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Fractionation of Interfacial Material Reveals a Continuum of

Acidic Species That Contribute to Stable Emulsion Formation
† ‡,§ §,‡ § ,§,†,‡
Amy C. Clingenpeel, Steven M. Rowland, Yuri E. Corilo, Phoebe Zito, and Ryan P. Rodgers*
†
Department of Chemistry and Biochemistry, Florida State University, 95 Chieftain Way, Tallahassee, Florida 32306 United States
‡
Future Fuels Institute, Florida State University, 1800 East Paul Dirac Drive, Tallahassee, Florida 32310-4005 United States
§
National High Magnetic Field Laboratory, 1800 East Paul Dirac Drive, Tallahassee, Florida 32310-4005 United States

ABSTRACT: The acidic components of Athabasca bitumen interfacial material (IM) were isolated and subsequently
fractionated based on hydrophobicity by a modified aminopropyl silica (MAPS) method to determine whether low-molecular-
weight IM acids are preferentially ionized in negative-ion electrospray ionization (ESI (−)) and, thus, bias the compositional
information obtained by direct infusion (dilute and shoot) mass spectral analysis. Characterization by negative-ion electrospray
ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) revealed that MAPS fractionation of IM
acids extends the detection of high-m/z (>600-Da) IM compounds by 2-fold, yields an approximate 10-fold increase in the
number of assigned formulas, and exposes a continuum of acidic species that includes the first definitive identification of doubly
charged acids in interfacial material. Comparison of the heteroatom contents of singly and doubly charged O x species,
combined with the acid-targeted extraction procedure, strongly suggests that the chemical functionalities are similar for the two
ion types and are largely composed of mono- and dicarboxylic acids. Excitation emission matrix spectroscopy (EEMS) revealed
that the most hydrophobic IM fractions approach the size and aromaticity of bitumen asphaltenes, but despite the increase in
hydrophobicity, these asphaltene-like acids form the tightest emulsions, as revealed in simple bottle tests. Thus, the most
surface-active material from Athabasca bitumen comprises low-molecular-weight, acidic, resin-like species, as well as larger
(higher-molecular-weight) acidic asphaltene-like compounds.

1. INTRODUCTION characterized by negative-ion electrospray ionization Fourier

transform ion cyclotron resonance mass spectrometry [ESI (−) FT-
The production of heavy unconventional oils will continue to
1,2 ICR MS], low-molecular-weight NAP acids are preferen-tially
grow in the future. The Canadian oil sands constitute one ionized and mask the presence of higher-molecular-weight NAP
such unconventional crude oil source. Production of Canadian
bitumen crude oil is complicated by extremely high viscosity acids.11 To characterize the high-molecular-weight NAP acids, a
5
(>5 × 10 cP at 22 °C); thus, steam is often injected into the modified aminopropyl silica (MAPS) extraction technique was
3
well to reduce the viscosity prior to recovery. As a result, one developed to fractionate NAP acids based on hydrophobicity. 11 In
inherent problem in bitumen production is the formation of the current work, Athabasca bitumen IM, isolated from the whole
4 crude oil, was further separated by MAPS extraction to better
stable emulsions. Emulsions formed during bitumen recovery
determine the contributions of high-molecular-weight
are often desirable, as in the case of steam-assisted gravity
drainage (SAGD). However, these emulsions must be treated acids/asphaltenes to emulsion stability. We found that, similar to
prior to refining to avoid corrosion problems associated with NAP acids, low-molecular-weight IM acids are preferentially
5 ionized when the whole IM sample is analyzed. Fractionation was
entrained salts in production waters. An understanding of the
found to alleviate this limitation, with mass spectral analysis of
chemical composition of emulsion-stabilizing compounds,
referred to here as interfacial material (IM), is paramount to the IM MAPS fractions revealing the presence of both singly and
the treatment of emulsions prior to refining. doubly charged Ox and OxSy IM acids (up to 1200 Da). Excitation
Heavy crude oils, enriched in asphaltenes, often form emission matrix (EEM) spectra of the most hydrophobic IM
particularly stable emulsions. Asphaltenes are, therefore, fractions revealed that these fractions approach the size and
4,6−9 aromaticity of bitumen asphaltenes. Although the most surface-
believed to play the largest role in emulsion stability.
However, a previous systematic study of IMs isolated from active material was found to be a combination of both maltene and
Athabasca maltenes and asphaltenes revealed that both asphaltene compounds, emulsion stability tests revealed that the
fractions contribute to IM when analyzed separately, as most hydrophobic IM fractions (i.e., asphaltene-like) generate the
10 most stable emulsions. Thus, surface-active “classical” asphal-
well as in the analysis of the whole crude oil. Although
tenes appear to disproportionately contribute to the overall
solubility tests revealed that the IM isolated from the whole
emulsion stability.
crude oil was insoluble in n-heptane (asphaltenic), the most
abundant species contained high heteroatom content, but
were present at low double-bond equivalents (DBEs) (i.e.,
indicative of polar resin-like species). Received: February 17, 2017
Recently, Rowland et al. reported that, when naphthenic Revised: May 2, 2017
(NAP) acids from Athabasca bitumen are collectively

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2. METHODS
2. 1. Materials. High-performance-liquid-chromatography-
(HPLC-) grade dichloromethane (DCM), methanol (MeOH), n-
heptane, toluene, and water were obtained from J.T. Baker
(Phillipsburg, NJ). Chromatographic silica gel (Merck, 70−230 mesh,
type 60 Å) was used to isolate IM. Fractionation of IM was performed
on an Agilent Bond Elut NH 2 2g solid-phase extraction (SPE)
cartridge, which is described in detail below. Formic acid (MS grade,
∼98%; Sigma-Aldrich, St. Louis, MO) was used to elute acidic
species from the SPE cartridge. Tetramethylammonium hydroxide
(TMAH, 25 wt % in MeOH; Acros Organics, Fair Lawn, NJ) was
used to aid in the deprotonation of acids for ESI (−) analyses.
2.2. Interfacial Material Isolation. Silica gel was dried overnight
in an oven at ∼110 °C. After the silica gel had been dried, water
(HPLC-grade) was added to generate a water-saturated silica gel. IM
was isolated from 18.75 g of Athabasca bitumen with 75 g of the
water-saturated silica gel by the “wet silica” method, which was
12
described previously. After isolation, the IM was dried under N 2.
The IM was then reconstituted in DCM and vacuum-filtered with a
0.20 μ (25-mm-diameter, polypropylene back) Whatman membrane
filter (GE Healthcare Bio-Sciences, Pittsburgh, PA) to remove silica
that bled from the column during IM isolation. The IM was dried
under N2 after filtration.
2.3. MAPS Fractionation of IM. Isolated IM was further
separated with an aminopropyl silica (APS) SPE cartridge according
11
to the MAPS extraction method. The method for IM fractionation is
outlined in Figure 1, where elution solvent and percentage recovery
Figure 1. Separation scheme for MAPS fractionation of
Athabasca bitumen IM. Elution solvent and percentage recovery
are listed for all fractions.
are listed for all MAPS IM fractions. Before being used for the
separation, the SPE cartridge was conditioned with 12 mL of
DCM. Approximately 129.5 mg of isolated IM was dissolved in 1
mL of DCM and loaded dropwise onto the SPE cartridge. The IM
was allowed to equilibrate with the stationary phase for 15 min.
The nonpolar and moderately polar IM species were collected by
washing with approximately 12 mL of DCM and 12 mL of 50:50
(v/v) DCM/ MeOH, respectively. After collection of the
moderately polar compounds, the mobile phase was switched to a
reverse phase composition with MeOH and 70:30 (v/v)
MeOH/H2O. Formic acid was then added to the eluent, and acidic
species were eluted according to Figure 1.
2.4. Mass Spectrometry and Data Analysis. Athabasca bitumen
IM and fractionated IM samples MA 1−9) were diluted to final
−1
concentrations of 250−500 μg mL in 50:50 DCM/MeOH with
0.125−0.250% (v/v) TMAH solution. FT-ICR MS analyses were
performed on a custom-built 9.4-T FT-ICR mass spectrometer, which
is extensively described elsewhere.
13−16
Data acquisition was
B DOI: 10.1021/acs.energyfuels.7b00490
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performed with a modular ICR data station (PREDATOR). 17 Peak
picking was limited to mass spectral peaks with a signal
magnitude greater than six standard deviations (6σ) above the
root-mean-square (RMS) noise. Mass spectra were phase-
corrected and processed as described previously. 18−20 Molecular
formula assignments and data visualization were performed with
PetroOrg software.21 The mass spectral analysis of fractions MA
1−5 yielded high-quality data, whereas efforts to analyze fractions
MA 6−9 were unsuccessful (discussed later).
2.5. Excitation Emission Matrix Spectroscopy (EEMS). The
fractionated IM samples (MA 1−9), C5−7 bitumen asphaltenes, and
C7+ asphaltenes (isolated by Institute of Petroleum method IP 143/
90)were diluted to a final concentration of 2.5 μg mL−1 in DCM. The
spectra collected with a Horiba Scientific Aqualog benchtop
fluorometer were DCM-blank-subtracted and corrected for Rayleigh
and Raman scattering and instrument bias in excitation and emission
22
prior to correction for any inner filter effects. Validation was
performed with sealed water cell blanks collected prior to analysis to
test instrument stability using the Raman peak of water, at 350-nm
excitation and 340−420-nm emission. Weekly emission tests were also
collected. Excitation wavelengths ranged from 240 to 800 in 5-nm
increments, whereas emission wavelengths were collected every 2 nm
from 245 to 800 nm. Fluorescence intensity was normalized to
quinine sulfate units (QSUs).
23
3. RESULTS AND DISCUSSION
3.1. FT-ICR Mass Spectra. To determine whether low-
molecular-weight acids are preferentially ionized during the
analysis of whole Athabasca bitumen IM, the molecular weight
distribution of the whole IM sample was compared to the
distributions of fractionated IM samples MA 1−5 characterized by
ESI (−) FT-ICR MS (Figure 2). The mass spectral analysis
Figure 2. ESI (−) 9.4-T FT-ICR mass spectra of the collectively
isolated IM before MAPS fractionation and IM MAPS fractions
MA 1−5. Chemical noise peaks have been rescaled for visual
comparison of the spectra.
of fractions MA 6−9 was unsuccessful. These fractions were
believed (and later shown) to contain more asphaltenic
compounds and, therefore, aggregated at the concentrations
necessary for FT-ICR MS analysis. Sample results for
fractions MA 6−9 are discussed in a later section.
The mass spectrum of the whole IM sample extends to
∼850 Da and is centered at ∼425 Da. Approximately 8000
unique elemental formulas are assigned in the whole IM
spectrum. By comparison, there are approximately 76000
assignments
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collectively in the five IM MAPS acid fractions MA 1−5 (Figure
2). Upon first inspection of the mass spectra displayed in Figure 2,
MAPS fractionation of the IM sample does not appear to have
greatly extended the detection of high-molecular-weight IM
compounds. The mass spectral distribution of MAPS fractions
extends to the highest value in MA 4, which is ∼900 Da.
However, closer inspection of the mass spectra reveals that
fractions MA 3 and MA 4 display bimodal distributions. Figure 3
reveals that the first distribution in MA 3 is predominantly
Figure 3. ESI (−) 9.4-T FT-ICR mass spectrum of IM MAPS fraction
MA 3. The first distribution in MA 3 represents doubly charged IM
acids, and the enlarged inset above shows the 0.5-Da spacing between
13
the O4 and O4 C1 peaks (i.e., z = 2). The second distribution is
composed of singly charged acids, and the enlarged inset shows the 1-
Da spacing between the peaks. Doubly charged IM acids were also
detected in IM MAPS fractions MA 2, 4, and 5.
doubly charged acids, as demonstrated by the 0.5-Da
13
spacing between isolated O4 and O4 C1 peaks (i.e., z = 2)
whereas the second distribution (at higher m/z) contains
mostly singly charged acids and displays a 1-Da spacing
between isolated IM peaks.
Doubly charged acids were detected in MA fractions 2−5.
The onset of the doubly charged acids begins in MA 2,
accounting for 263 assignments, whereas doubly charged acids
account for a larger percentage and number of assignments in
MA fractions 3, 4, and 5 (9955, 10929, and 13301 doubly
charged acid species, respectively). Because the doubly
charged acids extend to ∼600 m/z in MA 5 and z = 2,
fractionation by the MAPS extraction method extends the
characterization of the isolated IM acids to ∼1200 Da.
Although these higher-molecular-weight (>850-Da) IM
species are present in the whole IM sample, they are clearly
masked by the presence of the low-molecular-weight IM acids
that ionize more efficiently. Thus, characterization of high-
molecular-weight IM acids requires fractionation.
3.2. Singly-Charged IM Acids. Analysis by ESI (−) FT-ICR
MS revealed that, although IM fractions MA 1−4 were separated
based on increasing hydrophobicity, the same heteroatom classes
were typically present in the four IM fractions, as well as in the
whole IM sample (Figure 4). Singly charged IM acids, in both the
whole IM and the MAPS fractions, were enriched in O x and OxSy
species, with O3S1 and O4 acids as the two most abundant
heteroatom classes. However, MAPS fractionation also revealed a
marked decrease
C DOI: 10.1021/acs.energyfuels.7b00490
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Figure 4. Heteroatom class distributions for the singly charged
acids in the collectively isolated IM sample and IM MAPS
fractions MA 1−4 determined by ESI (−) 9.4-T FT-ICR MS.
Fraction MA 5 is not shown because doubly charged acids were
detected throughout the entire distribution.
in relative abundance of the O 3S1 class and a concurrent
increase in O4 species with increasing hydrophobicity.
Figure 5 compares the compositional space coverage for
three commonly observed IM heteroatom classes by
isoabundance-contoured plots of double-bond equivalents
(DBEs, equal to the sum of the number of rings and the
number of double bonds to carbon) versus carbon number.
In every case, the compositional space coverage of fraction
MA 1, the most hydrophilic IM fraction, was comparable to
that of the whole IM sample. These results further support
the hypothesis that low-molecular-weight IM acids are
preferentially ionized and mask the presence of higher-
molecular-weight IM acids in the whole IM sample.
For the O2 class, fraction MA 1 contained predominately
DBE 7 and 10 carboxylic acids with up to ∼34 carbon atoms
(Figure 5). DBE 7 carboxylic acids can contain alicyclic rings
with a carboxylic functionality or one aromatic ring with
saturated alicyclic rings. The stepwise increase of 3 DBEs (to
equal DBE 10) is most likely due to the addition of an aromatic
ring. Although the carbon-number range of isolated O 2 IM
acids increased in each successive MAPS fraction, the most
abundant DBE range remained between 7 and 10 DBE.
However, the most abundant DBE range for fraction MA 4 was
DBE 3 and 4. Therefore, in higher molecular weight ranges
(MA 4), nonaromatic carboxylic acids between C35 and C55 are
most abundant. Similar trends in carbon-number range were
also observed in the O4 class (Figure 5, bottom). Here, the
most abundant DBE range for all isolated IM compounds
typically remained at 4−5. Future MS/MS experiments are
necessary to determine the structures of the species that make
up this heteroatom class.
With regard to the O3S1 acids, fractions MA 1 and MA 2
showed composition ranges similar to those observed in the
collectively isolated IM (Figure 5). Previous fragmentation results
for this class in the collectively isolated IM revealed fragments at
m/z 80, corresponding to O3S1 ions.24 Therefore, the most
abundant O3S1 species at DBE 4 in the collectively isolated IM
sample, fraction MA 1, and fraction MA 2 are believed to be a
combination of natural petroleum and anthropogenic sulfonates.
However, a shift in the compositional
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Figure 5. Heteroatom class-specific (O2, O3S1, and O4) DBE vs carbon number isoabundance color contour plots for the singly charged
acids observed in the collectively isolated IM and IM MAPS fractions MA 1−4.

space coverage of this class occurred in fractions MA 3 and MA only O ≥ 4, strongly suggesting that they were dicarboxylic
4. The most abundant O3S1 species in these fractions exhibited acids. OxSy (x ≥ 4) acids were also detected in low relative
abundance in fractions MA 2−5. Comparison of the
a bimodal distribution at DBE 4−5 and DBE 7. O3S1 species at isoabundance-contoured plots of DBE versus carbon number
DBE 4−5 are likely thiophenic carboxylic acids, whereas
species at DBE 7 are likely benzothiophene-containing (Figure 7) for the dicarboxylic (O4) acids revealed that the
carboxylic acids. Petroleum sulfonates are common surfactants
25,26
added to crude oils to alter wetting characteristics and
were likely added during the bitumen recovery process. These
surfactants are known to be water-soluble, and therefore, they
26
typically span low carbon-number ranges (<30). Therefore,
the change between MA 2 and MA 3 is consistent with a
change from petroleum sulfonates (MA 1 and 2) to thiophenic
acids (MA 3 and 4).
3.3. Doubly-Charged IM Acids. Figure 6 reveals that
doubly charged IM acids were enriched in species that contain

Figure 7. Heteroatom class-specific (O4 and O4S1) carbon

number vs DBE isoabundance color contour plots for the doubly
charged acids observed in IM MAPS fractions MA 2−5.

most abundant DBE compounds remained at DBE 4−6

Figure 6. Heteroatom class distributions for the doubly charged acids
in the IM MAPS fractions MA 2−5 determined by ESI (−) 9.4-T FT-
ICR MS.
D DOI: 10.1021/acs.energyfuels.7b00490
throughout the MAPS fractions despite the increase in carbon-
number range with each successive MAPS fraction. This
suggests that the O4 compounds from the IM were alicyclic
dicarboxylic acids. However, the O4S1 class displayed an
increase in both DBE and carbon-number range for the most
abundant compounds with MAPS fractionation. For fractions
MA 2−4, the most abundant species were at DBE 9 and 10.
However, for fraction MA 5, the most abundant species shifted
to DBE 13 and 14. This shift is commonly observed for
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Figure 8. EEMS fluorescence intensity contour plots for the IM MAPS fractions (MA 1−9), bitumen C5−7 asphaltenes, and C7+ asphaltenes.
thiophene-containing compounds and is likely indicative of
11
thiophenic dicarboxylic acids.
3.4. Orientation of IM Species at the Oil/Water
Interface. Although the molecular mechanisms behind
emulsion stability remain unknown, the identification of
doubly charged acids in the IM fractions introduces new ideas
as to how these species orient at the oil/water interface.
Because the charged head groups must be well separated from
one another to yield doubly charged gas-phase ions, two
orientations of these compounds at the interface can be
proposed. First, each acidic headgroup can ionize and partition
to the water interface. As the compounds partition to the water
interface, an alicyclic, aromatic, and/or alkyl backbone can
provide the steric hindrance necessary to prevent the dispersed
emulsion droplets from coalescing. Second, it is also possible
that only one headgroup partitions to the water interface,
whereas another headgroup interacts with other species (i.e.,
asphaltenes) in the crude oil to generate multiple molecular
layers around the interface to prevent droplet coalescence.
Therefore, it is possible that the most surface-active species
remain present at the oil/water interface whereas aging effects
the molecular rearrangement only in the layers surrounding the
most surface-active species. Future experiments will address
whether emulsion aging time affects the composition of the
most surface-active species.
3.5. Excitation Emission Matrix Spectroscopy (EEMS).
Because fractions MA 6−9 were hypothesized to aggregate at
the concentrations necessary for ESI (−) FT-ICR MS analyses
(500 μg/mL), as similar ionization behavior has been
27
previously documented, EEMS spectra were collected for all
IM MAPS fractions to determine the size and conjugation of
the IM fractions and confirm the presence/absence of an IM
acid continuum. EEMS was selected because samples can be
analyzed at concentrations much lower than the critical
−1 28
nanoaggregate concentration (CNAC) of ∼50 μg mL .
EEMS spectra were collected for a total of 11 samples
E DOI: 10.1021/acs.energyfuels.7b00490
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(fractions MA 1−9, bitumen C5−7 asphaltenes, and bitumen
C7+ asphaltenes). Spectra of asphaltene samples were
collected and were included in the data set to determine
whether fractions MA 6−9 approached the size and
conjugation similar to those of bitumen asphaltene species.
Figure 8 reveals that the IM MAPS acid fractions become larger
and more aromatic with each successive MAPS fraction. The
number of fused aromatic rings present in the sample dictates the
maximum emission wavelength: Benzene maximum emission
occurs at 280−290 nm, naphthalenes emit at 310−
320 nm, three- and four-ring aromatics emit at 340−380 nm,
and species containing five or more aromatic rings emit above
400 nm.29 Thus, larger aromatic compounds were present in the
higher IM MAPS acid fractions as the maximum emission
wavelengths increased with each successive MAPS fraction. The
C5−7 asphaltenes and the C7+ asphaltenes displayed maximum
emission wavelengths between 450 and 550 nm and excitation
wavelengths out to 550 nm. IM MAPS fractions MA 7−9 also
displayed similar maximum emission wavelengths between 450
and 550 nm and similar excitation wavelength ranges. Therefore,
these results suggest that the most hydrophobic IM MAPS
fractions (MA 7−9) are similar in aromaticity to the bitumen
asphaltenes, and the mass spectral results (lack thereof) for the
same fractions suggest that these species aggregate. Thus, the
most surface-active material from Athabasca bitumen is a
combination of low-molecular-weight, resin-like species and
higher-molecular-weight, asphaltene-like compounds that have
now been shown to contain both singly and doubly charged
acids.30 The importance of similar species has been suggested by
previous studies.31,32
3.6. Emulsion Stability Tests. To determine whether
differences in emulsion stability were present in the different
IM MAPS fractions, simple bottle tests were performed. In this
case, 2 mg of each IM MAPS fraction was dissolved in 2 mL
of a 1:1:1 DCM/n-heptane/toluene mixture and added to
separate vials with 2 mL of pH ∼11 water. The samples were
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then shaken by hand for 2 min to generate an emulsion, and the
emulsion stability was assessed over a 24-h period (Figure 9).
Figure 9. Emulsion stability tests. (Top) Two milligrams of each
sample was dissolved in 2 mL of a 1:1:1 DCM/n-heptane/toluene
mixture and added to 2 mL of pH ∼11 water. Vials were shaken
by hand, and the emulsions generated were assessed over a 24-h
period. The image shows the emulsions present at the end of the
24-h equilibration period. (Bottom) After the 24-h equilibration
period, each sample was centrifuged for 5 min at 4500g. The
image displays the emulsions present after centrifugation.
After the 24-h equilibration period, fractions MA 6−8 were
the most stable emulsions, with the smallest volumes of
free organic/aqueous phase (Figure 9, top). Each sample
was then centrifuged for 5 min at 4500g to assess which
emulsions were most stable (Figure 9, bottom). After
centrifugation, fractions MA 6−8 remained the most stable
emulsions. Thus, the higher-molecular-weight IM fractions
are believed to contribute most to the emulsion stability in
whole crude oil and whole IM samples.
3.7. Future Directions. The literature extensively stresses the
importance of asphaltenes to emulsion stability. However, the data
herein suggest that a continuum of molecules contribute to
emulsion stability and that these molecules span both maltenic
and asphaltenic compositional space. Simply put, the stabilizing
molecules are a subfraction of asphaltenes that display structural
motifs of both maltenic and asphaltenic species. It is their
chemical functionality (polarity) that determines their solubility
class and that was shown to be crucial for interfacial activity.
Thus, as suggested by Czarnecki and co-workers, the conventional
terminology regarding saturates, aromatics, resins, and
asphaltenes (SARA) impedes our understanding of the underlying
chemistry responsible for emulsion formation.28 It is the interplay
among chemical functionality, aromaticity, and type/extent of
alkyl substitution that ultimately determines interfacial activity,
and this cannot be captured and understood by coarsely attributing
it to one solubility class of petroleum. The difficulties associated
with the mass spectral characterization of fractions MA 6−9,
combined with their tendency to form the tightest emulsions and
the EEMS data revealing that they approach and then overlap with
those of asphaltenes, strongly suggest that these fractions can self-
assemble and exist as aggregates under the mass spectral analysis
conditions. If true, the data suggest that the enhanced emulsion
behavior of these fractions can be attributed to aggregate
formation, driven by an ever-increasing hydro-phobicity (aromatic
core size) and increasing heteroatom
F DOI: 10.1021/acs.energyfuels.7b00490
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content. Thus, the molecular-level data afforded by FT-ICR
MS combined with the fluorescence data strongly suggest that
the formation of the tightest emulsions involves a continuum
of surface-active species, combined with an overlapping
continu-um of increasingly aromatic species that exist as
stable aggregates, similar to the model proposed by Czarnecki
30,33
and co-workers, and support the presence and effects of
aggregated asphaltenes in interfacial material/at the oil/water
34
interface as proposed by Xu and co-workers. Future studies
will address emulsion aging affects to determine whether
molecular rearrangement occurs with the most surface-active
material or only in outer molecular layers.
4. CONCLUSIONS
Use of the MAPS extraction method extends the detection of
high-m/z, isolated IM compounds (from ∼850 to >1200 Da)
and yields an approximate 10-fold increase in the number of
elemental formula assignments (from ∼8000 to ∼76000) by
ESI (−) FT-ICR MS. These results indicate that differences in
ionization efficiency exist across the IM distribution and that,
when collectively analyzed, only the most ionizable species are
observed (low-molecular-weight, singly charged acids). MAPS
fractionation also provides the first identification of doubly
charged acids in the IM and reveals that isolated IM is enriched
in O3S1 species as well as doubly charged O 4 acids. EEMS
spectra of IM fractions revealed that the most hydrophobic
fractions (MA 7−9) approach the size of bitumen asphaltenes.
Thus, the results presented here demonstrate that the most
surface-active Athabasca bitumen compounds are extremely
polar and comprise both small, resin-like species and larger,
more aromatic asphaltene-like compounds.
■ AUTHOR INFORMATION
Corresponding Author
*Tel.: +1 850 644 2398. Fax: +1 850 644 1366. E-mail:
rodgers@magnet.fsu.edu.
ORCID
Ryan P. Rodgers: 0000-0003-1302-2850
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by NSF Division of Materials
Research (DMR-1157490), Florida State University, the
Florida State University Future Fuels Institute, and the
State of Florida. The authors also thank Robert Spencer,
Donald F. Smith, David C. Podgorski, Chad R. Weisbrod,
John P. Quinn, and Greg T. Blakney for their assistance in
instrumental maintenance, experimental design, data
analysis, and editorial contributions.
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G DOI: 10.1021/acs.energyfuels.7b00490
Energy Fuels XXXX, XXX, XXX−XXX