
gression calibration curve based on the PEGs is required as foun-
4
N. Boegelsack, C. Sandau, D.W. McMartin et al. Journal of Chromatography A 1635 (2021) 461717

Table 2
Second-dimension retention indices for calibration compounds using Lee indices (LI2 ) for the KLI
system and PEG indices (PI2 ) for the PEGs system.

Aromatic tR 1 (min) tR 2 (s) tR 2 corr. (s) KI1 LI2 Ring number

Toluene 7.5 3.9 1.4 778 100 1

Naphthalene 24.1 5.2 2.7 1218 200 2
Phenanthrene 43.6 1.9 3.4 1794 300 3
Chrysene 59.6 2.4 3.9 2495 400 4
Benzo(a)pyrene 67.5 3.1 4.6 2850 500 5

PEG tR 1 (min) tR 2 (s) tR 2 corr. (s) KI1 PI2 EG units

Ethylene glycol 6.1 4.6 2.1 726 11 1

Diethylene glycol 15.7 5.6 3.1 1000 21 2
Triethylene glycol 25.7 5.6 3.1 1261 31 3
Tetraethylene glycol 34.7 5.7 3.2 1533 41 4
Pentaethylene glycol 42.8 5.8 3.3 1819 51 5
Hexaethylene glycol 49.9 5.9 3.4 2109 61 6
Heptaethylene glycol 56.2 6 3.5 2400 71 7
Octaethylene glycol 61.8 6 3.5 2689 81 8
Nonaethylene glycol 66.8 6.1 3.6 2976 91 9
Decaethylene glycol 70.6 3.3 4.8 3200 101 10

dation for the calculation of the second-dimension retention index

500 Benzo(a)pyrene
for compounds of interest.
The approach for calculating RI1 , stage 2, is similar for all three
400 Chrysene
systems (Fig. 1). The non-isothermal Kovats equation is applied Phenanthrene
to convert retention times into system-independent constants, de-
300
noted as KI1 in Tables 1 and 2. Retention times for decaethylene Naphthalene
LI2

glycol and benzo(a)pyrene in Table 2 exceeded that of triacontane;

thus, their KI1 needed to be extrapolated.
RI2 calculation, the third stage in the workflow (Fig. 1), used the
Lee index and normalized compounds to calibration compounds
with various aromatic rings (Table 2), denoted as LI2 . Although
toluene had an added functional group, it was chosen as a cali-
bration compound representing monoaromatics. Benzene, based on
its structure, would have been more accurate but it exceeded the
data boundary by eluting before the first n-alkane and ahead of
the uniform temperature ramp. For the PEG system, the RI2 cal-
culation stage repeats steps from the data preparation stage, but
applies them to compounds of interest instead of the PEG calibra-
tion compounds. It is denoted as PI2 in Table 2 and relates results
to the corresponding number of ethylene glycol units.
The range of tR 2 and tR 2 corr. values in Table 2 show a large
difference between systems. The KLI system displays a 1.2 s differ-
ence between naphthalene and chrysene and even spacing across
the second dimension, whereas the PEG system has several over-
lapping retention times and a 0.5 s difference between diethylene
glycol and nonaethylene glycol. Previous work [34] showed more
even spacing across the second dimension for PEGs using a 12 s
modulation period as opposed to the 4 s modulation used in this
study. Longer modulation periods are commonly used in thermally
modulated GC×GC systems, improving separation in the second di-
mension and reducing wrap-around. In flow-modulated systems,
however, shorter modulation periods are required to retain a pres-
sure equilibrium. Longer modulation periods often result in instru-
mental errors, such as over- or under shooting the sample loop and
pressure inconsistencies, which affect peak shapes. An RI system
used on flow-modulated GC×GC systems must therefore be able to
perform under shorter modulation periods.
Area percent calculations assessing the percentage of total chro-
matographic area covered by each RI system was used to evalu-
ate the breadth of application of each system. The greater the area
of a chromatogram covered, the greater the unknown compounds
which can be normalized to a unitless constant for identification.
Within their respective data boundaries n-alkanes covered 9% of
the total chromatographic area, the PEG system covered 79%, and
the KLI system covered 86%. All systems can expand their range by
200
Toluene
100 Heptadecane Heptacosane
Heptane
0
500 1000 1500 2000 2500 3000
KI1
Fig. 2. KLI retention index for calibration compounds highlighting the relationship
between increasing carbon number (first dimension) and number of aromatic rings
(second dimension). Brackets highlight heptane, octane and triacontane as com-
pounds outside of linear alkane alignment.
adding calibration compounds with higher carbon number alkanes,
more ethylene glycol units, or aromatic rings as required, high-
lighting the overall flexibility in application for RI systems.
The KLI system required half the number of compounds to
cover a similar chromatographic area as the PEG system (see
Table 2). Compounds were readily available as certified reference
standards and are very stable. PEGs on the other hand are not so
readily available and are susceptible to photodegradation. In com-
bination with the application of a universal zero in the first stage,
the KLI workflow was inexpensive, quick to apply, and user-friendly
with its simple 3-step design.
3.2. Evaluation of performance
3.2.1. Comparison to predicted and published results
In the current set-up, separation in the first and second dimen-
sion is driven by boiling point and polarity, respectively (Fig. 2).
This is demonstrated in Fig. 2 by the progression of n-alkanes,
which have very regular boiling point increases due to their chem-
ical structure, with the succession from heptane to heptacosane
from the bottom left to the bottom right.
The separation in the second dimension in GC×GC represents
the difference in polarity. A regular increase in secondary column
interaction occurs with the addition of aromatic rings. This can
be seen with the progression from the light and non-polar com-
pounds in the bottom left (toluene) to heavy and increasingly polar

5
N. Boegelsack, C. Sandau, D.W. McMartin et al. Journal of Chromatography A 1635 (2021) 461717

Table 3 changes is smaller than the rounding factor, making this model ap-
Comparison of expected (expct.) and calculated (calc.) retention index results to
plicable in the second dimension.
structures of verification compounds.
The expected value for KI1 was determined by taking the boil-
KI1 LI2 ing point of each verification compound and comparing it against
Compound Structure
expct. calc. expct. calc. the boiling points of n-alkanes. Substituting retention times in the
non-isothermal Kovats index calculation with boiling points, de-
rived the expected RI value in Table 2. Light to medium range com-
Benzene 650 693 100 67 pounds (as defined for ILR analysis by ASTM E1618) are very close
and within rounding parameters to their predicted value, except
Naphthalene, 2-methyl- 1350 1332 200 185 for benzene. As benzene exceeded the data boundaries and was an
extrapolated result, it was excluded from the analysis for the pur-
Naphthalene, 1-methyl- 1350 1350 200 192 pose of this paper.
Heavy range compounds (anthracene and larger) display an in-
creasing discrepancy between their calculated result and their pre-
Acenaphthylene 1550 1497 250 250 dicted result, which is a known issue with n-alkane based reten-
tion indices [38]. As non-polar compounds, n-alkanes have a con-
Acenaphthene 1550 1530 250 250
sistent increase in boiling point with size, which is not affected by
surface interactions. Polar compounds have various surface interac-
Fluorene 1650 1636 250 233 tion effects influencing their boiling points, leading to larger com-
pounds having a boiling point range instead of a fixed point, since
Anthracene 1950 1862 300 283
larger (polar) surfaces allow more interaction effects to take place.
Another factor that may be leading to a consistently lower actual
Fluoranthene 2250 2155 350 340 retention index, as compared to the theoretical result, is the effect
of the average linear velocity on elution temperature of different
Pyrene 2500 2218 400 380 compound groups. As a theoretical approximation, linear velocity
is commonly considered stable in constant flow mode. However,
Benz(a)anthracene 2850 2584 400 414 fluctuations are observed in practice as the temperature program
increases the pressure and the flow is adjusted accordingly. This
Benzo(b)fluoranthene 3375 2912 450 429
becomes more obvious when directly comparing constant flow and
constant pressure configurations [38]. In this method, the inlet
pressure was regulated in constant flow mode.
Benzo(k)fluoranthene 3375 2924 450 429
RI results from other literature sources have several poten-
tial sources of variation. These include compound misidentifica-
tion, column attributes (length, inner diameter, film thickness,
and choice of stationary phase), and system operating parameters
compounds in the top right (benzo(a)pyrene) in Fig. 2. Heavy and [38,39,25]. Initial quality control of results in one-dimensional GC
non-polar compounds, such as heptacosane, remain at the lower is based on the existing RI-boiling point correlation [39,25]. Utiliz-
end of the y-axis. ing the same quality control approach to estimate how well this RI
Using calibration compounds, retention indices were calculated system performed, a regression analysis was applied to calculated
for verification compounds in the standard mixture. Calculated re- results, versus their boiling point in the first dimension (Fig. 3A)
tention indices for these compounds were compared against their and the number of aromatic rings present in the second dimen-
theoretical range based on boiling point and number of aromatic sion (Fig. 3B). The results are plotted in Fig. 3 with their respective
rings. An increase in expected column interaction, which fell be- 95% (dark grey shading) and 90% (light gray shading) upper and
tween aromatic rings, was generalized as an added value of 50 in lower confidence limits.
the expected LI2 . The regressions yielded r2 values of 0.970 for A and 0.988 for B,
Upon comparing structural information of the verification com- and standard errors of 21.1°C and 0.1 aromatic ring units, respec-
pounds to that of calibration compounds, verification compounds tively. Due to the very low standard error, less than 5 data points
fell into expected areas in the second dimension. Using the chem- lie just outside the 95% confidence interval. Using twice the stan-
ical structure, an expected LI2 was derived based on number of dard deviation as acceptance criteria, all compounds pass (except
aromatic rings. for benzene, which had been excluded from further analysis). This
For the majority of compounds, calculated values were com- demonstrates that the KLI system works well within a narrow error
parable with theoretical values (Table 3). However, compounds band. In addition, LI2 shows the capability to predict polarity be-
in the heavy range (as defined for ILR analysis by ASTM E1618) yond the number of aromatic rings, suggesting that further inves-
show more discrepancy between predicted and calculated re- tigation into the potential to differentiate other functional groups
sults, which is likely due to their surface polarity. The addi- may prove worthwhile.
tion of more aromatic rings means increased variety in their
surface shape (e.g. pyrene versus benz(a)anthracene), which has 3.2.1.1. Data boundaries and alignment feature. A visual indicator
a large impact on their surface polarity and therefore on for compounds exceeding physical data boundaries based on a uni-
where these compounds elute in the second dimension. Upon form temperature ramp can be seen in Fig. 2, where heptane, oc-
closer inspection, the largest observed discrepancy is 20 LI2 tane, and triacontane (highlighted in brackets) do not follow the
units (fluoranthene, benz(a)anthracene, benzo(b)fluoranthene and linear outline of remaining n-alkanes in the second dimension. In
benzo(k)fluoranthene), which is within rounding parameters as ex- these cases, RI results should be considered an approximation and
pected results were either considered full aromatic rings (100 LI2 be used with caution. This can present a more noticeable challenge
units) or “half” rings (50 LI2 units). Treating calculated results and in shorter runs. One of the ways to address this challenge is to ap-
predicted results the same, i.e. rounding to the nearest 50, they ply an alignment correction, which is a feature in the ChromSpace
align with their predicted LI2 since the effect of surface polarity software used for data analysis. For alignment, an algorithm is ap-

6
N. Boegelsack, C. Sandau, D.W. McMartin et al. Journal of Chromatography A 1635 (2021) 461717

600 5

500

Aromatic Ring Number

4
Boiling Point (°C)

400
3

300

2
200

100
A 1 B

0 0
500 1000 1500 2000 2500 3000 50 100 150 200 250 300 350 400 450
KI1 LI2

Fig. 3. KI1 -boiling point correlation (A) and LI2 -aromatic ring correlation (B) with their respective 95% (dark grey) and 90% (light grey) confidence limits.

as RIs are system independent, we postulate that changes should

500
not impact RI values. Compound concentration and solvent type
did not affect absolute retention times. Comparing concentration
400
curves of standard mixtures in DCM and methanol, absolute re-
tention times showed standard deviations < 0.1 minutes / seconds
300
in first and second dimension respectively. This was an expected
LI2

result, as these concentrations were within the linear operating

200
100
0
500 1000 1500 2000 2500
KI1
Fig. 4. Retention index for verification compounds (hollow dots) in standard mix-
ture normalized to calibration compounds (black dots) after applying the alignment
feature in ChromSpace.
plied to the chromatogram data after manually selecting target cor-
rection points (in this case n-alkanes). A best fit trend line is pro-
jected to these target correction points based on a selection of
settings, and the resulting equation is applied to the whole chro-
matogram with the aim of displaying more linear data in the sec-
ond dimension.
Fig. 4 shows the aromatic standard mixture, including both cal-
ibration compounds from Fig. 2 (black dots) and verification com-
pounds from Fig. 3 (hollow dots), after applying the alignment al-
gorithm. Although Fig. 4 shows an improvement in linearity of n-
alkanes, they do not depict a straight line, and alignment settings
need optimization for potential routine analysis. Looking at com-
pounds exceeding data boundaries, such as benzene (depicted by
the hollow dot in the bottom left corner of Fig. 4), the alignment
algorithm shifted its LI2 value closer to 100 than 50, providing a
more accurate LI2 result. This shows promise for the inclusion of
compounds exceeding data boundaries in routine analysis, and im-
proving RI results in the second dimension without the need to
change the run parameters. For the purpose of this study, it was
decided to continue without the use of the alignment feature to
avoid “overfitting” of the data when evaluating the performance of
this RI system.
3.2.2. Error analysis with system changes
Chromatographic system changes, such as column choice, and
inlet and oven settings, can affect absolute retention times, but
range of the instrument. Across the range of concentrations, each
compound was modulated into two to three splices, the ideal num-
ber of splices per compound. In GC×GC, it is widely accepted that
the number of splices per compound play an important role in the
3000 accuracy of the integration and quality of the data. When intro-
ducing the modulation period change, more wraparound was ob-
served for the 3 s modulation than in the 4 s modulation runs.
Although this required more manual data correction to account
for the wraparound, neither the number of splices per compound
nor the absolute retention times were affected. The standard de-
viations remained < 0.1 minutes / seconds in first and second
dimension.
Major changes to the number of splices per compound and
associated challenges were tested by changing the temperature
ramp. This drastically changed the pressure difference per minute
within the columns, one of the biggest sources for error in reten-
tion times. For absolute retention times, this meant up to 19 min-
utes difference in the first dimension, and up to 1.2 s difference in
the second dimension, between the shallowest and steepest ramp.
Due to these large differences in retention times from varying tem-
perature ramps, absolute errors were not meaningful. Therefore, a
scaled approach using CV% was used (Fig. 5) to evaluate differences
in standard deviation as they relate to the mean of their respective
group of results. The RI system reduced CVs in the first dimension
from 51% for absolute retention times to 1% for KI1 . In the second
dimension, CV% results showed a decrease from up to 47% for ab-
solute retention times, to as low as 2% for LI2 .
When using retention windows as part of compound identifica-
tion, the error range for the second dimension is ± 0.2 s for a 4
s modulation. Therefore, a 10% variance represents the limit of ac-
ceptability in the second dimension. A significant point to note in
Fig. 5 is that all LI2 CV% fall below 10%, thereby falling within the
limit of acceptability. This demonstrates that the RI system works
as intended. Using CV% for the error calculation provides a practi-
cal approach to apply error ranges to retention windows. They are
ready for application in automated target peak analysis for a vari-
ety of software packages and applications, making them immedi-
ately applicable to QA/QC processes.

7
N. Boegelsack, C. Sandau, D.W. McMartin et al. Journal of Chromatography A 1635 (2021) 461717

Table 4
ILR classification definitions and their respective translations into KLI coordinates based on ASTM E1618.

Condensed KLI
Class General Alkanes Cycloalkanes Aromatics Ring Aromatics Coordinates

Gasoline (A) Fresh C4 to C12 , aromatics in specific pattern P NS A P KI1 400-1300

LI2 30-250
Petroleum Homologous n-alkane series in Gaussian A P P M KI1 >400
Distillate (B) distribution of peaks predominant LI2 >30
Isoparaffinic Almost exclusively branched chain aliphatics A NS NS NS KI1 >400
Products (C) LI2 30-90
Aromatic Almost exclusively aromatics and condensed NS NS A M KI1 >400
Products (D) ring aromatics LI2 >80
Naphthenic- Mainly branched chain and cyclic alkanes A A NS NS KI1 >400
Paraffinic LI2 30-90
Products (E)
Normal Exclusively n-alkanes A NS NS NS KI1 >400
Alkane LI2 30-60
Products (F)
Oxygenated Major oxygenated compounds (alcohols, M M M NS KI1 400-1300
Solvents (G) esters, ketones) or mixture thereof with other (major <800)
compounds and products (toluene, xylene, LI2 30 - 190
distillate formulations) (major <100)
A: abundant, P: present, NS: not significant or absent, M: possible.

tR1 RI 1 tR2 RI 2 350

H
50% 300 M

40% 250 L
B
CV%

30% 200
LI2

20% 150 G
10% A D
100
0% C, E, F
50

0
500 1000 1500 2000 2500 3000
KI1

Fig. 5. Temperature ramp CV% comparison of absolute retention times, as repre-
sented by solid black and grey bars for first and second dimension respectively, and
KLI RI, as represented by striped black and dotted grey bars in first and second
dimension respectively.
Fig. 6. KLI contour map of ASTM E1618 ILR classes with arrows for light (L),
medium (M) and heavy (H) ranges (A - Gasoline, B - Petroleum Distillate, C -
Isoparaffinic Products, D – Aromatic Products, E – Naphthenic – Paraffinic Products,
F – Normal Alkane Products, G – Oxygenated Solvents).

between classes, highlighting the need for additional measures to

3.3. Application of retention time indices to ILR analysis
3.3.1. ILR mapping according to ASTM E1618
ASTM E1618 [4] prescribes categorization of detected ILRs into
defined classes within the light, medium, and heavy petroleum
range. As these ranges refer to their respective n-alkane carbon
number, which is equivalent to KI1 , the KLI system can be read-
ily applied to the current classification process of ILRs. Defining
the petroleum class can be further facilitated by incorporating LI2 .
For instance, n-alkane products and isoparaffinic products, such as
candle oils and aviation fuels, are expected to elute in the non-
aromatic to monoaromatic range, whereas petroleum distillates
are expected to contain polyaromatic compounds as well. Table 4
summarizes the definitions for the individual ASTM classifications
based on ASTM E1618, section 10 [4], and the presence and abun-
dance of compound classes including alkanes, cycloalkanes, aro-
matics, and condensed ring aromatics. The classification ‘Miscella-
neous / Other’ has not been included due to its broad definition.
Products which fall into more than one or none of the listed cate-
gories, such as synthetic mixtures containing only a few individual
compounds, are considered under Miscellaneous / Other.
The KLI coordinate contour map (Fig. 6) shows the areas that
the majority of compounds within each ILR classification are ex-
pected to elute in. As Table 4 and Fig. 6 show, there is overlap
distinguish between classes include identification of class-specific
target compounds and abundance ratios. For Gasoline, target com-
pounds are m-, p-, and o-ethyltoluene, 1,3,5-trimethyltoluene, and
1,2,4-trimethyltoluene in the aromatic range. In the condensed ring
aromatic range indan and methylindans are usually present, with
naphthalene and 1- and 2-methylnaphthalene commonly present
but possibly absent. For petroleum distillates, aromatics are nor-
mally always present in medium and heavy range in less abun-
dance than n-alkanes, but they can be significantly reduced or
entirely absent in de-aromatized products. Therefore, the individ-
ual compound distribution within compound classes must always
be comparable to a reference standard (e.g. gasoline) or known
formulation (e.g. isoparaffinic products). Abundance ratios are es-
pecially important when distinguishing normal alkane products,
isoparaffinic products and naphthenic-paraffinic products. While
normal alkane products almost exclusively contain n-alkanes, they
are not significant or absent in isoparaffinic products, which con-
sist almost exclusively branched chain aliphatics, and naphthenic-
paraffinic products, which contain a mixture of branched chain and
cyclic alkanes. Oxygenated solvents in a mixture can exhibit a char-
acteristic petroleum distillate alkane pattern. In these cases, iden-
tification is possible when the oxygenated compounds, typically
eluting before C8 , are at least one order of magnitude above other
matrix peaks.

8
N. Boegelsack, C. Sandau, D.W. McMartin et al. Journal of Chromatography A 1635 (2021) 461717

A B
350 350

300 300

250 250

200 200
LI2

LI2
150 150

100 100

50 50

0 0
500 1000 1500 2000 2500 3000 500 1000 1500 2000 2500 3000
KI1 KI1

Fig. 7. KLI contour map overlay on Gasoline (A) and Petroleum Distillate (B) in light (black crosses) and heavy (grey dots) range.

Fig. 7A shows a KLI map derived from the class definition of 350
gasoline in ASTM E1618 overlaid on a 21-petroleum station com-
300
posite gasoline sample (black dots). Petroleum distillates can occur
in light, medium, and heavy range, as represented in Fig. 7B by 250
lighter fluid (black crosses), and a 4-petroleum station composite
diesel sample (grey dots), for light and heavy ranges respectively. LI2 200
Fig. 7 shows that the compounds fall into their expected ranges
150
for different classes. While the mapping alone is not always suffi-
cient to distinguish ILR classes, it can highlight additional distin- 100
guishing characteristics at a glance.
50

3.3.2. Application to wildfire investigations
When investigating potential arson, fire debris samples on
scene must be collected and analyzed promptly not only due to
the volatile nature of ILRs but also to swiftly assist fire investiga-
tors with the case. However, determining a potential source of the
ILR can take time, and reference samples from a particular source
(e.g. gas station, suspect’s property etc.) for court comparison may
not be analyzed at the same time as the scene samples. In other
instances, investigations may point to the same arsonist, and sam-
ples would benefit from retrospective analysis to compare differ-
ent investigations. In rare circumstances, different labs may want
to compare analysis which cannot be done to this level using rou-
tine analysis.
With instrumental analysis, systematic changes regularly take
place over time, e.g. column and inlet maintenance, making di-
rect comparisons based on absolute retention times challenging.
Fire debris analysis, including ILR identification, classification and
source comparison, for wildfire investigation would therefore ben-
efit from the application of an RI system in several ways. This in-
cludes negating the effects of systematic changes, utilizing untar-
geted chromatography results for chemometric analyses, and estab-
lishing a standardized reference library.
As the application to neat ILRs was successful, the application
of the KLI system for ILR analysis to a scene sample encompassed
the next step in evaluating suitability. A previous comparison of a
fire scene sample from 2018 with the gasoline and diesel compos-
ite samples depicted in Fig. 7 based on absolute retention times
proved extremely challenging. Between these, a new column had
been installed with different internal diameter, which meant both
first and second dimension had shifted substantially. The scene
sample from 2018 was confirmed to be positive for ILR presence
and the ILR was identified as a mixture of diesel and gasoline.
Using the KLI system, Fig. 8 shows the overlay of a 2018 fire
scene sample with the ILR contour map.
0
500 1000 1500 2000 2500 3000
KI1
Fig. 8. Application of KLI ILR classification contour map to a fire scene sample.
Comparing a scene sample (Fig. 8) with neat ignitable liquids
(Fig. 7) shows the complexity of sample matrix and pyrolysis ef-
fects in the abundance of data points. Although petroleum distil-
late appears a better fit than gasoline upon first inspection, ad-
ditional means of compound identification, such as extracted ion
profiling and target compound analysis, confirmed the presence of
both gasoline and diesel in this sample.
The diversity and breadth of compounds in the wildfire sam-
ple (Fig. 8) shows the potential for GC×GC analysis to facilitate ILR
analysis. Comprehensive analysis of all compounds in ILRs, in ad-
dition to the current target compound analysis, brings future po-
tential to monitor within-class variation and source determination
based on marker compound identification within the currently un-
reported wealth of compounds. Using KLI RI values as part of a
data triangulation (RI coordinates, mass spectral data, and peak
abundance) in a reference library creates great potential for apply-
ing chemometrics to identify and compare ILRs more readily.
4. Conclusions
Building upon the existing workflow of one-dimensional GC
RI systems, we developed a simplified but robust RI system for
GC×GC. The proposed KLI system demonstrated a very straight-
forward yet successful approach. With a single injection of read-
ily available standard compounds, KLI RI can be calculated regard-
less of modulator restrictions as internal or external standards. The
composition of compounds allows a direct comparison to Kovats
and Lee indices in one-dimensional GC and pertains to applications
related to petroleum hydrocarbons. Overall, the KLI workflow was

9
N. Boegelsack, C. Sandau, D.W. McMartin et al.
inexpensive, quick to apply, and user-friendly with its simple 3-
step design.
The performance was comparable to, if not better than, exist-
ing RI systems, and showed very small error for correlation to pre-
dicted values. System changes did not affect results beyond the
limit of acceptability on standards or wildfire analysis samples, in-
dicating good robustness and suitability for the intended purpose.
Combining KLI RI and ILR classification as defined in ASTM
E1618, the application to wildfire analysis was successful. We de-
veloped an ILR classification contour map, which was used on neat
fuels and a fire scene sample to aid identification and classification
of ILRs present. The KLI standard composition allows for a wide
range of applications related to VOC analysis for easy standard-
ization and comparison of samples, as well as the development of
GC×GC-based databases.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
CRediT authorship contribution statement
Nadin Boegelsack: Conceptualization, Methodology, Investi-
gation, Formal analysis, Writing - original draft, Visualization.
Court Sandau: Conceptualization, Writing - review & editing.
Dena W. McMartin: Writing - review & editing, Funding acquisi-
tion. Jonathan M. Withey: Writing - review & editing, Funding ac-
quisition. Gwen O’Sullivan: Conceptualization, Methodology, Vali-
dation, Resources, Writing - review & editing, Supervision.
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