pubs.acs.

org/JPCA Article

Rate Coefficients for the Gas-Phase Reactions of Nitrate Radicals

with a Series of Furan Compounds
Fatima Al Ali, Cécile Coeur,* Nicolas Houzel, Houceine Bouya, Alexandre Tomas,
and Manolis N. Romanias
Cite This: https://doi.org/10.1021/acs.jpca.2c03828 Read Online

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ABSTRACT: The atmospheric reaction of a series of furan compounds (furan (F), 2-

methylfuran (2-MF), 3-methylfuran (3-MF), 2,5-dimethylfuran (2,5-DMF), and 2,3,5-
trimethylfuran (2,3,5-TMF)) with nitrate radical (NO3) has been investigated using the
relative rate kinetic method in the CHamber for the Atmospheric Reactivity and the
Metrology of the Environment (CHARME) simulation chamber at the laboratoire de Physico-
Chimie de l’Atmosphere (LPCA) laboratory (Dunkerque, France). The experiments were
performed at (294 ± 2) K atmospheric pressure and under dry conditions (relative humidity,
RH < 2%) with proton transfer mass reaction−time of flight−mass spectrometer (PTR-ToF-
MS) for the chemical analysis. The following rate coefficients (in units cm3 molecule−1 s−1)
were determined: furan, k(F) = (1.51 ± 0.38) × 10−12, 2-methylfuran, k(2‑MF) = (1.91 ± 0.32) ×
10−11, 3-methylfuran, k(3‑MF) = (1.49 ± 0.33) × 10−11, 2,5-dimethylfuran, k(2,5‑DMF) = (5.82 ±
1.21) × 10−11, and 2,3,5-trimethylfuran, k(2,3,5‑TMF) = (1.66 ± 0.69) × 10−10. The uncertainty
on the measured rate coefficient (ΔkFC) includes both the uncertainty on the measurement
and that on the rate coefficient of the reference molecule. To our knowledge, this work represents the first determination for the rate
coefficient of the 2,3,5-TMF reaction with NO3. This work shows that the reaction between furan and methylated furan compounds
with nitrate radical (NO3) is the dominant removal pathway during the night with lifetimes between 0.5 and 55 min for the studied
molecules.

1. INTRODUCTION identified as major constituents of the volatile organic

Biomass burning (BB) is the burning of living and dead compounds (VOCs) emitted during wildfire burning released
vegetation, which includes the human-initiated burning for from the pyrolysis of cellulose,9−12 comprising about 30% of
land clearing and land-use change, natural fires, and domestic the total number of VOCs identified in plumes, with significant
heating. Due to the increasing population rate and the extra atmospheric concentration levels ranging between 68 and 118
demand for food, the rate of land clearing and land use ppbv relative to 1 ppmv of CO formation. The concentration
(directly related to wildfires and BB events)1,2 has increased of VOCs emitted from biomass burning differs depending on
dramatically during the last few decades,3 and increasing trends the type of biomass and fire conditions. However, Stockwell et
al. (2015) characterizing the emissions from cooking fires,
are projected over the near future.4 BB emissions play a key
peat, crop residue, and other fuels showed that for the different
role in the oxidative capacity of the atmosphere. During the
biomass fuels, the furan emission factor (≅0.1−2.3 g Kg−1)
daytime, BB plumes can have OH concentrations 5−10 times
emitted was higher than that of phenolic compounds (≅0.05−
higher than background air,5 while an increase of more than
0.8 g Kg−1) but smaller than those of aromatic hydrocarbons
120% of the total OH reactivity during BB events has been
(≅0.2−5 g Kg−1).13 Furans have been demonstrated to
reported.6 During the nighttime, it has been recently shown
contribute significantly (≅20%) to overall NO314 and OH15
that the mixing of smoke-derived O3 with NOx in a BB plume
reactivity of emissions from the burning of common wildfire
leads to the production of NO3 radicals (the dominant
and residential fuels. For comparison, Decker et al. (2021)
nighttime oxidant) with a rate of approximately 1 ppbv h−1.77
showed in the FIREX-AQ aircraft data that the contribution of
As a consequence, significant nighttime chemical trans-
formations potentially occur inside the BB plume that could
strongly impact the oxidative capacity of the atmosphere and Received: June 2, 2022
air quality.8 Yet, these pathways are poorly explored in the Revised: October 17, 2022
literature.
The impact of BB emissions on air quality and climate is
related to the complex mixture of gases and particles released
into the atmosphere. Quite recently, furans have been

© XXXX American Chemical Society https://doi.org/10.1021/acs.jpca.2c03828

A J. Phys. Chem. A XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry A
furan compounds to OH reactivity (25%) is larger than the
contribution of phenolic compounds (16.4%) but smaller than
that of alkenes (33%). However, NO3 reactivity is mainly
governed by phenolic compounds (64.4%), which is much
larger than the contribution of furan compounds (19%) and
alkenes (5%).14 Other sources of furans include waste
incineration, fuel and biofuel combustion, temperature-based
industrial processes,16 and natural sediment and water
samples,17 and are toxic species and have direct adverse effects
on human health.18 Moreover, being promising future
alternative biofuels, 2-methylfuran and 2,5-dimethylfuran are
expected to highly increase in the upcoming years.19,20 They
are highly reactive compounds rapidly removed from the
atmosphere due to their gas-phase oxidation. Interestingly, a
recent experimental and model study showed that during the
daytime, furan degradation drives the chemistry inside a fresh
biomass plume,15 forming secondary pollutants that will
eventually lead to tropospheric ozone (O3) and secondary
organic aerosol (SOA) formation. Up to now, the contribution
of furan degradation on the nighttime tropospheric chemistry
is poorly addressed.
The atmospheric oxidation of furan compounds can be
governed by OH, NO3, O3, and Cl. There are several studies in
the literature reporting the tropospheric degradation of furan
and methylated furans by OH,21−23 chlorine,21,24 and
NO321,25,26 radicals under atmospheric pressure and room
temperature. All studies showed the formation of unsaturated
dicarbonyl products as major primary products from the
oxidation of methylated furan compounds. According to the
presented studies on the degradation mechanism of furan
compounds by NO3 radical, the major reaction pathway occurs
by NO3 addition to carbon C-2 or carbon C-5 on the ring due
to the formation of resonance-stabilized adducts. As a result,
unsaturated dicarbonyls are formed from the loss of NO2,
rearrangement of the intermediate, and ring opening.25,26
The very scarce kinetic data existing in the literature indicate
that the NO3-initiated oxidation of this class of compounds is
an extremely fast process and, consequently, their correspond-
ing role in nighttime chemistry is expected to be dominant and
more significant than that during the daytime. Methylated
furan compounds (2-MF, 3-MF, 2,5-DMF, 2,3,5-TMF) are an
important part of this family released during these fire events.27
At the same time, unlike their daytime atmospheric reactivity
with hydroxyl radical, their nighttime reactivity with NO3
radical is poorly studied in the literature. Moreover, the few
studies highlighting it reveals fast reactions.28−30 Thus, it is
important to study these reactions to understand furan
chemistry and its impact on the atmosphere.
The aim of the present study is to determine the rate
constants for the reactions of a series of furan compounds
(furan (F), 2-methylfuran (2-MF), 3-methylfuran (3-MF), 2,5-
dimethylfuran (2,5-DMF), and 2,3,5-trimethylfuran (2,3,5-
TMF)) with NO3 radical. The rate coefficients were measured
using the relative-rate method, and their atmospheric lifetimes
are determined.
2. EXPERIMENTAL SECTION
2.1. Description of the Chamber. The experiments were
performed in the dark at room temperature (294 ± 2 K) in
zero air at atmospheric pressure (760 Torr) and dry conditions
(RH < 2%) in the CHamber for the Atmospheric Reactivity
and the Metrology of the Environment (CHARME) indoor
simulation chamber located at Laboratoire de Physico-Chimie
B https://doi.org/10.1021/acs.jpca.2c03828
pubs.acs.org/JPCA Article
de l’Atmosphere (LPCA) in Dunkerque, France. CHARME is
a 9.2 m3 evacuable cylinder (diameter, ≈1.7 m; length, ≈4.0 m;
and surface to volume ratio, ≈3.5 m−1) made from stainless
steel (304 L) and electropolished. Four fans (stainless steel;
diameter 50 cm) are located at the bottom allowing the fast
homogenization of the reaction mixture. The humidity and
temperature within the chamber were monitored by a
combined T/RH probe (HMT334 series transmitters,
VAISALA). CHARME is coupled to a pump (Cobra
NC0100-0300B) to vacuum the pressure down to 0.4 mbar
and to an air generator (Parker Zander KA-MT 1-8)
connected to a compressor (SLM-S 7.5�Renner SCROLL-
Line) to fill the chamber with purified and dry air. The time
required to evacuate and reach the atmospheric pressure in the
chamber is around 1 h. CHARME is described in detail
elsewhere.31
2.2. Experimental Methods. In the present work, the
initial mixing ratios for reactants were in the range 500−1200
ppbv for both furans and reference compounds. The injection
of the organics into the chamber was performed using a glass
impinger in which known liquid volumes of the compounds
were under a low flow of gently heated purified air (2−10 L
min−1).
Nitrate radicals were formed in the chamber from the
thermal decomposition at (243 ± 5) K of dinitrogen pentoxide
(N2O5) under a flow of gaseous nitrogen (at ≅100 mL min−1)
according to reaction 1
N2O5 NO3 + NO2 (1)
N2O5 was first synthesized in an S-shaped tube (length = 2.5
m; diameter = 2 cm) from the gas-phase reaction of nitrogen
monoxide (NO) with ozone (O3) according to reaction 2
followed by reactions 3 and 4
NO + O3 NO2 + O2 (2)
NO2 + O3 NO3 + O2 (3)
NO2 + NO3 N2O5 (4)
Ozone was produced from O2 using a Corona discharge ozone
generator (Air Tree Ozone Technology, C-Lasky C-010-DTI).
Dinitrogen pentoxide crystals were collected at 193 K in a glass
cold trap introduced in a liquid nitrogen/ethanol bath and
stored at the same temperature in a freezer for few days before
being used. N2O5 was continuously injected into the chamber
until ≥98% consumption of both the furan and the reference
compounds. However, only until 50−80% consumption of 2-
MF was retained in the relative rate plots since the plots are
nonlinear beyond these limits (see Figure 1).
The VOC concentrations were continuously recorded
(every 10 s) with a PTR-ToF-MS (proton transfer reaction−
time of flight−mass spectrometer 1000, IONICON Analytik,
Innsbruck, Austria). The air from the chamber was sampled at
50 mL min−1 through an inlet polyether ether ketone (PEEK)
capillary line of 100 cm heated at 333 K to reduce the loss of
the VOCs during their sampling and then ionized in the drift
tube (E = 600 V cm−1; E/N = 136 Td) operating at 2.2 mbar
and 333 K. The organics were monitored from the intensity of
their parent ion [M + H]+: F (m/z 69.1), 2-MF and 3-MF (m/
z 83.1), 2,5-DMF (m/z 97.1), 2,3,5-TMF (m/z 111.1), α-
terpinene (α-T), γ-terpinene (γ-T), α-pinene (α-P) and β-
pinene (β-P) (m/z 137.2), 2-methyl-2-butene (2-MB) (m/z
71.1), and 2,3-dimethyl-2-butene (DMB) (m/z 85.1).
J. Phys. Chem. A XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry A
Figure 1. Kinetic data plots for the reaction of 2-methylfuran with
nitrate radicals at 294 ± 2 K using 2-MB (black squares), γ-T (red
triangles), and DMB (blue cross) as reference compounds.
The wall losses of organic compounds were determined in
the dark from the decay of their concentrations before N2O5
introduction. The cleanliness of the reaction chamber was
evaluated in all of the experiments by measuring the
background levels of the monitored ions for both furan and
reference compounds for a time range of 10−15 min.
Background concentrations were negligible compared to the
initial experimental concentrations. Acetonitrile was injected in
the chamber as a dilution tracer, and the signal was followed by
a PTR-MS-TOF.31
Preliminary tests were performed for each VOC to control
the linearity of the PTR-MS signal with respect to the injected
VOC concentrations. Furthermore, the possible contribution
of degradation products to the ion peaks used to monitor the
furan or reference compounds was also evaluated and was
found to be negligible. In these experiments, each compound
of interest was individually introduced in the chamber and left
to react with NO3 until its complete consumption. The
products formed resulted in various mass peaks in the PTR-
MS, but in all cases, they did not interfere with the mass peaks
selected to monitor the furans or reference compounds.
2.3. Materials. The compounds used in this study, their
manufacturer, and stated purity were O2 (Praxair, 99.5%),
nitrogen monoxide (Praxair, 99%), furan (>99%, Sigma-
Aldrich), 2-methylfuran (99%, Sigma-Aldrich), 3-methylfuran
(98%, Sigma-Aldrich), 2,5-dimethylfuran (99%, Sigma-Al-
drich), 2,3,5-trimethylfuran (99%, Sigma-Aldrich), α-terpinene
(>95%, Sigma-Aldrich), γ-terpinene (97%, Sigma-Aldrich), α-
pinene (98%, ACROS organics), β-pinene (>94%, TCI), 2-
methyl-2-butene (>99%, Sigma-Aldrich), 2,3-dimethyl-2-bu-
tene (98%, Sigma-Aldrich), and acetonitrile (Sigma-Aldrich, ≥
99.5%).
2.4. Relative Rate Kinetic Method. The rate coefficients
for the gas-phase reaction of furan compounds with NO3
radicals were determined using the relative-rate kinetic
method, i.e., comparing the decay rates of furan compounds
(FCs) and reference compounds. This method permits
determining the unknown rate coefficient of a compound
relative to a compound with a known NO3 rate coefficient. The
furan of interest and reference compound react simultaneously
with NO3.
C https://doi.org/10.1021/acs.jpca.2c03828
pubs.acs.org/JPCA Article
FC + NO3 products(kFC) (5)
reference + NO3 products(kRef ) (6)
Kinetic treatment of reactions 5 and 6 leads to eq I, that
represents the FCs and reference compounds changes as a
function of time
[FC]0 kFC [Ref]0
ln k wt = × ln
[FC]t kRef [Ref]t (I)
where kFC and kRef are the rate coefficients for the reactions of
the furan-based compound of interest and the reference with
NO3, respectively. [FC]0, [FC]t, [Ref]0, and [Ref]t are the
concentrations of the furan-based compound and of the
reference at time 0 and t, respectively. kw is the wall loss rate
coefficient, which was taken into account for furan (kw = (5−
7) × 10−5 s−1) while it was neglected for all other organic
compounds (kw < 5 × 10−5 s−1). The dilution effect was
negligible as the signal of acetonitrile remained constant
throughout the experiment. Plots of the kinetic data of eq I
should yield a straight line with zero intercept and a slope (b)
which is the rate coefficient ratio kFC/kRef.
The references chosen fulfill several requirements as follows.
The two compounds (studied and reference compounds)
should have comparable rate coefficients (0.2 < kFC/kRef < 5).
For each studied furan compound, two to three reference
compounds were used and at least three experiments were
performed relative to each reference at increasing concen-
trations of the organic compounds. The references used in this
study and their rate coefficients with nitrate radicals (in units
of cm3 molecule−1 s−1) were k(α‑terpinene) = (1.82 ± 1.04) ×
10−10,32k(γ‑terpinene) = (2.94 ± 0.81) × 10−11,32k(α‑pinene) = (6.20
± 1.42) × 10 − 1 2 , 3 3 k ( β ‑ p i n e n e ) = (2.50 ± 0.69) ×
10−11,33k(2‑methyl‑2‑butene) = (9.38 ± 0.47) × 10−12,34 and
k(2,3‑dimethyl‑2‑butene) = (4.50 ± 0.40) × 10−11.35 Except 2,3-
dimethyl-2-butene, the rate coefficient values of reference
molecules were IUPAC recommended. In the case of 2,3-
dimethyl-2-butene, the rate coefficient was retrieved by the
work of Lancar et al. (1991).35 The agreement of the rate
coefficient measured relative to the different references gives
confidence in the values of reference rate coefficients chosen.
In the following sections, the following abbreviations are used
to denote the reference compounds used: α-T for α-terpinene,
β-T for β-terpinene, α-p for α-pinene, β-P for β-pinene, 2-MB
for 2-methyl-2-butene, and DMB for 2,3-dimethyl-2-butene.
2.5. Error Analysis. In this section, a detailed explanation
is given for the potential uncertainties obtained from our
kinetic measurements. The standard deviation arising from the
least squares linear regression of the data (σ) resembles the
uncertainty of the slope. The uncertainty of the determined
rate coefficients included the error on the measurement and
the uncertainty on the value of the reference rate coefficient as
follows. Taking into consideration the slope (b), the known
kRef and their uncertainties (σ), and ΔkRef, the uncertainty on
the measured rate coefficient (ΔkFC) is calculated according to
eq II.36
kFC = × kRef + b × kRef (II)
The final average rate coefficient kaverage and its uncertainty
Δkaverage (standard error of the mean) were calculated using
eqs III and IV
J. Phys. Chem. A XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry A pubs.acs.org/JPCA Article

Table 1. Summary of All of the Rate Coefficients for the Reactions of Furan Compounds with NO3

a
Indicated error is twice the standard deviation arising from the linear regression analysis. bExpressed in cm3 molecule−1 s−1. cIndicated error
calculated using eq II. dAverage rate coefficients obtained from all reference measurements. eAverage error according to eq IV.

n
i=1
ki
kaverage =
n (III)
n
( ki)2
i=1
kaverage =
n (IV)
where ki and Δki represent the rate coefficient and the
uncertainties obtained in each experiment and n represents the
number of experiments.36
3. RESULTS AND DISCUSSION
The experimental conditions and the results are given in Table
1. Furan and reference concentrations ranged from ∼300 to
∼1400 ppbv. The relative rate plots in the form of eq I for the
experiments of 2-MF are presented in Figure 1. The plots of
the experiments for the other studied molecules (furan, 3-
methylfuran, 2,5-dimethylfuran, and 2,3,5-trimethylfuran) are
presented in Figures S1−S4 in the Supporting Information.
The obtained plots show good linearity with near zero
intercept. Each figure includes the experimental data of all of
the experiments.
The slopes (kFC/kRef) derived from the plots, the determined
NO3 rate coefficients (kFC) for each experiment, and the kFC
averages are displayed in Table 1.36 The rate coefficients using
D https://doi.org/10.1021/acs.jpca.2c03828
the two or three references are in accordance (relative
discrepancy lower than 10%) and lead to the following average
values (in cm3 molecule−1 s−1): k(F) = (1.51 ± 0.38) × 10−12,
k(2‑MF) = (1.91 ± 0.32) × 10−11, k(3‑MF) = (1.49 ± 0.33) ×
10−11, k(2,5‑DMF) = (5.82 ± 1.21) × 10−11 and k(2,3,5‑TMF) = (1.66
± 0.69) × 10−10. These rate coefficients are compared to the
available literature data.
3.1. Trends in Reactivity. Comparing the rate coefficient
obtained for furan with those of 2-MF and 3-MF, the addition
of a methyl group on the furan ring increases the rate
coefficient by ∼1 order of magnitude. This could be attributed
to the positive inductive effect of the methyl group, favoring
the NO3 addition because of the increase of the ring’s electron
density. However, the position of the methyl group whether on
C-2 or C-3 did not have an impact on the rate coefficient,
suggesting a negligible effect of the methyl group position on
the rate coefficient. Comparing single-alkylated furan rate
coefficients (2-MF and 3-MF) with that of 2,5-dimethylfuran
shows an increase by a factor of ∼3 attributed again to the
increase of the positive inductive effect on the ring. The same
trend is observed when comparing the NO3 rate coefficients of
2,5-dimethylfuran and 2,3,5-trimethylfuran. This was also
validated in another literature study.29
J. Phys. Chem. A XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry A pubs.acs.org/JPCA Article

Table 2. Comparison of the Average Rate Coefficient Measured in This Study with Those in the Literaturea
compound kFC (average) (this work) cm3 molecule−1 s−1 kFC (literature) cm3 molecule−1 s−1 setup/technique
furan (1.51 ± 0.38) × 10 −12
(1.40 ± 0.20) × 10−12 RR-ASC/GC-FID28
(9.98 ± 0.62) × 10−13 RR-FT/GC-FID29
(1.3 ± 0.2) × 10−12 AR-DFT/LIF37
(1.50 ± 0.23) × 10−12 RR-ASC/FTIR30
2-methylfuran (1.91 ± 0.32) × 10−11 (2.57 ± 0.17) × 10−11 RR-FT/GC-FID29
(2.37 ± 0.55) × 10−11 RR-ASC/FTIR30
3-methylfuran (1.49 ± 0.33) × 10−11 (2.86 ± 0.06) × 10−11 RR-FT/GC-FID29
(1.31 ± 0.46) × 10−11 RR-ASC/GC-FID38
(1.26 ± 0.18) × 10−11 RR-ASC/GC-FID, FTIR21
2,5-dimethylfuran (5.82 ± 1.21) × 10−11 (5.78 ± 0.34) × 10−11 RR-FT/GC-FID29
(1.10 ± 0.33) × 10−10 RR-ASC/FTIR30
2,3,5-TMF (1.66 ± 0.69) × 10−10 b

a
Abbreviations used in the table: Relative rate (RR) method, absolute rate (AR) method, atmospheric simulation chamber�Teflon or glass made
(ASC), discharge flow tube (DFT), flow tube (FT), laser-induced fluorescence (LIF), gas chromatography-flame ionization detection (GC-FID),
Fourier transform infrared (FTIR) spectroscopy. bNo data.

Table 3. Atmospheric Lifetimes of Furan Compounds with Respect to Their Reaction with Nitrate Radicals (NO3), Hydroxyl
Radicals (OH), and Ozone (O3)
τ(NO3) (min)a,b τ(NO3) (min)c
compound (nighttime) (daytime) τ(OH) (min)d τ(O3) (min)e τ(Cl) (min)f
44 45
furan 55 1103 199 8547(∼6 days) 8160 (∼5 days)43
2-methylfuran 4 87 11422 4380 (∼3 days)43
3-methylfuran 6 112 9522 1084 (∼1 day)38 4200 (∼3 days)43
2,5-dimethylfuran 1 29 6622 5441 3480 (∼2 days)43
2,3,5-trimethylfuran 0.5 10
a
This work. b[NO3] = 2 × 108 molecules cm−3 (average nighttime concentration).39 c[NO3] = 1 × 107 molecules cm−3 (average daytime
concentration).39 d[OH] = 2 × 106 12 h daytime average.40 e[O3] = 7.5 × 1011 molecules cm−3.41 f[Cl] = 1 × 104 molecules cm−3.46

3.2. Comparison with Literature Data. Literature
studies measuring the rate coefficients of the reactions of
furan compounds with NO3 are scarce. Table 2 summarizes the
rate coefficients kFC obtained in this study and in the literature
with different techniques used in each study. Atkinson et al.
performed relative rate room temperature kinetic measure-
ments to study the reaction of furan with NO3 radicals inside a
4000 L atmospheric pressure simulation chamber coupled with
a gas chromatography-flame ionization detector (GC-FID).
Trans-2-butene was used as a reference compound for the
furan rate coefficient measurement.28 Kind et al. performed
relative rate kinetic measurements inside a low-pressure flow
tube reactor, coupled with a GC-FID for the detection of
organic species.29 Trans-butene was used as a reference
compound to determine the furan reaction rate coefficient,
while 2,3-dimethyl-2-butene was used as a reference for 2-
methylfuran, 3-methylfuran, and 2,5-dimethylfuran measure-
ments. In the study of Cabanas et al., the rate coefficient was
measured as a function of temperature inside a low-pressure
(1.1−1.5 Torr) discharge flow tube reactor coupled with LIF
for the detection of NO3 radicals. Experiments were carried out
under pseudo-first-order conditions, i.e., following nitrate
radical decay with time to determine the rate coefficient of
the furan reaction.37 Alvarado et al. measured the 3-MF + NO3
rate coefficient in an atmospheric pressure simulation chamber
coupled with a GC-FID at room temperature using 2-methyl-
2-butene as a reference compound.38 This rate coefficient was
also measured by Tapia et al. using a 500 L atmospheric
pressure and room temperature smog chamber. 2-Methyl-2-
butene and α-pinene were used as reference molecules, and the
analysis of the kinetic profiles was achieved by deploying GC-
E https://doi.org/10.1021/acs.jpca.2c03828
FID and Fourier transform infrared (FTIR) spectroscopy.22 A
study determined the rate coefficient for the reaction of furan,
2-MF, and 2,5-DMF with NO3.30 They also used the relative
rate method in a 7300 L indoor simulation chamber by in situ
FTIR spectroscopy. Several references were used to measure
each rate coefficient (for furan: cyclohexene, α-P, camphene,
and α-angelicalactone; for 2-MF: 2-carene, 2,3-DMB, α-P,
pyrrole, and 2,5-DMF; for 2,5-DMF: 2-carene, 2,3-DMB, α-P,
pyrrole, and 2-MF).
For furan, all literature rate coefficients are in good
agreement with the value determined in the present study.
Besides the value of Kind et al., and considering the
experimental uncertainties, our measurement shows good
agreement with those provided in the literature, with
differences below 15%. The reasons for the lower value
obtained by Kind et al. are unclear. For the 2-MF + NO3
reaction, the present work shows a satisfactory agreement with
the only two studies in the literature with discrepancies below
25%. Regarding 3-MF, the present work is consistent with
Alvarado et al.38 and Tapia et al.,21 to within 15%, while the
rate coefficient obtained by Kind et al. is about two times
higher than the present one. As for furan, the reasons for the
disagreement are unclear. Regarding 2,5-DMF, there are only
two literature studies determining its rate coefficient: Kind et
al. report a measurement in excellent agreement with that
presented in this work; however, Newland et al.30 gave a 100%
higher rate coefficient. The reason for this discrepancy is
unknown, but for the common reference (2,3-dimethyl-2-
butene) between the two studies, the rate coefficient used by
Newland et al. is ≅1.3 times higher than the value used by us.
To the best of our knowledge, this work represents the first
J. Phys. Chem. A XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry A
work giving the rate coefficient for the reaction between the
2,3,5-trimethylfuran reaction with NO3.
3.3. Atmospheric Implications. From the rate coef-
ficients measured in this study, the atmospheric lifetimes of
furan and methylated furan compounds with respect to their
reaction with NO3 radicals can be determined. Table 3
includes lifetimes calculated in this work compared to lifetimes
due to reactions with hydroxyl radical, O3, and chlorine (Cl)
atoms. Assuming an average NO3 nighttime concentration of 2
× 108 molecules cm−3,39 the calculated lifetimes of the
investigated compounds are in the range of 0.5−55 min. The
lifetimes of these compounds due to their reactions with OH,
O3, or Cl were calculated using a 12 h daylight average OH
concentration of 2 × 106 molecules cm−3,40 an ozone
concentration of 7.5 × 1011 molecules cm−3,41 an average Cl
global concentration of 1 × 104 molecules cm−3, and the
corresponding OH, O3, and Cl rate coefficients. The lifetimes
were in the range of 66−199, 54−8547, and 3480−8160 min
with OH, O3, and Cl, respectively. Therefore, the nighttime
reaction with NO3 radicals is anticipated to be the principal
sink for these compounds. The reaction with ozone is
considered negligible for furan and 3-methylfuran, but it
could be competitive with OH radical in the case of 2,5-
dimethylfuran. For the reaction of these furanoids with NO3
during the daytime, the lifetimes were calculated using the
NO3 daytime concentration of 1 × 107 molecules cm−3.39 The
calculated lifetime was in the range 10−1103 min, and thus,
the competition between the reaction with NO3 and OH
during the daytime can be important for 2,5-DMF and 2,3,5-
TMF. This aspect was also observed in the reaction of
catechols (1,2-dihydroxybenzenes) with nitrate and hydroxyl
radicals.42 Regarding the reaction with chlorine atoms, it is not
significant compared to other reactions; however, it will be
much more important in coastal areas with higher Cl
concentrations.43 Yet, it is worth emphasizing that, in fire
plumes, where the concentration of nitrate radicals highly
increases, which may be fast (>0.5 ppbv h−1),7 the nighttime
reactivity of these compounds dominates with a lifetime in the
order of minutes. Moreover, temperature-dependent studies
are needed since the temperature in the plume could be higher
than ambient temperature. The present results will help in
better understanding the relevant chemistry in biomass
burning plumes. It is clear that methylated furans are expected
to be mainly present in fresh BB plumes; their tropospheric
oxidation will result in the formation of products in the gas and
perhaps the particulate phase anticipated to be present in aged
BB plumes.
4. CONCLUSIONS
In the present work, five heteroaromatic furan-based
compounds were investigated relative to their nighttime
atmospheric reactivity with NO3 radicals in the CHARME
atmospheric simulation chamber. Rate coefficients are
determined for the reaction of the studied compounds at
294 K and 760 Torr based on the relative rate method. These
values highlight the effect of the methyl group on increasing
the rate coefficient due to the inductive effect induced on the
ring. Also, this work sheds light on the importance of the
reaction with NO3 as a major atmospheric sink for this class of
compounds. This work is the first study reporting the rate
coefficient measured for the reaction of 2,3,5-trimethylfuran.
F https://doi.org/10.1021/acs.jpca.2c03828
pubs.acs.org/JPCA Article
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpca.2c03828.
Kinetic data plots for the reaction of furan with nitrate
radicals at 294 ± 2 K using α-P (green circles) and β-P
(pink triangles) as reference compounds (Figure S1);
kinetic data plots for the reaction of 3-methylfuran with
nitrate radicals at 294 ± 2 K using 2-MB (black squares),
γ-terpinene (red triangles) and α-P (green circles) as
reference compounds (Figure S2); kinetic data plots for
the reaction of 2,5-dimethylfuran with nitrate radicals at
294 ± 2 K using γ-T (red triangles) and DMB (blue
crosses) as reference compounds (Figure S3) (PDF)
■ AUTHOR INFORMATION
Corresponding Author
Cécile Coeur − Laboratoire de Physico-Chimie de
l’Atmosphère, Université du Littoral Côte d’Opale,
Dunkerque 59140, France; orcid.org/0000-0002-5643-
5148; Phone: +33 328 23 76 42; Email: coeur@univ-
littoral.fr
Authors
Fatima Al Ali − Laboratoire de Physico-Chimie de
l’Atmosphère, Université du Littoral Côte d’Opale,
Dunkerque 59140, France; Institut Mines Télécom Nord
Europe, Univ. Lille, Center for Energy and Environment, F-
59000 Lille, France
Nicolas Houzel − Laboratoire de Physico-Chimie de
l’Atmosphère, Université du Littoral Côte d’Opale,
Dunkerque 59140, France
Houceine Bouya − Laboratoire de Physico-Chimie de
l’Atmosphère, Université du Littoral Côte d’Opale,
Dunkerque 59140, France
Alexandre Tomas − Institut Mines Télécom Nord Europe,
Univ. Lille, Center for Energy and Environment, F-59000
Lille, France; orcid.org/0000-0002-0125-581X
Manolis N. Romanias − Institut Mines Télécom Nord Europe,
Univ. Lille, Center for Energy and Environment, F-59000
Lille, France; orcid.org/0000-0002-9049-0319
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpca.2c03828
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was supported by the CaPPA project (Chemical and
Physical Properties of the Atmosphere) funded by the French
National Research Agency (ANR-11-LABX-0005-01) and the
CLIMIBIO program supported by the Hauts-de-France
Regional Council, the French Ministry of Higher Education
and Research, and the European Regional Development Fund.
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