Environmental Pollution 305 (2022) 119284

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Comprehensive chemical characterization of gaseous I/SVOC emissions

from heavy-duty diesel vehicles using two-dimensional gas
chromatography time-of-flight mass spectrometry☆
Xiao He a, Xuan Zheng a, *, Yan You b, Shaojun Zhang c, d, Bin Zhao c, Xuan Wang e,
Guanghan Huang c, Ting Chen a, Yihuan Cao c, Liqiang He c, Xing Chang c, d, Shuxiao Wang c, d,
Ye Wu c, f
a
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, China
b
National Observation and Research Station of Coastal Ecological Environments in Macao, Macao Environmental Research Institute, Macau University of Science and
Technology, Macao SAR 999078, China
c
School of Environment, State Key Joint Laboratory of Environment Simulation and Pollution Control, Tsinghua University, Beijing 100084, China
d
State Environmental Protection Key Laboratory of Sources and Control of Air Pollution Complex, Beijing 100084, China
e
School of Energy and Environment, City University of Hong Kong, Hong Kong SAR, China
f
Beijing Laboratory of Environmental Frontiers Technologies, Beijing 100084, China

A R T I C L E I N F O A B S T R A C T

Keywords: Intermediate-volatility and semi-volatile organic compounds (I/SVOCs) are key precursors of secondary organic
GC × GC-ToF-MS aerosol (SOA). However, the comprehensive characterization of I/SVOCs has long been an analytical challenge.
I/SVOCs speciation Here, we develop a novel method of speciating and quantifying I/SVOCs using two-dimensional gas chroma­
HDDVs
tography time-of-flight mass spectrometry (GC × GC-ToF-MS) by constructing class-screening programs based on
Oxygenated-I/SVOCs
their characteristic fragments and mass spectrum patterns. Using this new approach, we then present a
SOA estimation
comprehensive analysis of gaseous I/SVOC emissions from heavy-duty diesel vehicles (HDDVs). Over three-
thousand compounds are identified and classified into twenty-one categories. The dominant compound groups
of I/SVCOs emitted by HDDVs are alkanes (including normal and branched alkanes, 37–66%), benzylic alcohols
(7–20%), alkenes (3–11%), cycloalkanes (3–9%), and benzylic ketones (1–4%). Oxygenated I/SVOCs (O–I/
SVOCs, e.g., benzylic alcohols and ketones) are first quantified and account for >20% of the total I/SVOC mass.
Advanced aftertreatment devices largely reduce the total I/SVOC emissions but increase the proportion of O–I/
SVOCs. With the speciation data, we successfully map the I/SVOCs into the two-dimensional volatility basis set
space, which facilitates a better estimation of SOA. As aging time goes by, approximate 45% difference between
the two scenarios after seven-day aging is observed, which confirms the significant impact of speciated I/SVOC
emission data on SOA prediction.

1. Introduction
Secondary organic aerosol (SOA) is a major component of atmo­
spheric fine particles, especially in urban environments (He et al., 2020;
Huang et al., 2014; Mancilla, Herckes, Fraser, & Mendoza, 2015).
Although great efforts have been made to better simulate SOA formation
in air quality models, there are still large discrepancies between model
results and field observations (Bloss et al., 2005; Jimenez et al., 2009).
Intermediate-volatility and semi-volatile organic compounds (I/SVOCs),
of which the effective saturation concentrations (C*) are in the range of
10− 1 to 106 μg m− 3, roughly corresponding to the volatility range of
C10–C32 n-alkanes, have been reported to be significant precursors of
SOA (Jimenez et al., 2009; Zhao et al., 2014). Chamber studies have
observed high SOA yields for representative I/SVOC species, such as
long chain alkanes, naphthalene, and alkyl-substituted naphthalenes,
and for multiple sources, such as biomass burning, cooking, biogenic
emissions, and mobile source emissions (Chan et al., 2009; Li et al.,
2017; Liu, Wang, Huang, Wang, & Chan, 2018; Palm et al., 2017; Presto

☆
This paper has been recommended for acceptance by Dr. Da Chen.
* Corresponding author.
E-mail address: x-zheng11@szu.edu.cn (X. Zheng).

https://doi.org/10.1016/j.envpol.2022.119284
Received 14 December 2021; Received in revised form 10 March 2022; Accepted 7 April 2022
Available online 15 April 2022
0269-7491/© 2022 Elsevier Ltd. All rights reserved.
X. He et al.
et al., 2009). Model performance in simulating SOA has been remark­
edly enhanced by incorporating IVOC emission data, although complete
interpretation has not achieved (Hodzic et al., 2010; Wu, Wang, Lu,
Shao, & Ling, 2019).
Nevertheless, the detailed characterization of I/SVOC emissions and
SOA formation is far from adequate. I/SVOCs are found to be largely
categorized as unresolved complex mixtures (UCMs) of coeluting com­
pounds that can hardly be separated by one-dimensional gas
chromatography-mass spectrometry (GC-MS) (Zhao et al., 2014). Coe­
luted compounds hinder the accurate quantification of I/SVOCs at the
molecular level. The species-level emission profiles of I/SVOCs typically
only report limited individual compounds such as polycyclic aromatic
hydrocarbons (PAHs), n-alkanes, and other molecular markers (Baalbaki
et al., 2018; Huang, Bohac, Chernyak, & Batterman, 2015; Liu et al.,
2010). More recently, the speciation of I/SVOCs has been extended to
i-alkanes, cyclic alkanes, and aromatics (Alam et al., 2018; Huo et al.,
2021; Lu, Zhao, & Robinson, 2018; Qi et al., 2019; Zhao et al., 2014;
Zhao et al., 2015). Nevertheless, the speciation of I/SVOC is still crude,
considering of un-speciated UCMs. One widely adopted approach to
quantify un-speciated UCMs is to use n-alkane as the metric to bin IVOCs
based on their volatility (or saturation concentration) and calculate the
concentration of I/SVOC mass in each bin (Zhao et al., 2014). Taking
n-alkanes as surrogates may induce large uncertainties because the
response factors of different compound categories vary dramatically and
replacing them with that of n-alkane would mask the real concentration.
In addition, the SOA yields of diverse compounds differ significantly,
and the semi-quantification method introduces aggregated uncertainty
to the SOA model results (Chacon-Madrid & Donahue, 2011; Chiappini
et al., 2019).
Multi-dimensional chromatographic technology has greatly
enhanced the separation capacity of complex mixtures. Comprehensive
two-dimensional gas chromatography (GC × GC) is noted for the
increased selectivity, peak capacity, and sensitivity due to the connec­
tion of two capillary columns with complementary stationary phases in
series (Tranchida, Franchina, Dugo, & Mondello, 2016). The combina­
tion of GC × GC and high-resolution mass spectrometry (e.g.,
time-of-flight mass spectrometry (ToF-MS)) provides a powerful tech­
nique that can help resolve the above challenges. Furthermore, in-depth
data processing of un-speciated UCMs distributed on the
two-dimensional chromatogram space screens out compound clusters of
I/SVOCs that possess similar chemical properties (Alam et al., 2018).
Heavy-duty diesel vehicles (HDDVs) are one of the major sources of
I/SVOCs, especially in urban environments (Dallmann et al., 2012; Li
et al., 2020; May et al., 2014). Strong evidences regarding the abundant
emissions of I/SVOCs and their subsequent high formation potentials of
both SOA and ozone have been reported (Chen et al., 2019; Li et al.,
2018). However, studies on the detailed speciation of I/SVOCs emitted
by HDDVs are rare and mostly conducted using GC-MS (Borillo et al.,
2018; May et al., 2013). Therefore, the detailed characterization of
I/SVOC emissions from HDDVs is inadequately reported. Further,
advanced aftertreatment technologies have been widely adopted in
modern diesel vehicles to comply with stringent emission standards. The
impact of aftertreatment technologies on regulated pollutants has been
reported by previous studies (Chirico et al., 2010; Gordon et al., 2014;
Zhang, Lou, Tan, Hu, & Li, 2019); however, how these aftertreatment
devices, especially diesel oxidation catalyst (DOC) and diesel particulate
filter (DPF), affect I/SVOC emissions is not well understood. For
example, the China VI emission standard (equivalent to Euro VI stan­
dard) is scheduled to be fully implemented nationwide (Zhang et al.,
2020), requiring the usage of DOC and DPF for almost all segments of
HDDVs. An improved understanding of I/SVOC emissions for HDDVs
using advanced aftertreatment devices can provide timely data to esti­
mate the impact from newly registered vehicles on air quality.
In this study, we use a two-dimensional gas chromatography time-of-
flight mass spectrometry (GC × GC ToF-MS) system to measure gaseous
I/SVOCs from HDDVs and establish a novel “three-step” approach to
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Environmental Pollution 305 (2022) 119284
speciate and quantify I/SVOCs comprehensively by a) calibrating with
authentic standards, b) constructing class-screening programs based on
their characteristic fragments and mass spectrum patterns, and c) for the
remaining unidentified peaks, constructing a data processing program to
iterate through all the known peaks and selecting the best surrogate for
individual unknown peaks. Twenty-one categories of compounds are
classified, many of which, to the best of our knowledge, are reported for
the first time (e.g., oxygenated compounds). The updated speciation of
gaseous I/SVOCs emitted by HDDVs would help provide a more accurate
estimation of SOA by incorporating them into air quality models in
future work.
2. Materials and methods
2.1. Test vehicles, cycles, sampling, and fuels
Measurements of I/SVOCs from HDDVs were conducted at the China
Automotive Technology & Research Center (CATARC) in Tianjin, a
national-level certified testing facility. Currently, the HDDVs complying
with China IV emission standard (equivalent to Euro IV standard) ac­
count for a major portion of the total HDDV fleet (China Mobile Source
Environment Management, 2019), and the latest released China VI
standard promotes the retrofitting of DPF and DOC. Based on this, three
in-use HDDVs were recruited in the measurement experiments (see
Table S1). One model year 2016 China IV HDDV (#1) was equipped
with a selective catalytic reduction (SCR) system. Two model year 2020
China VI HDDVs (#2 and #3) were equipped with SCR, DPF, and DOC
systems.
The HDDVs were tested on a chassis dynamometer (AIP-ECDM 72H/
2AXLE) following two driving cycles in succession: the cold-start China
heavy-duty commercial vehicle test cycle for heavy trucks (CHTC-HT)
and hot-start CHTC-HT test cycle. The exhausts were diluted in a con­
stant volume sampler (CVS, MEXA-7200DTR, Horiba) system with
ambient air filtered by high-efficiency particulate air filters. The average
temperature in the CVS system was 39.9 ± 0.9 ◦ C. Diluted diesel ex­
hausts in the CVS system were directed through a Teflon filter and into
two adsorbent tubes in series (Tenax TA, C1-AXXX-5003, Markes In­
ternational) where gaseous IVOCs and SVOCs were collected. Field
blank samples of background dilution air were collected with the same
protocol as real samples for each driving cycle. The emission factors
(EFs) of I/SVOCs reported hereafter are the sum of emissions from the
two Tenax TA tubes minus those from field blanks within respective
driving cycles. A more detailed description of dynamic sampling is
provided in the supporting information (S2). A systematic sampling
setup is shown in Fig. S1.
The CHTC-HT cycle was developed by the CATARC due to the good
representativeness of driving conditions for heavy-duty commercial
vehicles in China. All vehicles were preconditioned overnight prior to a
cold-start test. The speed trace and driving phase division for the CHTC-
HT cycle are plotted in Fig. S2. A full list of the experiments is sum­
marized in Table S2.
Market diesel fuels used for the chassis dynamometer experiments
complied with the China VI diesel fuel quality standard and were tested
separately. The total aromatic hydrocarbon content for HDDVs #1, #2,
and #3 was 23.6%, 22.1%, and 24.3%, respectively. PAHs are minor
constituents of diesel fuel, with a mass/mass ratio less than 3%. The
overall carbon content of the diesel fuels for HDDVs #1, #2, and #3 was
85.2%, 85.2%, and 85.4%, respectively, and the oxygen content was less
than 0.5%. The detailed fuel compositions are summarized in Table S3.
The carbon distribution of each diesel fuel is shown in Fig. S3.
2.2. Instrument analysis and peak assignment in two-dimensional gas
chromatography
Before analysis, each adsorbent tube was spiked with 2 μL internal
standard (IS) working solution to track the system matrix variation. The
X. He et al.
list of IS is provided in the supporting information (S1). The IS working
solution was blown into adsorbent tubes through a mild nitrogen flow
(CSLR, Markes International). Adsorbent tubes were then loaded onto a
thermal desorption autosampler (TD100-xr, Markes International),
where the tubes were heated to 315 ◦ C for 20 min (trap was held at
25 ◦ C). After tube desorption, the trap was heated to 330 ◦ C for 5 min
and purged onto the column in a split ratio of 8.7:1. During the injection,
the gas chromatography (GC, Agilent 7890B, Agilent Technologies)
oven temperature was maintained at 50 ◦ C, and the column flow was
1.3 mL min− 1. An Rxi-5ms capillary column (30 m × 0.25 mm × 0.25
μm, Restek) was used to separate the analytes as the first separation
column and an Rxi-17Sil MS (0.75 m × 0.25 mm × 0.25 μm, Restek)
capillary column as the secondary column.
An initial GC oven temperature of 50 ◦ C was held for 5 min and then
increased at 5 ◦ C•min− 1 to 300 ◦ C and held for 5 min. The temperature
of the secondary oven and modulator was offset by +5 ◦ C and +30 ◦ C,
respectively, relative to the GC oven temperature. The modulation
period was 4 s. The complete run time was approximately 3900 s. All
data collected were processed using LECO ChromaTOF software (LECO
Corporation).
For speciation and quantification of I/SVOCs, a “three-step”
approach was constructed. First, individual peaks were identified based
on the injection of authentic standards, elution sequences for homolog
series, built-in ToF-MS spectral libraries (mainlib and replib), and
representative functional group rearrangements. The uncertainty of
peak identification was proved to be low for peaks with a match possi­
bility threshold (forward match statistic) of 700 with respect to MS li­
braries; thus, the threshold for data processing was set to 650 (Worton
et al., 2017). The primary logics of selecting authentic standards are to
be well interspersed within the entire GC × GC chromatogram and to
comprise as many chemical categories as possible. The list of authentic
standards with the corresponding internal standards and retention times
is shown in Table S4. The calibration curves for all the authentic stan­
dards were well established (R2 ranging from 0.97 to 0.99), demon­
strating the robustness of this method.
Next, we tried to identify more peaks, for which no authentic stan­
dard was available, based on the fragmentation patterns and represen­
tative functional group rearrangements at 70 eV. To facilitate the
handling of excessive spectral data, scripting functions embedded in
ChromaTOF software are implemented, with the merit of only knowing
the formalities required. Programming expressions characterizing mass
spectral properties were defined for classification purposes. Computer
language for filtering target peaks in GC × GC chromatograms has been
discussed previously (Mohammed S. Alam et al., 2018; Alam,
Zeraati-Rezaei, Xu, & Harrison, 2019; Reichenbach, Kottapalli, Ni, &
Visvanathan, 2005), but the focuses were centered on hydrocarbons,
while oxygenated species were either not accounted for or lumped
together. To the best of our knowledge, this is the first study to provide a
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Environmental Pollution 305 (2022) 119284
comprehensive analysis of the classification of chromatographic peaks,
regardless of hydrocarbons or oxygenated chemical species. Taking
alkane as an example, the criteria are that the base mass fragments at 70
eV are m/z 43, 57, or 71 and that the ensuing fragment (of which the
intensity seconds to the prior one) is m/z 41, in conjunction with the 2nd
retention time longer than 0.5 s. The syntax for each category identifi­
cation is provided in the supporting information (S4). Basically, over
one-thousand compounds were filtered and classified into twenty-one
categories, accounting for over 40% of all the peaks eluted. A polygon
selection tool within ChromaTOF software was utilized to colorize and
locate the twenty-one categories, as shown in Fig. 1.
It is worth noting that half of the peaks still remained unidentified
(peak X). For peak X of which no authentic standards are available and
no mass spectrum patterns are extractable, we develop a data processing
program to iterate through all the known peaks and select the best
surrogate by minimizing the physical distance between X and the
coupled surrogate in the GC × GC chromatogram. We use surrogates to
semi-identify peak X assuming that they share similar chemical prop­
erties, regardless of the true structure layout. In effect, the assumption
stands from the perspective of atmospheric fate considering the adjacent
positions in the GC × GC chromatogram: they would undergo similar
aging processes once emitted into the atmosphere due to their compa­
rable volatility and polarity. The peak X is then empirically classified as
the surrogate category. Given the complex nature of I/SVOCs, we pro­
pose to use surrogates to semi-identify UCMs instead of simply binning
them on the basis of the 1st retention time (Zhao et al., 2014; Zhao et al.,
2015).
2.3. Emission factor calculation
The gaseous I/SVOC data are reported as fuel-based emission factors
(mg kg•fuel− 1) derived using the carbon mass balance approach:
( / )
ΔI SVOCs × 106
EF = × wC
Δ[CO2 ] × MC /MCO2 + Δ[CO] × MC /MCO
where EF is the emission factor of gaseous I/SVOCs emitted by diesel
vehicles (mg kg•fuel− 1); ΔI/SVOCs is the mass concentration of I/SVOCs
measured in the CVS system (mg), which is corrected for the background
contamination measured on the field blanks and column bleedings;
Δ[CO2 ] and Δ[CO] are the background-corrected CO2 and CO concen­
trations, respectively, expressed in units of carbon mass (mg); MCO2 ,
MCO , and MC are the molar weight of CO2, CO, and C atom; wC is the
mass fraction of carbon in the diesel fuel. We use EFs to describe the
averaged value of EF from the three duplicate tests for each vehicle
under each test cycle.
Fig. 1. A scatter plot of the chromatographic peaks of
diesel exhaust derived from the test ID 20201216-1
sample shown in the form of compound classifica­
tion. Over three-thousand peaks are identified in this
sample and labeled markers indicate compounds that
are classified into twenty-one categories. Bleedings
(green triangle) underneath alkane peaks are the
thermal breakdown products of the column stationary
phase, and they are not included in the following
discussion. (For interpretation of the references to
color in this figure legend, the reader is referred to the
Web version of this article.)
X. He et al. Environmental Pollution 305 (2022) 119284

3. Results and discussion
3.1. Chemical speciation and emission factors of diesel I/SVOCs
Over three-thousand compounds are identified, quantified, and
aggregated into twenty-one groups after three-step data treatment pro­
cesses. The few top relative contributors to the total identified EFs, from
high to low, are alkanes (including normal (n-) and branched (i-) al­
kanes, 37–66%), benzylic alcohols (7–20%), aliphatic alcohols (3–14%),
alkenes (3–11%), cycloalkanes (3–9%), benzylic ketones (1–4%), and C3
alkyl-substituted benzenes (0–12%). They amount to over 85% of the
total I/SVOC emissions.
The most abundant class is alkanes (including n-/i-alkanes), ac­
counting for 44–66% for CHTC-HT cold-start and 37–57% for CHTC-HT
hot-start driving cycles. Alkanes are mostly detected in the volatility
range of log10C* = 1 to 2 and 4 to 5 μg m− 3, as highlighted in light gray
shades in Fig. 2. The EFs of alkanes are 12.4 ± 0.7, 3.7 ± 0.04, and 1.4 ±
0.02 g kg•fuel− 1 for HDDVs #1, #2, and #3, respectively, with the
dominant few bins (e.g., log10C* = 5, 1, 2, and − 2 μg m− 3) contributing
over 50% of the aggregated alkanes. The results are comparable to the
mass concentration of alkanes (n-/i-alkanes) identified in diesel fuel
reported by Alam et al. (2018). Branched alkanes, which are estimated
by the total alkane mass subtracting the mass of n-alkanes, account for
approximately 90% of all the detected alkanes, while n-alkanes account
for only 10%. Based on previous reported data, a dimethyl branched
isomer belonging to the Cn+1 alkane could have the same volatility range
as a normal Cn alkane. The dimethyl structure can be shifted by ~100
delta-Kovats (~1 carbon number), whereas the trimethyl and
tetra-methyl structures can be shifted by ~150 and ~200 delta-Kovats,
respectively (Alam, Stark, & Harrison, 2016; Isaacman et al., 2012). This
may lead to an overestimation of n-alkanes with traditional
one-dimensional GC-MS but is not a concern for GC × GC because Cn
n-alkanes have different 2nd retention time in comparison with their
Cn+1 dimethyl-alkane homologs.
Oxygenated compounds are also detected at observable abundance,
especially for benzylic alcohols (7–20%), aliphatic alcohols (3–14%),
and benzylic ketones (1–4%). Acids are difficult to detect by GC-MS
without prior derivatization and may therefore be underestimated.
Less than 1% of acids are detected in the diesel exhaust samples. A more
detailed discussion of oxygenated I/SVOCs (O–I/SVOCs) is presented in
the section after next.
Alkenes account for 3–11% of the total identified I/SVOC mass,
whereas cycloalkanes account for 3–9%. Alkenes and cycloalkanes are
nonnegligible constituents of HDDVs-emitted hydrocarbons, although
their proportions are much lower than those of alkanes. The EFs of al­
kenes are 0.60 ± 0.02, 0.39 ± 0.001, and 0.24 ± 0.001 g kg•fuel− 1 for
HDDVs #1, #2, and #3, respectively, whereas those EFs for cyclo­
alkanes are 0.48 ± 0.03, 0.32, and 0.23 g kg•fuel− 1. C3 alkyl-substituted
benzenes contribute 1–12% to the total I/SVOCs, followed by C2 alkyl-
substituted benzenes (0–2%).
PAHs are minor fractions of the identified I/SVOCs, dominated by 3-
ring PAHs (2–8%) with and without alkyl substitutions. Other cate­
gories, including mono-aromatic compounds (benzene with C2–C6 alkyl
substitutions), 2-ring and 4-ring PAHs, and hopanes, account for less
than 1% of the total identified I/SVOCs. At current stage, this study
focuses on more abundant species. A detailed mass distribution of the
twenty-one categories is listed in Table S5.
The volatility distribution of I/SVOCs differs greatly among the
twenty-one chemical groups. For example, peak alkane concentrations
are observed between the range of log10C* = 1 to 2 μg m− 3, while
benzylic alcohols are mostly detected in relatively more volatile ranges:
log10C* = 4 to 5 μg m− 3 in this case. The number of compound groups
decreases substantially as the volatility decreases. Alkanes and aliphatic
alcohols and ethers are routinely measured, and aliphatic ketones and
esters are occasionally measured in volatility bins with log10C* ≤ 1.

Fig. 2. EFs of I/SVOCs under the CHTC-

HT cold-start driving cycle. #1 refers to
the China IV HDDV equipped with a
SCR system and #2 and #3 denote the
two China VI HDDVs equipped with
SCR, DPF, and DOC systems. Different
colored bars represent different com­
pound categories, as illustrated in the
above figure. Two emission peaks are
observed in the volatility range of
log10C* = 1 to 2 and 4 to 5 μg m− 3, as
highlighted in gray shades. O–I/SVOCs
are placed at the top position of each
column and highlighted with framed
color bars (cf. frameless color bars for
non-oxygenated species) and orange
background in the legend. Two distinct
compound categories before and after
log10C* = 3 μg m− 3 may manifest two
forms of oxygenated compounds. Circes
represent the mass fractions of O–I/
SVOCs, which are divided into two
major groups: high-volatility O–I/
SVOCs in the volatility range of log10C*
= 4 to 8 μg m− 3 (Group A, red circle)
and low-volatility O–I/SVOCs in the
volatility range of log10C* = − 2 to 3 μg
m− 3 (Group B, blue circle). The size of
each circle is proportional to the mass
fraction (scaling factor = 30) to intui­
tively show the mass distribution of O–I/SVOCs. The corresponding results for the hot-start driving cycle are shown in Fig. S4. The fraction of data that are
analytically resolved are 1.8–4% for step 1 and 53.9–65.8% for step 2 and fraction of mathematically reconstructed chromatographic peaks is 32.3–42.0%. (For
interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)

4
X. He et al.
3.2. Comparison with previous studies
Very few studies have reported I/SVOCs emitted from diesel exhaust,
and we find two relevant papers reporting IVOC EFs although the
driving cycles, vehicle engines, and aftertreatment differed (Alam et al.,
2019; Zhao et al., 2015). Generally, the EFs of I/SVOCs computed in this
work exhibit commensurate magnitude with the referred ones except
one test that was conducted under CHTC-HT cold-start driving cycle
without DPF and DOC devices. The EFs reported in this study spread
over a wider range (0.038–18.9 g kg•fuel− 1) than those reported by
Zhao et al. (2015) (0.017–5.3 g kg•fuel− 1), with various driving cycles
and aftertreatment devices. The EFs reported by Alam et al. (2019) were
derived from a light-duty diesel engine under steady-state conditions;
thus, a much lower value is expected (0.027–0.16 g kg•fuel− 1).
Utilizing the new approach, we have successfully resolved bulk I/
SVOCs into different compound categories with extractable rules. No
previous studies have speciated gaseous I/SVOC emissions at this
detailed and we clearly demonstrate the advancement of this innovative
approach for comprehensive analysis of I/SVOCs, from two significant
perspectives. First and the most important of all, the dominant fraction
of I/SVOCs, UCMs, is characterized explicitly and represented by
different compound categories, e.g., alkanes, monoaromatic com­
pounds, PAHs, and oxygenated compound groups, etc. Alkane accounts
for a major part of the total I/SVOC mass, which is consistent with
previous findings. However, the diversity of compound categories in­
dicates the intrinsic chemical complexity. In comparison, the UCMs
were sketchily split into speciated IVOCs, un-speciated branched alkane,
and un-speciated cyclic compounds in Zhao et al. (2015), leaving the
dominant fraction un-speciated (Alam et al., 2019). The diversity of the
compound category implies numerous evolution pathways of I/SVOCs
once emitted into the atmosphere and the speciated emission data is of
great benefits for better portray of atmospheric chemistry and SOA
estimation.
An in-depth discussion on SOA prediction using speciated emission
data is given in the final section and a significant SOA concentration
discrepancy is observed with and without speciation data. Second, O–I/
SVOCs are explored comprehensively. Alam et al. (2019) made an
attempt at speciating I/SVOCs and reported the EFs of several hydro­
carbon species. Oxygenated compounds were not included. Neverthe­
less, speciated O–I/SVOCs (e.g., acids, aliphatic alcohols and ethers,
aliphatic ketones and esters, benzylic ketones and esters, and phenols
and benzylic alcohols) are resolved and account for a significant portion
of the total I/SVOC mass. Vehicle emission has long been regarded as
non-oxidized ( Li et al., 2019). However, the finding that over 20% of
diesel emitted organic mass contains oxygen content suggests diesel
emitted organic aerosol (OA) is not restricted to hydrocarbons. The
discrepancy between our emission data and Alam et al. (2019) is
explainable, and the overall high comparability of EF data in this work
with the referred studies suggests the robustness of the analytical
protocol.
3.3. The comparison between cold and hot starts and the effectiveness of
aftertreatment technologies on I/SVOC emissions
Fig. 2 and Fig. S4 illustrate the volatility aggregated EF of I/SVOCs
from the three HDDVs under CHTC-HT cold and hot starts. The overall
EFs of I/SVOCs under CHTC-HT cold-start (CHTC-HT hot-start) driving
cycle are 18.9 (1.9), 8.4 (0.66), and 3.3 (0.04) g kg•fuel− 1 for HDDVs
#1, #2, and #3, respectively. Dramatic emission drops from cold-start to
hot-start are observed: the ratios are 90.0% for vehicle #1, 92.2% for the
vehicle #2, and 98.8% for vehicle #3. However, we found that the
volatility distributions of I/SVOCs between cold-start and hot-start do
not vary much. For example, the emission distribution of cold-start and
hot-start cycles both peak in log10C* = 1 to 2 and 4 to 5 μg m− 3 bins. The
transition of dominant O–I/SVOCs (high-volatility versus low-volatility)
in the two driving cycles lies in log10C* = 3 and log10C* = 4.
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Environmental Pollution 305 (2022) 119284
Consequently, further discussion on O–I/SVOCs and its implication on
SOA prediction are based on the CHTC-HT cold-start driving cycle unless
otherwise stated.
Fig. 3 compares the EFs of I/SVOCs derived from (DOC + DPF) ve­
hicles (#2 and #3) and non-(DOC + DPF) vehicle (#1) and from CHTC-
HT cold and hot starts. As expected, the installation of DOC and DPF
results in remarkable emission reduction, regardless of the driving cycles
or engine working conditions. Although there is vehicle-to-vehicle
variability within a given emission standard (e.g., vehicles #2 and
#3), a distinct amelioration trend is observed, with I/SVOC mass
reduction ratios of 55–83% and 65–98% for CHTC-HT cold-start and
CHTC-HT hot-start driving cycles, respectively. In terms of the mass
contribution of different categories, that of alkanes drops from 66% for
non-(DOC + DPF) vehicles to 44% for (DOC + DPF) vehicles. The shift in
the relative amounts of alkanes versus oxygenated I/SVOCs confirms the
effectiveness of DOC, which oxidizes certain constituents of the vehicle
exhaust. In contrast, the mass contributions of monoaromatic com­
pounds plus PAHs and the oxygenated species increased from 4.4% to
20% and 23% to 27%, respectively (Fig. 3).
3.4. Oxygenated I/SVOCs (O–I/SVOCs)
The oxygenated compounds, which are the combustion products of
diesel fuels (Alam et al., 2019), are resolved and quantified systemati­
cally for the first time in this work. The mass contributions of O–I/SVOCs
over the entire volatility range are shown in Fig. 2, and the overall
contribution of O–I/SVOCs to the total mass is shown in Fig. 3. The EFs
of O–I/SVOCs are 4.4, 2.3, and 0.67 g kg•fuel− 1 for HDDVs #1, #2, and
#3, respectively. O–I/SVOCs account for less than 1%–51% of the total
I/SVOCs depending on volatility bins and high loadings of O–I/SVOCs
distribute in the volatility range of log10C* = 4 to 6 μg m− 3, as shown in
Fig. 2. O–I/SVOCs overall present 23%, 27%, and 20% of the total
I/SVOCs for vehicles #1, #2, and #3, respectively.
We observe two distinct patterns and divide the identified oxygen­
ated compounds into two main groups: high-volatility O–I/SVOCs
(indicated as red circles in Fig. 2) are mostly detected in the compara­
tively volatile range of log10C* = 4 to 8 μg m− 3; low-volatility O–I/
SVOCs (indicated as blue circles in Fig. 2) are mostly detected in the
comparatively less volatile range of log10C* = − 2 to 3 μg m− 3. In terms
of speciation, the former group comprises aliphatic ketones/esters,
benzylic ketones, and phenols/benzylic alcohols; the latter group is
predominantly composed of aliphatic alcohols and ethers. Considering
the volatility distribution, high-volatility O–I/SVOCs are prone to
partition to the gas phase and exhibit higher chemical reactivity. For
example, the representative phenol benzylic alcohols are phenols con­
nected with multiple functional groups, which contribute to SOA for­
mation significantly in both gas-phase and aqueous-phase (George et al.,
2015; Yee et al., 2013). Low-volatility O–S/IVOCs are prone to partition
to the particle phase and may be a significant portion of primary aerosol
once further condensed. Combining the classification and volatility, we
may assume that low-volatility O–S/IVOCs include aliphatic alcohols
with long-chain carbon skeleton or polymers of short-chain aliphatic
alcohols. Few studies have focused on the O–I/SVOCs either due to the
deficiency of separation technologies or the crude classification of
organic compounds. By using a state-of-the-art GC × GC-ToF-MS tech­
nique and constructing two sets of compound-screening functions, we
successfully resolved O–I/SVOCs.
Compared with non-functionalized hydrocarbons, oxidized com­
pounds with the same vapor pressure tend to have lower SOA yields
(Chacon-Madrid & Donahue, 2011; Donahue, Epstein, Pandis, & Rob­
inson, 2011; Ziemann, 2011). However, the evolution of specific groups
in the atmosphere is complex and dynamic. On the one hand, func­
tionalization adds oxygen atoms to the carbon backbone (thus
increasing the O:C ratio), reduces the molecule’s vapor pressure, and
promotes molecule partitioning into the particle phase (Chacon-Madrid
& Donahue, 2011). On the other hand, the oxidized molecules are
X. He et al.
Fig. 3. The relative contributions of each compound category to the total I/SVOC EFs derived from vehicles #1 (non-(DOC + DPF), inner circle), #2 (DOC + DPF,
middle circle), and #3 (DOC + DPF, outer circle) under (a) CHTC-HT cold-start and (b) CHTC-HT hot-start driving cycles.
susceptible to fragmentation (carbon-carbon bond cleavage) at the
functionalized position, which makes the products more volatile and
likely to partition to the gas phase, resulting in a lower SOA yield. For
example, the ozonolysis of β-caryophyllene in the intra-annular car­
bon-carbon double bond results in two aldehyde groups with sufficiently
low vapor pressure and facilitates the product to partition to the particle
phase (Nguyen et al., 2009; Winterhalter et al., 2009). In contrast,
ozonolysis of the alkene double bond breaks the molecular bond and
forms two carboxyl groups (Chiappini et al., 2019). To summarize,
oxidized compounds are still considerable SOA sources, although they
are less effective than alkanes with similar vapor pressures. With regard
to the formation of SOA, vapor pressure alone is not enough to predict
the formation potential preciously. What matters is the functionality of
the moiety: n-alkanes tend to have the highest yields, followed by
n-ketones, and n-aldehydes have the lowest SOA yield (Chacon-Madrid
& Donahue, 2011).
3.5. Implication of speciated I/SVOCs on SOA prediction
The contribution of diesel vehicle emissions to SOA formation is
complex. Previous studies reporting SOA formation from diesel exhaust
were primarily based on laboratory experiments (Chirico et al., 2010;
Eluri, Cappa, Friedman, Farmer, & Jathar, 2018; Tkacik et al., 2014;
Woody et al., 2016). Undoubtedly, the incorporation of greater details
on emission profiles would likely better predict SOA formation from
diesel vehicles. In this work, over three-thousand organic compounds
are identified within one test cycle in gaseous I/SVOCs. The number of
compounds would be even higher if we include those detected in the
VOC range and in the particle phase (i.e., after analyzing the samples
collected by Summa canisters and quartz filters). Tracking the evolution
of individual compounds in the atmosphere is impractical. The great
complexity of I/SVOCs could be simplified by masking individual,
unique molecular properties and replacing them with bulk average
properties. Previous models were based on volatility bins to describe the
SOA formation potential, and mapping the emission factors of organics
from gasoline and diesel vehicles into the one-dimensional volatility
basis set (VBS) was already discussed in Lu et al. (2018) and Woody
et al., 2016. The next generation of models calls for more comprehensive
emission data, including speciation information and volatility distribu­
tion, as provided in this work. The two-dimensional VBS (2D-VBS) is a
case in point.
The 2D-VBS, which lumps organics based on saturation mass con­
centration (C0, in μg m− 3) and the O:C ratio, was developed by Donahue
et al. (2011) to address the volatility, mixing thermodynamics, and
chemical evolution of organic aerosol. The calculation of saturation
mass concentration is presented in the supporting information (S5). We
attempt to map the EFs of I/SVOCs from HDDVs into the 2D-VBS space.
6
Environmental Pollution 305 (2022) 119284
The absolute value of I/SVOC EFs distributed in each volatility and O:C
range is summarized in Table 1 and visualized in Fig. 4a, and the mass
fractions are shown in Table S7. Fragmentations that add functionalities
to the precursors would contribute to SOA formation. It has been
confirmed that the fragmentation ratios for lumped species increase
dramatically with increasing O:C (Donahue et al., 2012; Kroll et al.,
2009). An empirical estimation of the fragmentation ratio can be
described as (O:C)1/4, generating a fragmentation ratio of 56.2% for O:C
= 0.1 and 79.5% for O:C = 0.4 (Zhao et al., 2017).
The speciated I/SVOC emission data are incorporated into the 2D-
VBS framework according to the volatility and O:C of individual spe­
cies in comparison with the un-speciated emission data (assuming O:C
= 0 for all the peaks). The modeled OA concentration between the two
approaches is shown in Fig. 4b. The parameterization of the 2D-VBS
follows Donahue et al. (2012). Basically, the OH radical concentration
was estimated to be 3 × 10− 11 cm3 molec− 1 s− 1 and the heterogenous
reaction with OH radical was five times slower than the gas-phase OH
uptake. In general, OA concentration incorporating speciated emission
data is systematically lower than that using un-speciated data. The result
is consistent with previous findings that the SOA yields of alkane group
are higher than those of oxidized components (Chacon-Madrid &
Donahue, 2011; Donahue et al., 2011; Ziemann, 2011). The introduction
of O:C dimension corrects the biased OA concentration originated from
the lack of oxygenation information. As aging time goes by, the differ­
ence gradually increases to approximate 45% after seven-day aging,
which confirms the significant impact of speciated I/SVOC emission
data on SOA prediction. Over 20% (mass fraction) of I/SVOCs charac­
terized in this study are distributed into bins with O:C ≥ 0, and addi­
tional high O:C (≥ 1.2) compound clusters are occasionally found in
more volatile ranges (i.e., carbon number of n-alkane ≤ 10). In addition,
the overall oxidation state of diesel-emitted I/SVOCs is relatively low
(over 90% (mass fraction) of I/SVOCs having an O:C ratio smaller than
0.4) in comparison with other sources, e.g., domestic fuel (Stewart et al.,
2021). This means that diesel emitted I/SVOCs are mostly in the early
oxidation stage. As previously stated, the SOA yield of alkanes exceeds
that of all the other species with the same volatility, and the SOA yields
for alkanes and alkenes are at commensurate magnitudes. The func­
tionality of carbon backbones adds chemical reactivity and facilitates
molecule fragmentation. From these two perspectives, it is deduced that
the SOA formation from HDDVs is crucial.
4. Conclusions
In this study, we have conducted a chassis dynamometer test and
collected the gaseous I/SVOCs from three in-use HDDVs with/without
aftertreatment devices. We establish a laboratory-based analytical
approach using GC × GC-ToF-MS to measure the gaseous I/SVOCs and
X. He et al. Environmental Pollution 305 (2022) 119284

Table 1
The distribution of I/SVOC emissions (μg) separated by volatility and the O:C ratio.
log10C* (μg m− 3) O:C ratio

0–0.2 0.2–0.4 0.4–0.6 0.6–0.8 0.8–1.0 1–1.2 ≥ 1.2

− 4 0.003 0.135 0.000 0.000 0.000 0.000 0.000

− 3 0.109 0.066 0.006 0.007 0.000 0.000 0.000
− 2 0.190 0.054 0.167 0.002 0.000 0.000 0.000
− 1 0.165 0.187 0.055 0.002 0.000 0.000 0.000
0 0.715 0.251 0.079 0.015 0.000 0.000 0.000
1 0.369 0.039 0.005 0.000 0.000 0.000 0.000
2 0.339 0.148 0.003 0.001 0.000 0.000 0.000
3 0.296 0.025 0.002 0.001 0.000 0.000 0.000
4 0.090 0.027 0.005 0.000 0.000 0.000 0.000
5 0.064 0.064 0.007 0.000 0.000 0.000 0.000
6 0.127 0.059 0.005 0.009 0.000 0.001 0.000
7 0.263 0.023 0.004 0.002 0.000 0.001 0.000
8 0.399 0.020 0.061 0.012 0.000 0.089 0.000
9 0.399 0.016 0.013 0.008 0.000 0.071 0.000

I/SVOC compounds by their characteristic mass spectra. Rare studies

have speciated gaseous I/SVOC emissions at this detailed level as we did.
The combination of GC × GC-ToF-MS and self-constructed data pro­
cessing programs enables the mapping of speciated I/SVOCs into the 2D-
VBS space. With the improved data (although not resolved at the mo­
lecular level) being incorporated into models, approximate 45% differ­
ence of SOA concentration is observed.
We want to emphasize that the limited number of HDDVs, fuel types,
driving cycles, and operating conditions may introduce fortuitous re­
sults. Nevertheless, the uncertainties of the novel method are well
considered and fully addressed. It is of great help to carry out follow-up
tests, e.g., extensive samplings of in-use vehicles (complying with
different emission standards, with/without bio-fuels, with/without
aftertreatment devices, etc.) to further validate our results.

Notes

The authors declare no competing financial interest.

Author contribution

Xiao He (First Author): Conceptualization, Methodology, Validation,

Fig. 4. (a) Emission distribution of I/SVOCs on a 2D-VBS space (sample ID:
20201223-1, CHTC-HT cold-start, vehicle #2). Different colors indicate
different O:C ratios segmented into seven bins: 0–0.2, 0.2–0.4, 0.4–0.6, 0.6–0.8,
0.8–1.0, 1.0–1.2, and ≥ 1.2; (b) The modeled OA concentration by 2D-VBS
framework using speciated (orange line) and un-speciated (gray line) emis­
sion data respectively and the relative difference. The blue line, which is scaled
by the right axis, denotes the difference between two sets of modeled OA
concentration. (For interpretation of the references to color in this figure
legend, the reader is referred to the Web version of this article.)
Investigation, Formal Analysis, Writing-Original Draft, Data Curation,
Visualization, Funding Acquisition; Xuan Zheng (Corresponding
Author): Project Management, Validation, Writing-Review & Editing,
Funding Acquisition; Yan You: Validation, Writing-Review & Editing;
Shaojun Zhang: Validation, Writing-Review & Editing; Bin Zhao: Vali­
dation, Writing-Review & Editing, Software; Xuan Wang: Validation,
Writing-Review & Editing; Guanghan Huang: Methodology, Investiga­
tion; Ting Chen: Investigation; Yihuan Cao: Investigation; Liqiang He:
Investigation; Xing Chang: Software; Shuxiao Wang: Resources, Writing-
Review & Editing, Funding Acquisition; Ye Wu: Resources, Supervision,
Funding Acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.

establish a novel “three-step” approach to speciate and quantify them Acknowledgement

comprehensively. Over three-thousand compounds are identified and
classified into twenty-one categories, many of which, to the best of our The authors acknowledge the financial support of the National
knowledge, have been reported for the first time. Oxygenated I/SVOCs Natural Science Foundation of China (51978404, 42105100, and
are resolved systematically and over 20% of diesel emitted organic mass 41977180), the Basic Research of Shenzhen Science and Technology
contains oxygen content, suggesting that diesel emitted OA is actually Innovation Commission (JCYJ20190808145218827), the Guangdong
not “hydrocarbon-like”. This is an innovative way of (semi) quantifying Basic and Applied Basic Research Fund Committee
(2020B1515130003), the Samsung Advanced Institute of Technology,

7
X. He et al. Environmental Pollution 305 (2022) 119284

and the Tencent Foundation through the XPLORER PRIZE. The contents observation of enhanced formation of secondary organic aerosol during particulate
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