International Journal of Mass Spectrometry 356 (2013) 4145

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International Journal of Mass Spectrometry

journal homepage: www.elsevier.com/locate/ijms

Modifying PTR-MS operating conditions for quantitative headspace

analysis of hydro-alcoholic beverages. 1. Variation of the mean
collision energy to control ionization processes occurring during
PTR-MS analyses of 1040% (v/v) ethanolwater solutions
Guillaume Fiches a , Isabelle Dlris b,c, , Anne Saint-Eve c,b , Brigitte Pollet b,c ,
Pascal Brunerie a , Isabelle Souchon b,c
a

Pernod Ricard Research Center, 120 Avenue Marchal Foch, F-94015 Crteil, France
INRA, UMR782 Gnie et Microbiologie des Procds Alimentaires (GMPA), 1 Avenue Lucien Bretignires, F-78850 Thiverval-Grignon, France
c
AgroParisTech, UMR782 Gnie et Microbiologie des Procds Alimentaires (GMPA), 1 Avenue Lucien Bretignires, F-78850 Thiverval-Grignon, France
b

a r t i c l e

i n f o

Article history:
Received 16 July 2013
Received in revised form 4 October 2013
Accepted 4 October 2013
Available online 16 October 2013
Keywords:
PTR-MS
Ethanol
Fragmentation
Ionization
E/N
Ion kinetic energy

a b s t r a c t
The analysis of ethanol-containing headspace above alcoholic beverages using proton transfer reactionmass spectrometry constitute a real analytical challenge because, at standard operating conditions,
ethanol reacts with H3 O+ reagent ions and leads to their depletion as well as to the formation of several ions from the ethanol. It thus complicates the mass spectrum and has an impact on the stability of
ionization conditions. Different methods, mainly based on sample dilution, have been proposed in literature but are not easy to set up. In the present study, we aimed to gain insights into a simpler way to
control ionization processes by varying the mean collision energy in the drift tube during the analysis of
hydro-alcoholic solutions having an ethanol concentration in the liquid phase ranging between 10% and
40% (v/v). The variation of the E/N ratio enabled the modication of ion kinetic energies and of the density of gas particles in the drift tube. Results showed the abundances of H3 O+ reagent ions, (H2 O)n H3 O+
water clusters and ions issued from ethanol were controlled by varying E/N values from 250 Td to 450 Td,
depending on the ethanol content of samples. This study constitutes a rst step toward the quantitative
analysis of aroma compounds contained in more complex high ethanol-containing beverages.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Proton transfer reaction mass spectrometry (PTR-MS) relies on
chemical ionization to detect and to quantify most of the volatile
organic compounds (VOCs) present in the air. Air samples are continuously pumped into the PTR-MS through a ow drift tube reactor
and VOCs are analyzed by a quadrupole mass spectrometer [1,2].
H3 O+ reagent ions are produced from water gas by a hollow cathode
set in the source and perform, if energetically allowed, a nondissociative proton transfer reaction with VOCs in the drift tube,
according to the equation: H3 O+ + VOC H2 O + VOC H+ . One of the
conditions that must be respected is that reagent ions must be in
large excess in the drift tube to ensure that [VOC H+ ]  [H3 O+ ] and
allow quantitative analysis [35]. In recent years, PTR-MS has been

Corresponding author at: INRA, UMR782 Gnie et Microbiologie des Procds

Alimentaires (GMPA), 1 Avenue Lucien Bretignires, F-78850 Thiverval-Grignon,
France. Tel.: +33 (0)1 30 81 54 39; fax: +33 (0)1 30 81 55 97.
E-mail address: isabelle.deleris@grignon.inra.fr (I. Dlris).
1387-3806/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ijms.2013.10.001

widely used to characterize, authenticate and/or classify different

types of foods according to their volatile prole.
For some products, such analyses remain difcult due to ionization competition that occurs in presence of interfering molecules.
For example, the analysis of ethanol-containing samples with PTRMS raises a technical difculty since ethanol is a volatile compound
and its concentration in the headspace above alcoholic beverages
can be high, depending on the initial ethanol content in beverages
(up to 45% of the total liquid volume in beverages such as spirits). At PTR-MS standard operating conditions, which ensure low
compound fragmentation and low water cluster formation, H3 O+
reagent ions efciently react with the large amounts of ethanol supplied to the system (exothermic proton exchange between H3 O+
and ethanol), and the equation [VOC H+ ]  [H3 O+ ] is no longer
valid [68]. Studies in the literature showed that the ethanol limit
concentration under which this phenomenon was not observed
was about 100 parts per million by volume (ppmv) in the sample headspace [6] or 4% v/v in the hydro-alcoholic solution. It thus
concerns only beverages with low ethanol content [9,10]. In addition to the depletion of reagent ions, it was also shown that ethanol

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G. Fiches et al. / International Journal of Mass Spectrometry 356 (2013) 4145

percentage in samples can inuence VOC fragmentation patterns.

Depending on the ethanol content, several ion species from the
ethanol, especially protonated ethanol-based clusters, are likely to
be formed and can react with VOCs, leading to the complication of
the mass spectrum [6,11]. To overcome these limits, two main solutions have been proposed in the literature. One consists in diluting
sample headspace with a ow of ethanol-saturated nitrogen, leading to the total replacement of H3 O+ reagent ions by protonated
ethanol and protonated ethanol clusters [6]. Another solution proposed in the literature consists in sample dilution with a nitrogen
ow in order to minimize the ethanol content transmitted to the
drift tube and to maintain H3 O+ reagent ion abundance at an acceptable level [12]. Most PTR-MS studies in literature dealing with
alcoholic beverages focused on wine or on samples with an ethanol
content of above 1015% in the liquid phase [5,6,12]. Apra et al. [5]
notably studied fragmentation patterns and air/solution partition
coefcient of esters in 2.5%, 6.2%, 12.3%, 20.9%, 48%, and 96% (v/v)
ethanolwater solutions. Their results for solutions with ethanol
content above 12.3% (v/v) were not considered as exploitable,
mainly because of the overlapping effect of ions issued from the
ethanol on PTR-MS ngerprints [5]. According to our knowledge,
no PTR-MS study of headspace above liquid samples with ethanol
contents from 20 to 40% (v/v) was estimated as reliable enough.
In consequence, PTR-MS analyses of alcoholic beverages such as
liquors and spirits still represent a challenge to overcome.
From knowledge on PTR-MS principles, another way to control H3 O+ reagent ion depletion and the abundances of ion species
from ethanol can be proposed, based on the modications of PTRMS operating conditions. When performing PTR-MS assays, two
drift tube parameters can be easily modied by users: E, the
strength of the electric eld tube and N, the buffer gas density.
The electric eld strength E can be increased to enhance ion kinetic
energy. Decreasing the buffer gas density N leads to less numerous,
but more energetic collisions between analytes and neutrals from
buffer gas. As a consequence, increasing E/N ratio value favors the
desolvation of protonated aggregates [R,(H2 O)n H+ ] and also leads to
collision-induced dissociations (CID) (ion breakup due to collisions
with the buffer gas) [13,14].
In this context, the present study investigates the inuence of
the variation of mean collision energy on PTR-MS ngerprints of
headspaces above 1040% (v/v) ethanol-water solutions. Its main
goal is to gain insights on the effects of modications of E/N ratio
impact ionization processes in PTR-MS, depending on the ethanol
contents of aqueous solutions. The nal objective of this work is
to propose operating conditions compatible with the analysis of
high ethanol-containing beverages by PTR-MS without the use of
dilution and saturation techniques.
2. Materials and methods
2.1. Samples
Hydro-alcoholic solutions were prepared with mineral water
(Evian, Danone, France) and food-grade anhydrous ethanol with
purity higher than 99.5% (Carlo Erba Reagents, France). Four levels
of ethanol content were tested (10%, 20%, 30% and 40% v/v). For
each ethanol concentration and each experimental condition, three
replicates were performed.
2.2. Data acquisition
Measurements were performed using a High Sensitivity Proton Transfer Reaction Quadrupole-Mass Spectrometer (Ionicon
Analytik, Innsbruck, Austria). Twenty mL of solution were placed
in 200-mL Schott asks. Before measurements, samples were

maintained for 24 h at 20 C to ensure the establishment of thermodynamic equilibrium. Analysis began with the measurement
of the room air signal for 3 min (background signal) and continued with the measurement of sample headspace signal for 3
more min. The SCAN mode was used to record a complete scan
from mass/charge ratio (m/z) 21200, with a dwell time per mass
of 0.1 s. Ion signal intensities were recorded in counts per second (cps). Headspaces were stripped by a controlled 8 mL/min air
ow (5860S mass owmeter, Brooks Instruments, USA). H2 O ow
rate and the electron current intensity of the source were set at
7 sccm (standard cubic centimeter) and 7 mA, respectively. PTRMS drift tube voltage Udrift , pressure pdrift and temperature Tdrift
were varied according to a 33 complete experimental design: Udrift
(400600800 V), pdrift (0.81.42 mbar), and Tdrift (406080 C).
Data were collected using PTR-MS control software (Ionicon Analytik, Innsbruck, Austria).
2.3. Data handling
2.3.1. Ionization conditions
E/N ratios were calculated from drift tube parameters according
to Eq. (1), in which E refers to the electric eld and N to the density
of buffer gas molecules [15].
E
U
R Tdrift
= drift
N
L
Nav pdrift 104

(1)

where L (cm): drift tube length; Nav : Avogadros constant (mol1 );

R (J K1 mol1 ): molar gas constant; and Udrift (V), pdrift (mbar)
and Tdrift (K): drift tube voltage, pressure and temperature, respectively. The experimental design dened in Section 2.2 allowed
the screening of E/N values from 91 Td to 512 Td (1 Td = 1
Townsend = 1017 cm2 V) [3]. The standard operating conditions
generally used correspond to an E/N ratio of approximately
120140 Td (and are approximately equivalent to Udrift = 600 V,
pdrift = 2 mbar, Tdrift = 60 C with the PTR-MS equipment used in this
study).
2.3.2. Ion signals
The mean intensity values for each m/z ion were calculated by
averaging all values from the three replicates during the last 3 min
of the recording session (sample analysis). For H3 O+ reagent ions,
background intensity (without ethanol) was calculated by averaging all values from the 3 replicates during the rst 3 min of the
recording session. All values were corrected by ion transmission
rates. For each ion, the proportion with regard to the total signal
was determined. The total signal was calculated by adding mean
intensity values (in cps) of all ions from m/z 21 to 200. Only ions
representing more than 1% of the total signal were considered in
Section 3.
3. Results and discussion
3.1. Product ion identication
Eleven main ion species were common to all four ethanol
contents (10, 20, 30 and 40% v/v ethanolwater solutions): m/z
19 (calculated through m/z 21 ions), 37, 29, 47, 48, 75, 93, 94,
121, 139. The identication of ion species formed during PTR-MS
analyses relies on the fact that many proton transfer reactions are
non-dissociative due to the soft ionization conditions (low energy).
Many VOCs thus lead to the formation of ions with m/z ratio equal
to compound molecular mass plus one, due to the addition of a
proton [7]. The identication of product ions from water and from
ethanol is well established in the literature for standard conditions (in vitro; standard operating conditions: E/N = 120140 Td)

G. Fiches et al. / International Journal of Mass Spectrometry 356 (2013) 4145

Fig. 1. Variation in the normalized intensities of main product ions (in reference to
H3 O+ intensity) according to E/N ratio (Td) during the analysis of 10 (a) and 40% (b)
(v/v) ethanol-containing solutions by PTR-MS.

and can be used to interpret the present results [6,11,12,14,16,17].

We can remind that ions m/z 29 (C2 H5 + ), 47 (C2 H5 OHH+ ), 75 (C2 H5 +
(C2 H5 OH)), 93 (C2 H5 OHH+ (C2 H5 OH)), 121 (C2 H5 + (C2 H5 OH)2 ) and
139 (C2 H5 OHH+ (C2 H5 OH)2 ) can be related to ions issued from
ethanol. Ions m/z 21 corresponded to hydronium ions H3 18 O+ ,
which are preferentially measured to preserve the detector, since
H3 16 O+ (m/z 19) are present in excessive amounts (natural isotopic
ratio 18 O/16 O 0.0025) [1]. When analyzing humid air with the
PTR-MS, H3 O+ reagent ions are hydrated and lead to the formation
of water cluster ions ((H2 O) H3 O+ , m/z 37).
3.2. Effect of E/N ratio and ethanol content on reagent and
product ions
Fig. 1a and b represent the variation of normalized intensities
of main product ions according to E/N ratio during the analysis of
10% and 40% (v/v) ethanol-containing solutions by PTR-MS, respectively (results for 20 and 30% ethanol-containing solutions were not
shown as they were intermediate). When the E/N ratio increased,
the most abundant species were successively m/z 93 ions (for low
and medium values of the E/N ratio: 90170 Td), corresponding to
the protonated ethanol cluster C2 H5 OHH+ (C2 H5 OH), m/z 47 ions
(for medium values of the E/N ratio: 170300 Td), corresponding to the protonated ethanol C2 H5 OHH+ , and m/z 19 ions (for
high values of the E/N ratio: 300500 Td), corresponding to H3 O+
reagent ions. At PTR-MS standard operating conditions (120140
Td), ethanol in the air massively reacted with H3 O+ reagent ions,
thus leading to their total depletion (Fig. 1), regardless the ethanol

43

content. In the presence of ethanol in the air, the percentage of the

total signal for m/z 19 ions started to increase for E/N values above
150 Td for all ethanol concentrations, and progressively reached
a plateau from 340 Td. The increase in the mean collision energy
can have two main consequences on ethanol PTR-MS ngerprints:
the desolvatation of cluster ions are more likely to occur due to the
increase in the internal energy of the system and fragmentation
phenomena are favored. High-weight ethanol clusters (m/z 75, 93,
121 and 139) are more easily desolvated due to the application of
high mean collision energies and/or low buffer gas densities and
fragment ions (m/z 29) are more likely formed. Another parameter
that plays a role on ethanol ngerprints is the amount of ethanol
in the sample (and, thus, the ethanol headspace concentration),
as it was shown for PTR-MS by Boscaini et al. [6] and for selected
ion ow drift tube-mass spectrometer (SIFT-MS) by Dryahina et al.
[11]. Boscaini et al. highlighted that the abundances of the main
ions from the ethanol above 5, 10 and 99% (v/v) ethanolwater
solutions at standard PTR-MS operating conditions can vary according to the percentage of ethanol in the liquid phase: m/z 47, 75
and 93 ions were mainly produced with 5 or 10% ethanol/water
solutions, whereas it was m/z 93 and 139 ions in the case of absolute ethanol (99%) [6]. Increasing the ethanol concentration in the
air above solutions induced the formation of ethanol clusters. The
results of the present study are in accordance with the ones found
in the literature [11] (Fig. 1): ethanol ions (m/z 47) and ethanol cluster ions (m/z 75, 93, 121 and 139) represented higher proportions
of the total signal when the ethanol content in samples increased.
In consequence, the energy required to desolvate the same proportion of ethanol clusters also increased when the ethanol content
in samples increased: for a given E/N value, a greater proportion
of ethanol clusters were desolvated during the analysis of the 10%
ethanol-containing solution than for the 40% ethanol-containing
solution (Fig. 1). The dependence of the m/z 19 level on sample
ethanol content is also in agreement with data in the literature
[6]. The higher the ethanol content is, the higher the E/N ratio that
must be applied to obtain a given level of H3 O+ reagent ions. The
increase in the H3 O+ abundance with the increase of the E/N ratio is
partly due to an increased breaking-up of water cluster ions. However, Smith et al. showed that another phenomenon can explain the
dependence of the H3 O+ level to the mean collision energy when
analyzing ethanol-containing solutions: H3 O+ reagent ions can also
result from ethanol fragmentation, as illustrated in Eqs. (2a) and
(2b) [17].
C2 H5 OH2 + H3 O+ + C2 H4

(2a)

C2 H5 OH2 + C2 H5 + + H2 O

(2b)

Eq. (2b) can explain the increase in m/z 29 fragment ions when
performing analyses at E/N ratios greater than 340 Td (Fig. 1). Concerning H2 OH3 O+ water cluster ions (m/z 37), their abundance
generally represented less than 2% of the total signal, even if a maximal proportion (around 57% of the total signal) was observed at
E/N values between 230 and 260 Td.
3.3. E/N ratio optimization
To ensure optimal conditions for sample quantitative analysis,
notably in presence of high amounts of ethanol, two main criteria can be used [12]: the depletion of H3 O+ reagent ions must
not exceed 5% during analysis, and the ratio between protonated
ethanol ions (m/z 47) and H3 O+ reagent ions (m/z 19) in the drift
tube must remain lower than 10%. Fig. 2 represents the depletion
percentage of the reagent ion according to sample ethanol content and to E/N values. A negative or positive percentage means
H3 O+ ion depletion or increase when analyzing ethanol-containing
samples, respectively. E/N values higher than 259 Td370 Td made

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G. Fiches et al. / International Journal of Mass Spectrometry 356 (2013) 4145

Fig. 2. Variations in H3 O+ ion intensity (m/z 19) between background and sample
signals during the analysis of 10, 20, 30 and 40% (v/v) ethanolwater solutions and
according to the variation of the E/N ratio (Td).

it possible to respect the 5% depletion criteria for 1040% (v/v)

ethanolwater solutions, respectively. The pertinence of the second
criterion can be discussed since it only takes the m/z 47 ion signal
into account, whereas for certain conditions (notably for E/N ratios
below 150 Td), three different ions from the ethanol coexisted with
similar abundances (m/z 47, 75 and 93) and may represent a large
proportion of the total signal (depending on headspace ethanol
concentration). With the objective of considering all species related
to ethanol, the percentage of the total signal represented by all
ions from ethanol was calculated. The ratio between the sum of
the intensities of all these ions and that of reagent ions was also
calculated. Since we considered the main ions from the ethanol
and not only m/z 47, it was decided to extend the 10% limit to
30%. The 30% value was selected since at standard operating conditions (used in [12]), the abundance of m/z 47 ions represented
almost 1/3 of the sum of abundances of ions m/z 47, 75 and 93.
With the objective of analyzing more complex beverages products
in future studies, we decided to select the lowest E/N value possible
in order to avoid excessive VOC fragmentations while respecting
dened criteria. Interesting E/N values for analyzing 10, 20, 30 and
40% (v/v) ethanolwater solutions were 256, 341, 341 and 454 Td,
respectively. In addition to criteria previously discussed, the distribution percentages per species must also be considered. For 40%
(v/v) ethanolwater solutions, for example, the main ion released
from the ethanol at 454 Td was the m/z 47 ion, which represented
12% of the total signal. Other species from the ethanol, m/z 29 and
m/z 27, only represented 6 and 2% of the total signal, respectively.
In consequence, they probably did not participate in the ionization
processes and thus did not complicate the nal mass spectrum.
4. Conclusions and perspectives
This work leads to the determination of operating conditions
for the analysis of the headspace above high ethanol-containing
beverages without any modication of the PTR-MS system. Results
showed that modications of the E/N ratio could be used to favor
the level of the reagent ion signal and to decrease ions from the
ethanol during headspace analyses of ethanol-containing beverages. Depending on the ethanol concentration in air in the drift
tube, the E/N ratio must be increased to achieve the desired conditions. Criteria must be dened to select appropriate operating
conditions, the most important point being to know and to control ionization conditions: it is notably essential to minimize the

number of reagent species and to favor the most abundant one (ideally, the one with the greatest proton afnity). Increasing E/N values
to analyze ethanol-containing samples can constitute a promising
technique, notably in the case of in vivo analysis, for which sample
dilution can be difcult to perform. Yet, some issues remain to be
claried. Maintaining the level of the H3 O+ reagent ion signal and
reducing the proportion of ethanol-based ions may take place at the
expense of greater fragmentation mechanisms. In consequence, the
usual fragmentation pattern of VOCs can be substantially modied
by the application of higher E/N ratios: higher ion kinetic energies can lead to a decrease in VOC detection on their protonated
molecular ion form and an increase in the proportions of lower
mass fragments could be observed. A predictable difculty is that
it could be even more difcult, especially in complex products, to
nd m/z product ions that could be specically or mainly related
to a unique parent molecule (the probability decreases with the
mass). In addition, PTR-MS detection linearity at high E/N values
also needs to be checked. These questions need to be investigated
in more details before applying this method to more complex alcoholic beverages for which numerous volatile compounds may be
released in the headspace, probably leading to high background
noise in the PTR-MS mass spectrum.
Acknowledgements
The authors thank Professor Jean Claude Tabet (Universit Pierre
et Marie Curie, Paris, France) for his expertise in ion chemistry and
for his invaluable support. The authors also thank Gail Wagman for
her precious help in checking the English spelling.
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