Atmos. Meas. Tech. Discuss.

, 2, 3099–3126, 2009 Atmospheric

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ment Techniques (AMT). Please refer to the corresponding final paper in AMT
if available.

A liquid nitrogen-free preconcentration

unit for measurements of ambient N2O
isotopomers by QCLAS
J. Mohn, C. Guggenheim, B. Tuzson, M. K. Vollmer, and L. Emmenegger
Laboratory for Air Pollution & Environmental Technology, EMPA, Dübendorf, Switzerland

Received: 12 November 2009 – Accepted: 26 November 2009 – Published: 4 December 2009

Correspondence to: J. Mohn (joachim.mohn@empa.ch)
Published by Copernicus Publications on behalf of the European Geosciences Union.

3099

Abstract

Important information about the biogeochemical cycle of nitrous oxide (N2 O) can
be obtained by measuring its three main isotopomers, 14 N15 N16 O, 15 N14 N16 O, and
14 14 16
N N O, and the respective site-specific isotope ratios δ 15 Nα and δ 15 Nβ . Absorp-
5 tion laser spectroscopy in the mid-infrared is a direct method for N2 O isotopomer analy-
sis, yet not sensitive enough for atmospheric N2 O concentrations (320 ppb). To enable
a fully-automated high precision N2 O isotopomer analysis at ambient concentrations,
we built and optimized a liquid nitrogen-free preconcentration unit to be coupled to a
quantum cascade laser (QCL) based spectrometer. Rigorous tests were conducted,
10 using FTIR and quantum cascade laser absorption spectroscopy (QCLAS), to investi-
gate recovery rates, conservation of isotopic signatures and spectral interferences af-
ter preconcentration. We achieve quantitative N2 O recovery of >99% with only minor,
statistically not significant isotopic fractionation and no relevant spectral interferences
from other atmospheric constituents. The developed preconcentration unit also has the
15 potential to be applied to other trace gases and their isotopic composition.

1 Introduction

Nitrous oxide (N2 O) is currently the most important anthropogenic ozone depleting
substance and exerts the third largest greenhouse warming potential (Ravishankara et
al., 2009). Since pre-industrial times, N2 O concentrations in the troposphere increased
−9
20 from 270 ppb (parts per billion, 10 molar) to the current level of 320 ppb at a rate of
−1
0.26% yr . The predominant sources of N2 O on a global scale are enhanced microbial
production in expanding and fertilized agricultural lands, as well as biomass and fossil
fuel burning. While the major sink, stratospheric destruction, is well quantified, the
strengths of N2 O sources remain largely uncertain (Solomon et al., 2007).
25 Important information about the biogeochemical cycle of N2 O can be obtained by
measuring the intramolecular distribution of 15 N in atmospheric N2 O (Billings, 2008;
3100
 Bernard et al., 2006; Ishijima et al., 2007; Rahn and Wahlen, 2000; Röckmann et al.,
2003; Röckmann and Levin, 2005; Yoshida and Toyoda, 2000). N2 O is a linear three-
atom molecule with one nitrogen atom in the centre (2 or α site) and one at the end
(1 or β site) which has four possible stable isotopic species with respect to nitrogen
14 14 16
5 isotopes. The most abundant N2 O isotopic species in the atmosphere are N N O
15 14 16 14 15 16
(99%), N N O (0.37%) and N N O (0.37%) (Werner and Brand, 2001; Yoshida
and Toyoda, 2000). Isotope abundances are usually reported in the δ-notation, where
δ 15 N denotes the relative difference in ‰ of the 15 N/14 N ratio of the sample versus the
reference material (atmospheric N2 ), analogically δ 15 Nβ denotes the corresponding
10 ratio for 15 N14 N16 O vs. 14 N14 N16 O.
The bulk nitrogen isotope ratio (δ 15 Nbulk = (δ 15 Nα + δ 15 Nβ )/2) of tropospheric N2 O
is enriched by approximately 7.0‰ relative to air-N2 , with a strong site preference
(SP=δ 15 Nα − δ 15 Nβ ) of 18.7‰ for the central nitrogen atom (Yoshida and Toyoda,
2000). Tropospheric N2 O concentrations and isotopic composition are largely con-
15 trolled by back injection of stratospheric N2 O as well as N2 O emissions from microbial
activity and combustion processes. In the stratosphere, the abundance of the heavier
isotopomers and the SP increases with altitude to values as high as 100‰ at 35 km,
mainly due to isotopic fractionation during UV-induced photolysis and oxidation, while
the N2 O mixing ratio decreases to 10–20 ppb (Toyoda et al., 2001). Isotopomer ratios
20 of different N2 O emission sources were found to vary largely between approx. −50‰
(soil) to 10‰ (coal combustion) for δ 15 Nbulk and −5‰ (soil) to 35‰ (ocean) for the
SP (Toyoda et al., 2009, and references therein). The required analytical precision for
15 α 15 β
δ N and δ N depends strongly on the application and may vary between <0.1‰
for firn air analysis to 1‰ for subsoil N2 O studies.
25 Currently, the only technique for N2 O isotopic measurements at ambient concentra-
tions is laboratory-based isotope-ratio mass-spectrometry (IRMS) in combination with
flask-sampling. However, isotopomers such as 14 N15 N16 O and 15 N14 N16 O cannot be
distinguished directly by IRMS, as they have the same mass. To determine the site-
15 + +
selective isotopic composition, the N content of the NO and N2 O ions has to be
3101

analyzed (Brenninkmeijer and Röckmann, 1999; Toyoda and Yoshida, 1999). There-
fore, the masses m/z 44, 45, and 46 (for N2 O) and m/z 30 and 31 (for NO) are mon-
itored either simultaneously (on last generation IRMS) or after two separate sample
injections. Although IRMS is a well-known method with excellent precision (0.05‰–
5 0.9‰) and accuracy (Röckmann and Levin, 2005; Well et al., 2008; Yoshida and Toy-
oda, 2000), it has some disadvantages such as the large size of the instrument, which
hinders field measurements. The required field sampling and sample storage strongly
limits its use for the characterization of variations in N2 O isotopic species at time-scales
relevant to many environmental processes.
10 Laser spectroscopy is a valuable alternative, because compact and continuously-
operating instruments can be developed that allow for extended field measurements.
This offers the possibility for process studies and opens a completely new field of ap-
plications. Furthermore, the method is inherently selective, even for molecules with the
same mass, because it is based on the highly characteristic rotational-vibrational tran-
15 sitions of the different N2 O isotopomers. The absorption lines of the various species
can be easily resolved at low cell pressure. However, there are only a few spectroscopic
measurements on isotope ratios of N2 O, and these were performed on pure N2 O sam-
ples (Gagliardi et al., 2005; Nakayama et al., 2007; Uehara et al., 2001, 2003) with the
exception of two recent studies (Wächter et al., 2008; Wächter and Sigrist, 2007). The
20 reported precisions range between 0.2‰ and 9‰.
Recent advances in laser technology provided a new class of mid-infrared (IR) semi-
conductor lasers: the unipolar intersubband quantum cascade lasers (QCL). They have
the advantage of operating at non-cryogenic temperatures (quasi room-temperature)
with high spectral purity and relatively high power output (Faist et al., 1994). The ap-
25 plication of these light sources for high-precision isotope ratio measurement has been
recently demonstrated for CO2 by Nelson et al. (2008) and Tuzson et al. (2008a, b).
Spectroscopy in the mid-IR region is particularly effective for molecules that exhibit
strong fundamental vibrations, such as CO2 and N2 O, with line intensities about two
orders of magnitude higher than in the near-IR. We recently demonstrated a precision

3102
 of 0.5‰ for δ 15 N at N2 O concentrations of 90 ppm (Wächter et al., 2008) using a pulsed
QCL emitting at 4.6 µm (Alpes Lasers, Switzerland). Atmospheric N2 O concentrations
(320 ppb), however, are more than two orders of magnitude lower and are therefore
currently not accessible for direct isotopic analysis by laser spectroscopy.
5 For these reasons we suggest to combine laser spectroscopy with preconcentration
techniques to increase N2 O concentrations from ambient levels to ∼60 ppm. The de-
veloped custom-built preconcentration unit enables us to make use of the precision and
site specificity of QCLAS at a temporal resolution of approx. 30 min. The preconcentra-
tion technique we employ is fully automated and is based on a commercial closed-loop
10 cryogenic unit and thereby free of consumables like liquid nitrogen. Here we describe
the most important properties that were obtained through systematic optimization and
characterization: (a) excellent recovery of N2 O and other trace gases; (b) conservation
of the N2 O isotope ratios, and (c) negligible impact of other atmospheric constituents
(e.g. CO2 , H2 O, CO, O3 , CH4 and C2 H2 ) on the analyzed N2 O isotopomer ratios. Our
15 results also indicate that the coupling of preconcentration and laser spectroscopy may
be feasible for other trace gases and their isotopes (e.g. many VOCs, CH4 , CO).

2 Experimental

2.1 Instrumental

2.1.1 Preconcentration unit

20 The technology of our preconcentration unit is based on a previously developed system

called “Medusa” which was originally designed for halogenated compounds measure-
ments by gas-chromatography mass-spectrometry (Miller et al., 2008). We re-designed
and optimized the system for the preconcentration of N2 O isotopomers and their subse-
quent quantification by laser spectroscopy. One main reason to choose this system is
25 the combination of a relatively mild adsorbent trap with a low-temperature refrigeration
3103

◦
unit reaching <−150 C. Our preconcentration unit differs from “Medusa” by the follow-
ings: a simplified setup with two instead of five valves and one instead of two adsorbent
traps. Furthermore, all gas flows are regulated by mass flow controllers (MFC, Red-
y Smart Series, Vögtlin Instruments, Switzerland) and the complete preconcentration
5 unit is controlled and monitored by LabVIEW (National Instruments Corp., USA) pro-
gramming.
The instrument flow scheme is illustrated in Fig. 1, showing one particular position
of the valves (Valco Instruments Inc, Switzerland), which are used to isolate or com-
bine various sections of the sample pathways. The 6-port valve is equipped with an
10 elongated-groove rotor and driven by a multi-position actuator which enables more
than 2 valve positions. Rotating the 4-port valve will change the flow direction through
the HayeSep D trap. The preconcentration trap consists of stainless steel tubing
(ID 1.6 mm, OD 2.1 mm) filled with 200 mg HayeSep D (100–120 mesh, Hayes Sep-
arations Inc., USA) and coiled onto an aluminium tube standoff. The standoff is at-
15 tached to a copper base-plate cooled by the refrigeration unit (PCC: Polycold Compact
Cooler, Brooks Automation, USA), and located in a vacuum chamber. The trap reaches
◦ ◦
temperatures of ∼−150 C and can be heated resistively to >100 C, using a custom-
built trap heating unit coupled with an Omega PID controller (CN77354-C2, Omega
Engineering Inc., USA).
20 The operation sequence and parameter settings (e.g. flow rates, temperatures and
timing) of the preconcentration unit were optimized to obtain a sharp N2 O concentra-
tion profile during desorption. The principle of operation is described in the following
paragraphs (see Figs. 1 and 2).
After an initialization phase that sets all parameters to their starting values, the
25 HayeSep D trap is purged by back-flushing with 50 sccm (standard cubic centimetre per
◦
minute) of high purity synthetic air (79.5% N2 , 20.5% O2 ) and heated to approx. −50 C
(phase I). This phase assures the absence of residual N2 O on the preconcentration trap
and reproducible starting conditions but may be omitted during continuous operation to
improve the temporal resolution. After cooling the trap down to ∼−150◦ C, the loading

3104
 (phase II) is initialized by setting the sample gas flow to 500 sccm, flushing the lines
and rotating the 6-port valve to the loading position. H2 O and CO2 are removed from
TM
the measuring gas by a Nafion drier (MD-050-72S-1, PermaPure Inc., USA) and a
chemical trap filled with Ascarite (3 g, 10–35 mesh, Fluka, Switzerland) bracketed by
5 Mg(ClO4 )2 (2×3 g, Fluka, Switzerland). To purge residual gas molecules onto the trap,
a short post-flush with synthetic air is applied at the end of phase II. Rotating the 4-port
valve to position 2 (backward flow) and adjusting the flow of synthetic air to 50 sccm
◦
initiates the desorption (phase III). After setting the trap temperature to −50 C, an im-
mediate release of N2 O can be observed by FTIR spectroscopy (see Fig. 2). Finally, all
10 parameters and conditions are set back to their initial values.The duration of trap load-
ing (phase II) and desorption (phase III) are adjusted based on the desired/available
sample volume (standard procedure: 20 min at 500 sccm sampling flow results in 10 l
sample volume) and the desired N2 O output concentration, usually around 60 ppm for
high precision N2 O isotopomer analysis by QCLAS. The minimal desorption time for
15 quantitative N2 O recovery depends on the molar N2 O input and was determined by
on-line FTIR spectroscopy to be between 60 s for 140 nmol and 180 s for 4000 nmol
N2 O. Typically a 10 l ambient air sample is focused into 50 ml desorption volume, cor-
responding to a concentration factor of 200.

2.1.2 On-line FTIR concentration measurement

20 We employed a Nicolet Avatar 370 MCT spectrometer (Thermo Nicolet Corp., USA)
◦
equipped with a heated (40 C) low-volume (50 ml) flow-through gas cell with 1 m
pathlength (Model LFT-210, Axiom Analytical Inc., USA). An infrared spectrum with
0.5 cm−1 optical resolution was recorded every three seconds, and trace gas (N2 O,
CO, CH4 , CO2 and H2 O) concentrations were retrieved by classical least square fit-
25 ting in selected wavelength regions (Mohn et al., 2004; Mohn et al., 2008). Calibration
spectra were recorded under identical instrumental and spectroscopic conditions from
certified and diluted calibration gases or by continuous injection of liquids into nitrogen.
The detection limits (VDI, 1995) for the trace gases in the undiluted gas were: 100 ppb
3105

N2 O, 200 ppb CH4 , 1 ppm CO2 , 200 ppb CO, 10 ppm H2 O. The expanded standard un-
certainty for these components is around 10% (95% confidence level). The response
time (t95 ) for the experimental setup (sampling line, FTIR gas cell) was 55 s at the ap-
plied flow rate of 50 sccm and 13 s employing a fed-in flow of 450 sccm synthetic air in
5 front of the gas cell to determine the minimal desorption time of the preconcentration
unit.

2.1.3 Analysis of N2 O isotopomers by QCLAS

The QCL based spectrometer used in the present project is an improved version of
the instrument used by Wächter et al. (2008). The experimental setup consists of
10 a single-mode, pulsed quantum cascade laser emitting at 4.6 µm, a multipass ab-
sorption cell (optical path length 56 m, volume 500 ml; Aerodyne Research Inc., USA)
and a detection system with pulse normalization. Laser control, data acquisition and
real-time signal processing are performed by the TDLWintel software (Aerodyne Re-
search Inc., USA). The main updates include: (a) a new RT-QCL (Alpes Lasers SA,
15 Switzerland) with about 10 times more power and a considerably narrower line width
of 0.0068 cm−1 ; (b) a new generation thermo-electrically cooled detector (PVI-3TE-5,
Vigo System, PL) with a specific detectivity (D*) >1011 at 4.5–4.6 µm, coupled to a
miniaturized preamplifier and TEC-controller (MTCC-01, Vigo System, PL). The detec-
tor assembly is mounted on a water-cooled cold-plate, which maintains a stable heat-
◦
20 sink temperature of 15±0.1 C. Further improvements were achieved by redesigning
the laser current and temperature control unit, optimizing the laser pulser electronics
and the 3-D-alignment stage of the collimating optics for a better alignment stability.
The selected absorption lines for this study are shown in Fig. 3. They are located
within the scanning range of the laser and have sufficiently strong line strength with
25 similar absorbance for each isotopic species. Mixing ratios for the different species are
obtained by simultaneously fitting a low-order polynomial to the spectral baseline and a
Gaussian-convoluted Voigt profile to the observed absorption lines, taking into account
the measured path length, gas temperature (∼307 K), pressure (8 kPa) and laser line
3106
 width. For the site-specific isotope ratios δ 15 Nα and δ 15 Nβ , a precision of 0.2–0.3‰
was obtained at 90 ppm N2 O using the Allan variance approach (Werle et al., 1993,
data not shown). N2 O concentration measurements (Sect. 2.2.1) were performed at
−1
2188.19 cm . The QCL spectrometer was operated with a continuous input gas flow
5 of 50–70 sccm.

2.2 Validation of N2 O preconcentration unit

To validate the N2 O preconcentration unit, tests were performed on the quantitative

recovery of N2 O and other trace gases (Sect. 2.2.1), on the conservation of the N2 O
isotope ratios (∆δ 15 N=δ 15 Nprecon -δ 15 Noriginal ) (Sect. 2.2.2), and on the composition of
10 preconcentrated ambient air and its potential interferences with N2 O isotopic analysis
(Sect. 2.2.3).
To investigate the trace gas recoveries and isotopic fractionation effects, gas mix-
tures with known concentrations and/or isotopic composition were prepared from stan-
dard reference gases by dynamic dilution with synthetic air (N2 O<0.3 ppb) and/or pres-
15 surized air using a pair of MFCs. Standard reference gases applied include 9.0 ppm
and 90 ppm N2 O in synthetic air (Messer Schweiz, Switzerland) to determine the trace
gas recoveries and gravimetrically prepared 90.8 ppm N2 O in synthetic air with known
15 α 15 β
isotopic composition (δ N = δ N =25.4‰ versus medical grade N2 O) to investigate
the conservation of the N2 O isotope ratios (Wächter et al., 2008). Table 1 summarizes
20 the gas mixtures used during the various validation experiments. For the study of
spectral interference we relied on ambient air sampled with a membrane pump (PTFE
coated membrane, N 035 AT.18, KNF Neuberger, Switzerland).

3107

2.2.1 Trace gas recovery

For the determination of the trace gas recovery, 1 to 10 l of a gas mixture were supplied
at a flow rate of 100 sccm, containing N2 O, CH4 and CO at ambient concentrations and
H2 O and CO2 at sub-ambient concentrations (Table 1). While these tests were based
5 on the standard preconcentration procedure, no chemical trap was employed to in-
vestigate the influence of H2 O and CO2 traces on the N2 O adsorption. On-line FTIR
measurements were performed to obtain time-resolved information on the trace gas
concentrations desorbed from the HayeSep D trap. The molar amount of desorbed
trace gases were calculated as the integrals over time of the output trace gas concen-
10 trations and the flow rates of synthetic air applied for desorption. The chosen approach
has the advantage of analyzing the recovery for different trace gases under standard
operation conditions but does not allow a highly precise budgeting because it relies on
a fast integration over a wide concentration range and on MFCs and gas flows that are
different during adsorption and desorption.
15 To achieve an even better precision for the determination of the N2 O recovery, a sec-
ond approach was used. These further experiments were designed to yield the same
concentration before and after the preconcentration step due to the use of the same
MFC (MFC2) and flow parameters (2400 s and 100 sccm) during adsorption and des-
orption, and by collecting the desorbed sample in a 10 l Tedlar bag (Product No. 245-08,
20 SKC Inc., USA). The sample gas was dynamically diluted from a tank, containing either
9.0 or 90 ppm N2 O in synthetic air, with synthetic air to ambient (350 ppb), intermedi-
ate (900 ppb) or process (9.0 ppm) concentrations (Table 1). N2 O concentrations in the
sample gas and in the desorbed sample (Tedlar bag) were compared based on QCLAS
−1
at 2188.19 cm . Experiments at every concentration were replicated thrice. Small dif-
25 ferences (<1%) between the adsorbed and desorbed gas volumes, as recorded by
LabVIEW from the MFC output, were corrected.

3108
 2.2.2 Isotopic fractionation

To validate the conservation of isotopic signatures, a N2 O reference gas (90.8 ppm

15 α 15 β
N2 O) with known isotopic composition (δ N = δ N =25.4‰ versus medical grade
N2 O) was diluted using high-purity synthetic air prior to preconcentration, followed by
5 Tedlar bag sampling and QCLAS analysis (Table 1). Ambient (350 ppb), intermediate
(900 ppb) and process (9.0 ppm) N2 O concentrations were deployed for preconcentra-
tion. The standard preconcentration procedure was applied with an adsorption flow
rate of 500 sccm during 20 min and 50 sccm (60–150 s) desorption flow. At elevated
N2 O input concentrations (9.0 ppm) the desorbed sample gas was dynamically diluted
10 by 1:10 during desorption as a fed-in flow, resulting in concentrations of ∼60 ppm for all
experiments. A series (n=5−70) of preconcentration cycles were pooled in one Ted-
lar bag to obtain a gas sample of 3 to 5 l. Experiments at every concentration were
replicated three to five times.
The N2 O isotopic composition of these samples after preconcentration was com-
15 pared to the same reference gas diluted with synthetic air to a comparable N2 O
15 15 15
concentration (±1 ppm) to calculate ∆δ N =δ Nprecon − δ Noriginal . All measure-
ments (n=4−8) were done on a relative scale using medical grade N2 O (91.1 ppm
15 α 15 β
N2 O) which we define as δ N = δ N =0‰ and a gravimetrically prepared enriched
15 α 15 β
gas (90.8 ppm N2 O, δ N = δ N =25.4‰ versus medical grade N2 O) for calibration
20 (Wächter et al., 2008).

2.2.3 Spectral interference

To evaluate potential spectral interferences from ambient air, samples were taken
through a 5 m, 6 mm outer diameter PTFE tube from outside the laboratory build-
ing. The corresponding trace gas concentration values were taken from the routine
25 measurements at the ∼300 m distant station Dübendorf of the Swiss National Air
Pollution Monitoring Network (NABEL). Where no NABEL data were available (N2 O

3109

and CO2 ), we assumed typical ambient concentrations as shown in Table 1. The

standard preconcentration procedure (Sect. 2.1.1) was followed, and the desorbed
gaseous species were analyzed either continuously (O3 , N2 O, CO2 , H2 O, CH4 , CO)
or after Tedlar bag sampling (C2 H2 , O2 ). Continuous data after preconcentration were
5 obtained by FTIR (Sect. 2.1.2) for N2 O, CO2 , H2 O, CH4 , and CO. Ozone was measured
using an UV absorption O3 analyzer (TEI 49C, Thermo Fisher Scientific Inc., USA) af-
ter dynamic dilution with synthetic air. Oxygen was determined with an O2 analyzer
(Servomex 570A, Spectris plc, UK), and acetylene concentrations were obtained us-
ing a GC-FID (Agilent 6890 with Plot Al2 O3 (KCl) column) after preconcentration with
10 a Peltier cooled HayeSep D trap. The concentrations and corresponding preconcen-
tration factors were then used to simulate absorption spectra and evaluate possible
spectral interferences.

3 Results and discussion

3.1 Trace gas recovery

15 Quantitative recovery of the adsorbed trace gases is a prerequisite to assure the rep-
resentativeness of the analyzed gas sample and to avoid fractionation effects. Two
different approaches were chosen to tackle this subject: (i) determination of the trace
gas recovery with increasing adsorption volume to examine the trap capacity (Fig. 4);
(ii) high-precision recovery of N2 O at different concentration levels (Table 2).
20 The capacity of the adsorbent trap for different trace gases was evaluated based on
a sequence of experiments where 1 to 10 l of a gas mixture with constant composition
(see Table 1) were first adsorbed on the preconcentration trap and then desorbed with
a flow of 50 sccm of synthetic air and analyzed by on-line FTIR spectroscopy. For
every trace gas the molar amounts in the input and output gas volume were calculated,
25 integrating over time the respective concentrations and gas flows.

3110
 The CO concentration in the output flow was below the FTIR detection limit of
200 ppb and the amount of desorbed CH4 was nearly constant and did not depend
on gas sample volume (Fig. 4). This indicates that the mild adsorbent HayeSep D
◦
does not quantitatively retain CH4 and CO at a trap temperature of approx. −150 C
◦ ◦
5 which is above their respective boiling points of −161 C and −191.5 C.
For high precision N2 O isotopomer analysis by QCLAS the loss of CO is an advan-
tage because of its absorption in the selected spectral region. The application of the
preconcentration unit for CO and CH4 may still be envisaged by employing a stronger
adsorbent (i.e. Molsieve 5Å) or an alternative refrigerant reaching a lower adsorption
10 temperature.
As shown in Fig. 4, for N2 O and CO2 a linear relation in the molar amounts be-
tween the trap output and the sample volumes was obtained, with expanded standard
uncertainties for the regression lines of less than 1%. The linearity holds for the full
investigated range, while the slight deviation from unity of 2% to 6%, is well below the
15 uncertainty due to potential systematic offsets in the input and output gas concentration
measurements by FTIR or in the input and output gas flows.
The efficiency of N2 O recovery is critical, because the adsorption/desorption pro-
cesses may lead to significant isotopic fractionation (Bertolini et al., 2005; Brand, 1995;
Werner et al., 2001). Therefore, a second, more precise approach was applied which
20 allows the direct comparison of the sample gas before and after preconcentration by
precise QCLAS measurements (Sect. 2.2.1). Using this experimental setup, the in-
put and output concentrations agreed within 0.2% at ambient (350 ppb), intermediate
(900 ppb) and process levels (9.0 ppm) (Table 2). Apart from the standard deviation for
repetitive measurements, systematic deviations from e.g. subtle differences between
25 the adsorbed and desorbed gas volumes cannot be excluded. However, such effects
are considerably smaller than 1%, corresponding to a >99% recovery and thus, we
expect only minimal, if any, isotopic fractionation.

3111

3.2 Isotopic fractionation

To further confirm the conservation of isotopic signatures the isotopic composition

of samples at ambient (350 ppb), intermediate (900 ppb) or process concentrations
(9 ppm) were compared before and after preconcentration as described in Sect. 2.2.2.
5 All experiments were done with gases that were enriched in δ 15 Nα and δ 15 Nβ at a level
of 25.4‰.
Agreement of the N2 O isotopic composition with/without preconcentration was in
15 α
general very good (see Table 3). The δ N isotope ratio of N2 O after preconcentration
are within 0.1‰ with the unprocessed calibration gas. For δ 15 Nβ , the data seems
15 β
10 to indicate a slight increase in the δ N values after preconcentration, particularly
at lower N2 O input concentrations. The uncertainty of the mean values is however
rather large, and in a one-sided student’s t-test the effect is not significant at the 0.05
significance level. We, nevertheless, plan to repeat the experiments in the future with
the next generation of QCLAS and a directly coupled preconcentration unit. It should
15 also be noted that the calibration routine will include the preconcentration step and can
thus be expected to largely account for small fractionation effects if they really occur.

3.3 Spectral interference

At the precision levels needed for N2 O isotope ratio analysis, even very weak spectral
interferences of other compounds may be detrimental. To analyze spectral interfer-
20 ences of ambient air constituents the following approach was applied: (i) identification
of molecular species (based on HITRAN database) that may cause spectral interfer-
ences through their absorption features; (ii) quantitative analysis of these components
after preconcentration of ambient air, and (iii) assessment of spectral interferences
based on spectral simulations.
25 Although the chosen absorption lines are free of any strong or obvious interferences,
we have considered all molecules in the HITRAN database (Rothman et al., 2005) for
lines in the relevant wavelength region. The line strengths of the relevant molecules are
3112
 plotted in Fig. 5(b), weighted for their ambient molecular abundance (Table 1). Based
on this abundance weighted representation, the most relevant interfering compounds
are H2 O and CO2 , followed by CO, O3 and C2 H2 . Apart from its spectral interference,
the water content in the measuring gas has to be reduced considerably to avoid clog-
5 ging of the adsorption trap. This is accomplished by permeation drying and Mg(ClO4 )2 ,
while CO2 is largely removed by the Ascarite trap. For the other gas compounds, the
preconcentration procedure is quite selective, as will be shown below.
Concentrations of H2 O and CO2 were efficiently reduced during preconcentration,
below their FTIR detection limits of 10 and 1 ppm, respectively. Both H2 O and CO2
10 were shown to be efficiently removed by chemical trapping with Mg(ClO4 )2 and As-
carite to ppm or even ppb levels, respectively (Röckmann and Levin, 2005; Mohn et
al., 2007). The average ozone output concentration was only about six times the am-
bient concentration which corresponds to a 3% recovery, assuming a concentration
factor of 200. This can be expected because ozone is subject to rapid decomposition
15 during desorption at hot metal surfaces. CH4 and CO are not efficiently trapped by the
preconcentration unit, due to their low boiling points, as reflected by a breakthrough of
>98%. The C2 H2 output concentration was around 125 ppb, which would correspond
to an input concentration of 0.62 ppb assuming a quantitative recovery. This value is
in-between the annual average C2 H2 concentrations observed at the remote NABEL-
20 station Rigi-Seebodenalp and the urban station Zurich with 0.4 and 1.0 ppb (FOEN and
EMPA, 2009), respectively, which is in accordance with the suburban character of the
sampling station Dübendorf.
O2 and N2 are to a large extent lost during trapping. The remaining bulk gases
increased the O2 /N2 ratio by 2–3% in the synthetic air employed for desorption, most
25 probably due to the larger N2 loss during trapping as a result of the difference in boiling
◦ ◦
points of −183.0 C and −195.8 C of O2 and N2 , respectively. This slight change in
the gas matrix should, however, not have any significant effect on the isotope ratio
measurements since the reference gases will also be supplied in synthetic air and
treated similarly.

3113

A hypothetical absorption spectrum was generated, based on the analyzed

output concentrations and typical conditions employed for QCLAS measurements
(Sect. 2.1.3). To obtain a meaningful representation, the spectrum of preconcentrated
ambient air was multiplied by a factor of 1000 (Fig. 5), reflecting the required precision
5 for the N2 O isotopomer ratios in the sub-per mille range. The only relevant signals
might be due to very weak O3 , CO and C2 H2 absorption. The resulting effect on the
isotopomer concentrations is, however, below 1% (even with a 1000× magnification)
in a typical retrieval of concentrations from measured spectra, which translates into a
shift of less than 0.01‰ on the δ-scale.

10 4 Conclusions

We built, optimized and validated a liquid nitrogen-free fully-automated preconcentra-

tion unit to increase N2 O concentrations by a factor of 200 from ambient levels to
about 60 ppm. The key element is the combination of a relatively mild adsorbent with
a low temperature refrigeration unit, achieving trapping temperatures of approximately
◦
15 −150 C. During standard operation, 140 nmol of N2 O are adsorbed from 10 l of am-
bient air within 20 min and desorbed in 50 ml of high purity synthetic air. The valida-
tion experiments showed quantitative N2 O recovery with only minor, statistically not
significant isotopic fractionation, and negligible spectroscopic interferences from other
atmospheric constituents on the analyzed N2 O isotopomer ratios.
20 Based on these encouraging results we intend to directly couple the preconcentration
15
unit to a QCL spectrometer to permit fully-automated high precision (<0.5‰ for δ N)
N2 O isotopomer analysis at ambient concentrations (∼320 ppb) with a temporal resolu-
tion of less than 30 min. Expected spectroscopic improvements, e.g. using continuous
lasers and/or spectral ratio methods will provide enhanced precision without signifi-
25 cant modifications in the instrumental setup. Future modifications of this basic setup
may permit to analyze other trace gases that are not directly accessible by currently
available spectroscopic techniques (i.e. many VOCs) and to quantify isotopologues of
3114
 substances at relatively low concentrations, such as CH4 , CO and organic compounds
by employing a stronger adsorbent (i.e. Molsieve 5Å) or an alternative refrigerant reach-
ing a lower adsorption temperature.
Acknowledgements. We acknowledge the support of Matthias Hill, Angelina Wenger and Ben-
5 jamin R. Miller for the construction of the preconcentration unit, based on their extensive knowl-
edge of the original “Medusa” for GC-MS. Wilhelm Gutjahr helped to conduct the numerous
experiments needed to optimize the experimental conditions. Davide Ferri provided the FTIR
gas cell, and Erwin Pieper and Willy Knecht contributed with their competence in mechanical
design and electronics.

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3118
Table 1. Trace gas concentrations and N2 O isotopic composition (δ reference point: medical
grade N2 O).

N2 O δ 15 Nα δ 15 Nβ CO2 CH4 CO O3 H2 O
[ppm] [‰] [‰] [ppm] [ppm] [ppb] [ppb] [ppm]
trace gas recovery1 0.39 n.a n.a 35 2.0 350 – 25
0.35 n.a. n.a. – – – – –
0.90 n.a. n.a. – – – – –
9.0 n.a. n.a. – – – – –
isotopic fractionation2 0.35 +25.4 +25.4 – – – – –
0.90 +25.4 +25.4 – – – – –
9.0 +25.4 +25.4 – – – – –
spectral interference3 0.35 n.a. n.a. 400 2.0 200–450 62–65 1–2%

n.a.: not analyzed

1
gas mixtures prepared from 9 or 90 ppm N2 O reference gas and synthetic air; line 1: addi-
tionally with pressurized air and concentrations determined by FTIR.
2
gas mixtures prepared from a 90.8 ppm N2 O reference gas with known isotopic composition
and synthetic air.
3
ambient air; N2 O and CO2 concentrations based on estimates, all other concentrations taken
from routine measurements of the Swiss National Air Pollution Monitoring Network (NABEL).

3119

Table 2. High-precision recovery of N2 O after preconcentration (n=3). Error bars represent the
expanded uncertainty (95% confidence level).

N2 O input concentration Recovery [%]

350 ppb 100.1±0.1
900 ppb 100.2±0.4
9.0 ppm 100.0±0.1

3120
 15 15 15
Table 3. Changes in the N2 O isotopomer ratios (∆δ N=δ Nprecon − δ Noriginal ) after dilution
and preconcentration compared to the unprocessed calibration gas (n=3−5). Error bars repre-
sent the expanded uncertainty (95% confidence level).

15 α 15 β
N2 O input concentration ∆δ N ∆δ N
[‰] [‰]
350 ppb 0.06±0.31 0.34±0.52
900 ppb 0.08±0.42 0.19±0.40
9.0 ppm −0.05±0.38 0.07±0.80

3121

nafion
counterpurge to FTIR or
Tedlar bag + QCLAS
adsorption 4-port
dryer valve nafion 2
MFC 2

desorption in
synth. air

P sensor
6-port
dry gas out valve
vent
filter

MFC 1
H2O + CO2 removal
nafion 1

vacuum on/off
gauge valve
MFC 3 adsorbent trap diffusion
T ~ -150 °C pump
N2O ref

measuring gas in
pressure

backing
release

PCC pump
cold end vacuum
MFC 4 chamber
synth. air

compressor
preconcentration unit
unit

Fig. 1. Process chart during trap loading (phase II) with N2 O in synthetic air.

3122
 600 60

MFC1 [sccm]

MFC2 [sccm]
400 MFC1: sample gas 40
MFC2: synthetic air (purge, desorb)

200 20
(a)
0 0

trap temperature [°C] valve position

3
6-port: 1 trap isolated, 2 in-line
2 with 4-port valve, 3 loading
4-port: 1 forward flow, 2 backward
1
(b)
0
-50

-100

-150
(c)
-200
Phase I: Phase II: Phase III:
N2O [ppm]

150 Conditioning Loading Desorption

100

50
(d)
0

0 500 1000 1500 2000

time [s]

Fig. 2. Typical N2 O adsorption/desorption process (adsorption of 500 sccm of 350 ppb N2 O in

synthetic air; 10 l sample volume) with preceding trap conditioning: (a) sample gas flow (MFC1)
and flow of synthetic air (MFC2); (b) position of 6-port and 4-port valves; (c) trap temperature;
(d) N2 O concentration profile as analyzed by on-line FTIR spectroscopy.

3123

-3
60x10
(a)
50

40
Absorbance

30

20

10

0
-18
Line strength [cm /(molecule cm ]
-2

10
(b)

-19
10
15 14 16 14 15 16 14 14 16
N N O N N O N N O
-20
-1

10

-21
10

-22
10

2187.8 2187.9 2188.0 2188.1

-1
Wavenumber [cm ]

Fig. 3. (a) Measured (dots) and fitted spectrum (solid line) of the N2 O isotopes at 90 ppm
and (b) the corresponding line strengths. The tail of a strong absorption line of 14 N14 N16 O
−1 −1
(2188.19 cm ) is clearly visible and was considered in the fit up to 2188.1 cm .

3124
 200
(a)
150

100

50
CH4
0
200 400 600 800 1000
200
0
-200
3
20x10
(b)
Output [nmol]
15
10
5
CO2 out [nmol] = (29.6±57.2) + (1.054±0.012) x CO2 in [nmol]
0
3
5 10 15 20x10
2.0
0.0
-2.0
200
(c)
150
100
50
N2O out [nmol]= (-0.66±0.42) + (0.982±0.004) x N2O in [nmol]
0
0 50 100 150 200
Input [nmol]

Fig. 4. Amount of (a) CH4 , (b) CO2 , and (c) N2 O concentrated on the HayeSep D trap de-
pending on the sample volume from 1 to 10 l (adsorption: 100 sccm of 390 ppb N2 O, 35 ppm
CO2 , 2.0 ppm CH4 , 350 ppb CO, 25 ppm H2 O in 80% N2 and 20% O2 ). Error bars represent the
expanded standard uncertainty. For CO2 and N2 O deviations from linearity are given in nmol.

3125

-3
100x10 60 ppm N2O
(a)
gas matrix after preconcentration (x 1000)
80
Absorbance

15 14 16 14 15 16 14 14 16
60 N N O N N O N N O

40

20

0
Abundance weighted line strength

-24
10
(b) N2O H2O CO2 CO
-25
(cm /molecule cm )

10
-2

O3 C2H2 CH4
-26
10
-27
10
-28
10
-29
-1

10
-30
10
-31
10
-32
10
2187.7 2187.8 2187.9 2188.0 2188.1
-1
Wavenumber [cm ]

Fig. 5. (a) Simulated absorption spectra of N2 O and preconcentrated ambient air (magnified
by a factor 1000). (b) Absorption lines of atmospheric constituents in the wavelength region
selected for N2 O isotopomer analysis.

3126