ADVANCES IN ATMOSPHERIC SCIENCES, VOL. 27, NO.

6, 2010, 1322–1330

A New Carrier Gas Type for Accurate

Measurement of N2O by GC-ECD
WANG Yinghong ( ), WANG Yuesi∗ ( ), and LING Hong (  )
State Key Laboratory of Atmospheric Boundary Layer Physics and Atmospheric Chemistry,

Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing 100029

(Received 2 December 2009; revised 29 January 2010)

ABSTRACT
The accurate measurement of concentration is the basis for determining emission sources and sinks of
nitrous oxide (N2 O). The detection of N2 O showed that the presence of carbon dioxide (CO2 ) biased the
N2 O response when pure nitrogen (N2 ) was used as a carrier gas for gas chromatography (GC) equipped with
an electron capture detector (GC-ECD). In this study, laboratory experiments were carried out to explore
how the presence of CO2 interferes with the accurate determination of N2 O. The aims were to address the
extent of the influence to try and explain the underlying mechanism, and to uncover technical options for
solving the problem. Three GC carrier gases are discussed: pure nitrogen (DN); a mixture of argon and
methane (AM); and a high concentration CO2 , which was introduced into the ECD cell with a low flow rate
based on DN (DN-CO2 ). The results show that when DN was used, the existence of CO2 in the ECD cell
greatly enhanced the response of N2 O, which increased with CO2 content and remained constant when the
content reached a limit. Comparisons between the three methods show that the DN method is defective for
the accurate determination of N2 O. The bias is caused by different electron capture mechanisms of CO2 and
N2 O and depends heavily on the detector temperature. New GC carrier gas types with make-up gases that
can remove the CO2 -induced influence, such as the DN-CO2 and DN-CH4 methods reported in this paper,
are recommended for the accurate measurement of N2 O.
Key words: nitrous oxide, gas chromatography, electron capture detector, carbon dioxide, overestimation
Citation: Wang, Y. H., Y. S. Wang, and H. Ling, 2010: A new carrier gas type for accurate measurement
of N2 O by GC-ECD. Adv. Atmos. Sci., 27(6), 1322–1330, doi: 10.1007/s00376-010-9212-2.

1. Introduction worth and Freeman, 1973; Mosier and Mack, 1980;

Arah et al., 1994; Loftfield et al., 1997; Hadi et al.,
Nitrous oxide (N2 O) is one of the most important 2000; Wang and Wang, 2003; Butterbach-Bahl et al.,
long-lived greenhouse gases in the atmosphere. It con- 2004; Akimoto et al., 2005). Another type is based
tinues to rise approximately linearly (0.26% yr−1 ) and on closed-path tunable diode laser infrared absorption
reached 319×10−9 mol mol−1 in 2005 (Forster et al., spectroscopy analyzers (De Klein et al., 1999; Edwards
2007). Studies show large uncertainty in N2 O sources, et al., 2003; Pattey et al., 2006; Phillips et al., 2007),
such as soil, agriculture, combustion, and the sea. and the third on long open-path and Fourier trans-
These studies are all reliant upon the accurate mea- form infrared spectroscopy (Hashmonay et al., 2001).
surement of atmospheric N2 O concentration, what- Among them, GC-ECD is the most mature and stable
ever the long-term variation, and source distribution technique, demonstrating a high level of precision and
or emission uncertainty. is applied widely. The majority of available data con-
In general, there are three kinds of technology ap- tributing to present global or regional inventories were
plied in the measurement of N2 O concentration. First, obtained by this method.
N2 O content can be analyzed with gas chromatogra- As a sensitive detector, ECD has been used for de-
phy (GC) equipped with an electron capture detec- termining N2 O concentrations since the 1970s (Went-
tor (ECD), known as the GC-ECD method (Went- worth and Freeman, 1973; Mosier and Mack, 1980).
∗ Corresponding author: WANG Yuesi, wys@dq.cern.ac.cn, wys@mail.iap.ac.cn
© China National Committee for International Association of Meteorology and Atmospheric Sciences (IAMAS), Institute of Atmospheric
Physics (IAP) and Science Press and Springer-Verlag Berlin Heidelberg 2010
NO. 6 WANG ET AL. 1323

However, the detailed mechanism of ECD is not very 2. Material and methods
clear, even today. Different types of carrier gas affect
the stability and sensitivity of ECD. High purity N2 , 2.1 Instrumental methods
high purity Ar and Ar-CH4 , a mixture of argon and
A HP5890II GC system (Hewlett Packard, Palo
methane, have been most commonly used as carrier
Alto, California, USA) equipped with an ECD was
gases for ECD. Maggs et al. (1966) proved that using
used to measure N2 O. Two stainless steel columns were
Ar-CH4 can provide higher ECD sensitivity than N2
used to separate N2 O, both the precolumn (length,
or Ar. Although N2 does not give the best sensitiv-
1 m) and the main column (length, 3 m) were packed
ity for ECD analysis, it has still been widely adopted
with Porapak Q. An oven temperature of 55◦ C and
because of certain advantages, such as its inexpensive-
a carrier gas flow rate of 35 mL min−1 were applied.
ness, its convenience in terms of supply, its safety in
CO2 concentrations were analyzed using the Agilent
transportation, and its compatibility with other detec-
6820 GC-FID system (Agilent Technologies Limited
tors like the flame ionization detector (FID). In fact,
Co., Shanghai, China) coupled with a nickel catalytic
approximately one-third of all published research on
converter.
the measurement of N2 O used N2 as the carrier gas
The carrier gas methods used were (1) high purity
of the ECD. However, Zheng et al. (2008) reported
N2 , written as DN hereafter; (2) Ar-CH4 , a mixture
that when they used N2 as the carrier gas of the ECD,
gas with 10% CH4 in argon, written as AM hereafter;
N2 O concentrations were generally overestimated in
and (3) N2 -CO2 , high purity N2 as the carrier gas and
the presence of elevated CO2 . Unfortunately, most
a mixture gas (10% CO2 in N2 ) introduced into the
laboratories worldwide are not aware of the potential
ECD with a 2 mL min−1 flow rate as the make-up
interference between CO2 and N2 O when using N2 as
gas, written as DN-CO2 hereafter.
the carrier gas. This has significant implications for
Series gases were employed in the experiments: (a)
existing estimates of N2 O emissions from terrestrial
standard gases with N2 O concentrations at 94×10−9,
systems, since CO2 interference with N2 O may have
137×10−9, 330×10−9 and 520×10−9 mol mol−1 ; (b)
positively biased many flux measurement results. In
dry ambient air with N2 O and CO2 concentrations of
this paper, experiments were designed to explore how
330×10−9 mol mol−1 and 403×10−6 mol mol−1 , re-
the presence of CO2 interferes with the accurate de-
spectively; and (c) the same dry ambient air as with
termination of N2 O. Different carrier gases were com-
(b), but with CO2 concentrations modified by the ad-
pared and a new carrier gas type is recommended for
dition of pure CO2 . As a small amount of pure CO2
accurate measurement of N2 O concentrations by GC-
gas (0.1–3 mL) was added to a large air volume (800
ECD.
mL), the resulting change in N2 O concentration was
negligible.

Table 1. An overview of the laboratory experiments.

Experiment Carrier gas type Make-up gas ECD temperature (◦ ) Gases series∗∗
concentration
in the ECD cell
(10−6 mol mol−1 )∗
1 DN-CO2 0–900 330 (a)
2 DN 230, 250, 270, (b)
290, 310, 330,
350
AM 250, 330
DN-CO2 1000 250, 330
3 DN 250, 290, 330, 380 (c)
AM 250, 290, 330, 380
DN-CO2 1000 330, 380

Note: ∗ Make-up gas: 10% CO2 in N2 ; ∗∗ (a) standard gases with N2 O concentration at 94×10−9 , 137×10−9 , 330×10−9 and
520×10−9 mol mol−1 ; (b) dry ambient air with N2 O and CO2 concentrations of 330×10−9 mol mol−1 and 403×10−6 mol mol−1 ,
respectively; (c) the same dry ambient air as (b) but with CO2 concentrations modified by the addition of pure CO2 . As a small
amount of pure CO2 gas (0.1–3 mL) was added to a large air volume (800 mL), the resulting change in N2 O concentration was
negligible.
1324 A NEW CARRIER GAS TYPE VOL. 27

2.2 Experiments
The laboratory experiments were designed to com-
pare (1) the ECD signals of N2 O at different CO2 con-
centrations in the ECD pool; (2) ECD signals of N2 O
and CO2 at different temperatures of ECD; and (3)
ECD signals of a fixed N2 O concentration to differing
CO2 concentrations under different methods of carrier
gas. Table 1 provides an overview of all the experi-
ments.
In Experiment 1, using the DN method, the ECD
temperature was kept at 330◦ C. A mixture gas (10%
CO2 in N2 ) was introduced into the ECD through the
make-up gas channel. The flow rate of make-up gas
could be adjusted by a controller from 0–4 mL min−1
and the CO2 content in the ECD pool changed from
0 to 1000×10−6 mol mol−1 . Gases eluted from the
ECD were collected at each make-up flow rate, and
actual CO2 concentrations were detected by the GC-
FID. Standard gases in series (a) were analyzed at each
make-up gas flow rate.
Under the DN method in Experiment 2, ECD tem-
peratures changed from 230◦ C to 350◦ C at intervals of Fig. 1. (a) GC-ECD-yielded nitrous oxide (N2 O) sig-
20◦ C. Dry ambient air was measured at different ECD nals peak area in response to the CO2 content in
ECD. Different symbols represent different given N2 O
temperatures (230◦ C, 250◦ C, 270◦ C, 290◦ C, 330◦ C,
concentrations in ECD, with ppb denoting 10−9 mol
and 350◦C). Dry ambient air was also analyzed at ECD mol−1 and the curves fit Michaelis-Menten equa-
temperatures of 250◦C and 330◦ C under the AM and tion: 94 ppb, y=32137.27x/(53.479 + x), r 2 =0.972;
DN-CO2 methods, respectively. 172 ppb, y=52937.46x/(40.61 + x), r 2 =0.967; 330
Finally, in RXN 3, gases of (c) series were mea- ppb, y=95346.61/(38.62 + x), r 2 =0.966; 520 ppb,
sured under the DN, AM and DN-CO2 methods at y=144133.2x/(37.27 + x), r 2 =0.963; (b) The CO2 limit
different ECD temperatures. When the ECD temper- caused constant N2 O response were decreased with the
ature was set to 250◦ C and 290◦C, only the DN and N2 O concentration.
AM methods were involved; and when the tempera-
ture rose to 330◦ C and 380◦C, the DN-CO2 method affected by the content of CO2 . When CO2 concen-
was added into the comparison. The precision of each trations ranged between 0 and 100×10−6 mol mol−1 ,
method was compared by dry ambient air, which was the N2 O signal increased quickly. However, the speed
analyzed for N2 O every five runs (n6, n is the repe- decreased with an increase in the content of CO2 and
tition number of ambient air). remained constant when the content reached a limit.
For example, the sample signal area of 330×10−9 mol
2.3 Statistical analysis mol−1 was 11 080 when the CO2 concentration was
The software package SYSTAT 5.0 (SPSS Inc., 10×10−6 mol mol−1 , increased to 72 900 when the con-
Chicago, USA) was used for statistical data analy- centration was 100×10−6 mol mol−1 , and remained
sis. The significance levels between any two GC–ECD stable at 88 000 when the concentration was larger
methods were determined using paired t-tests. than 400×10−6 mol mol−1 . The relationship between
the N2 O signal and CO2 content could be described by
the Michaelis-Menten equation, although there were
3. Results
different mechanisms behind the phenomena:
3.1 The influence of CO2 content in the ECD Y = (b1 × X)/(b2 + X) , (1)
pool on N2 O signals
where Y is the ECD response signal for N2 O, X is
Experiment 1 was designed to compare the ECD the CO2 content in the ECD, b1 is the maximum N2 O
signals of N2 O at different CO2 concentrations in the signal (Ymax ), and b2 is the CO2 content that caused
ECD pool. The results of Experiment 1 are shown in half of Ymax . The correlation coefficient (r2 ) of the
Fig. 1, which demonstrates that the N2 O signals were fitted equations were 0.972, 0.967, 0.966 and 0.963 for
NO. 6 WANG ET AL. 1325

N2 O concentrations of 94×10−9, 172×10−9, 330×10−9
and 520×10−9 mol mol−1 , respectively. According to
Eq. (1), for each N2 O concentration there is a Ymax
and a corresponding CO2 content limit resulting in
a constant signal at that particular N2 O level. It is
impossible to obtain the Ymax value according to the
equation; instead, a close value of 95% Ymax was used
to obtain the CO2 limit at each N2 O level. As Fig.
1b shows, with an increase in N2 O concentration, the
CO2 limit decreased.
This phenomenon shows that the CO2 content in
the ECD can affect the N2 O signals. Usually, the CO2
concentration of air samples varies from 380×10−6 to
2000×10−6 mol mol−1 ; it would be diluted to less than
50×10−6 mol mol−1 by the N2 in the ECD cell, which
can cause an abnormal increase of N2 O response. On
the other hand, the phenomenon also indicated that if
enough CO2 exists in the cell, a more stable and sen-
sitive response of N2 O will be obtained. The relation-
ship between N2 O concentrations and the response sig-
nal could be described by linear regression (r2 >0.999).
The response factor (Rf) where no CO2 was added into
the ECD was defined as the base; Rfs at different CO2
concentrations were compared with it and normalized
Rfs obtained. These normalized Rfs increased rapidly
from 1 to 8.31 when the CO2 concentration increased
from 0 to 51×10−6 mol mol−1 , then increased slowly
from 8.31 to 12.02 when CO2 increased from 51×10−6
to 369×10−6 mol mol−1 , and remained constant when
the CO2 concentration was higher than 400×10−6 mol
mol−1 .
Therefore, with N2 as the carrier, the authors intro-
duced 10% CO2 into the detector and made the CO2
content in the ECD cell greater than 1000×10−6 mol
mol−1 and obtained a new carrier type, DN-CO2 .
3.2 Influence of ECD temperature on ECD
response signals of CO2 and N2 O
The influence of ECD temperature on signals of
CO2 and N2 O was investigated in Experiment 2, and
the results are shown in Fig. 2. The responses of CO2
and N2 O signals were different as the temperature in-
creased. As Fig. 2 shows, the CO2 and N2 O in the
gas samples could be separated perfectly in the experi-
ment. For N2 O, the signal increased with temperature,
the response signal maintaining a positive linear corre-
lation with ECD temperature (y=2.865x−466.47,
r=0.99, n=6, p<0.001). For CO2 , when the ECD was

Fig. 2. Chromatograph signals of N2 O and CO2 in dry ambient air as a response to

different ECD temperatures under the DN method: (a) 230◦ C; (b) 250◦ C; (c) 270◦ C;
(d) 290◦ C; (d) 290◦ C; (e) 310◦ C; (f) 330◦ C; (g) 350◦ C. The concentrations of N2 O
and CO2 in dry ambient air were 330×10−9 mol mol−1 and 403×10−6 mol mol−1 ,
respectively. Both N2 O and CO2 peaks were detected by the ECDs. The solid arrow
points to the CO2 signal and the dashed arrow to the N2 O signal. Definition of the
DN method is provided in section 2.
1326 A NEW CARRIER GAS TYPE VOL. 27

Fig. 3. Chromatograph signals of N2 O and CO2 in dry ambient air as a response to different
methods at ECD temperatures of 250◦ C and 330◦ C. (a), (b) and (c) show results for a detector
temperature of 250◦ C in the DN, AM and DN-CO2 methods, respectively; (d), (e) and (f) for a
detector temperature of 330◦ C, again in the DN, AM and DN-CO2 methods, respectively. The
concentrations of N2 O and CO2 in dry ambient air were 330×10−9 mol mol−1 and 403×10−6 mol
mol−1 , respectively. Both N2 O and CO2 peaks were detected by the ECDs. Definitions of the DN,
AM and DN-CO2 methods are provided in section 2.

at lower temperatures (230◦ C–270◦C), a positive peak
appeared and the signal decreased with an increase in
temperature (Figs. 2a, 2b, 2c). When the tempera-
ture continued to increase (290◦ C–380◦C), the posi-
tive peak disappeared and was replaced by a negative
peak; the negative signal also increased slowly with
temperature (Figs. 2d, 2e, 2f). It is apparent that the
inherent response mechanisms of CO2 and N2 O in the
ECD were totally different.
Figure 3 shows the changes in the signals of CO2
and N2 O at lower (250◦ C) and higher (330◦ C) ECD
temperatures under the DN, AM and DN-CO2 meth-
ods. At lower temperatures, the ECD demonstrated a
good detection ability for CO2 , with a positive peak
under all three methods, as shown in Figs. 3a–3c. The
Rfs of CO2 at 250◦ C were 53.59, 29.82, 15.60 for DN,
AM and DN-CO2 , respectively; and the Rfs of N2 O
were 8.29, 32.07, 24.42 for DN, AM and DN-CO2 , re-
spectively. When the ECD temperature rose to 330◦ C,
it was incapable of detecting CO2 ; it had a negative
peak in the DN method, no peak in the AM method,
and a weak positive peak in the DN-CO2 method, as
shown in Figs. 3d–3f. However, the Rfs of N2 O were
enhanced to 29.01, 72.96 and 79.56. The AM and DN-
CO2 methods were apparently more stable in detecting
N2 O at high temperatures than the DN method. The
coefficients of variation (CVs) of dry ambient air were
1.5%, 1% and 1.5% at 250◦ C and 1.2%, 0.6%, 0.7% at
330◦ C for the DN, AM and DN-CO2 methods, respec-
tively.
NO. 6 WANG ET AL. 1327

3.3 Comparisons between the DN, DN-CO2 creased, giving rise to a significant difference to the
and AM methods AM and DN-CO2 methods when the temperature was
at 330◦ C and 380◦ C (Figs. 4b, 4c, 4d).
Experiment 3 was designed to compare the anti-
For the DN method, the response signals of N2 O
interference ability of each method for CO2 . The N2 O
increased gradually with an increase in the content of
response signal for the air sample without CO2 added
CO2 . At a temperature of 330◦C, the CO2 concentra-
is defined as A0 ; and the signals of samples with added
tion of gas samples changed from 400 to 3121×10−6
CO2 is expressed as Ai , where i is the number of gas
mol mol−1 , and the rate of (Ai − A0 )/A0 ranged from
bags to which CO2 was added, ranging from 1–20. The
−1.3% to 15.2%. When the CO2 content was below
ratio of (Ai − A0 )/A0 denotes the N2 O signal variation
820×10−6 mol mol−1 , the augmentation of the N2 O
caused by the increase in CO2 concentration; it also
peak area was not significant, and the overestimated
represents the overestimated part of N2 O concentra-
part changed at a range of −1.3% to 2.5%, which fell
tion. Experimental error might be caused by sample
into the acceptable variation range. When the CO2
error or instrument error. In most cases, sample error
content exceeded 900×10−6 mol mol−1 , the overesti-
is less than 0.5% because no more than 3 mL pure CO2
mated part extended to 6.1%–15.2%. The relationship
was added into 800 mL ambient air. Instrument error
between CO2 content and the overestimated part of
by the DN, AM, and DN-CO2 methods is less than
the N2 O signal was logarithmic [y=7.3282ln(x)−44.9,
2.5%, 1.0% and 1.0%, respectively. Therefore, the to-
r2 =0.899, n = 25, p<0.001]. At a temperature of
tal experimental error should be within 3%. Then,
380◦ C, the CO2 concentration of gas samples changed
the (Ai − A0 )/A0 values at −3% to 3%, can be consid-
from 400 to 2809×10−6 mol mol−1 ; the rate of (Ai −
ered within the experimental error; beyond this range,
A0 )/A0 ranged from 1.5%–19.7%, and the relation-
meaning that there existed a significant impact.
ship between CO2 content and the rate could be ex-
As Fig. 4 shows, at a lower ECD temperature
pressed as y = 10.421ln(x)−64.885 (r2 =0.951, n=25,
(250◦ C), the difference between the DN and AM meth-
p<0.001).
ods was not significant (Fig. 4a); as the temperature
For the AM method, the N2 O signals maintained
increased, the variation in the DN method also in-

Fig. 4. The influence of detector temperature on the bias of N2 O in the different methods. N2 O concen-
tration was 330×10−9 mol mol−1 : (a) 250◦ C; (b) 290◦ C; (c) 330◦ C; (d) 380◦ C. Dark circles represent the
DN method, triangles the AM method, and empty circles the DN-CO2 method. The solid arrow points to
the CO2 signal and the dashed arrow to the N2 O signal. Definitions of the DN, AM and DN-CO2 methods
are provided in section 2.
1328 A NEW CARRIER GAS TYPE
stable values, although the CO2 content ranged from
400 to 3121×10−6 mol mol−1 ; the ranges of the over-
estimated parts were −1.3% to 0.4%, −1.8% to 1.5%,
−2.3% to 0.9%, and −0.1% to 0% at temperatures of
250◦ C, 290◦ C, 330◦ C, and 380◦C, respectively. This
shows that the existence of CO2 did not affect the
actual analysis of N2 O. Similarly, when the DN-CO2
method was applied, the stabilities of the N2 O signals
were better than in the DN method, and close to those
for the AM method. The ranges of the overestimated
parts were −2.4% to 1.2% and −1.4% to 1.1% at tem-
peratures of 330◦ C and 380◦ C, respectively. There was
no significant difference between the AM and DN-CO2
methods in the 5890II system (paired test, p=0.515).
The results show that the influence of CO2 on
N2 O depends on the ECD temperature. For the DN
method, when the ECD temperature was 250◦ C and
290◦ C, the stability of the instrument was worse, but
the existence of CO2 did not influence the signal of
N2 O obviously. When the ECD temperature was
higher, the influence became more and more obvious.
It seems that the operating temperature of the ECD
also greatly influenced the overestimation: the higher
the detector temperature, the greater the overestima-
tion.
The results of this experiment showed that the CO2
content in gas samples can exaggerate the ECD re-
sponse signal for N2 O and give overestimated concen-
trations under the DN method. Experiments carried
using other GC systems from different manufacturers,
such as Shimadzu, Agilent and Varian, led to a sim-
ilar conclusion (data not given here). This is a com-
mon phenomenon and an important one for researchers
working in this field. Compared to the DN method,
the AM and DN-CO2 methods were able to resist the
influence of CO2 and provide more stable and sensitive
responses to N2 O. Furthermore, the concentrations of
N2 O detected under these two GC methods were close
to actual values.
4. Discussion
4.1 The possible electron capture mechanism
of CO2 and N2 O
When an electronegative compound AB enters the
ECD, there are two mechanisms for electron capture
and the formation of negative ions. Mechanism I is
an exothermic and non-dissociative reaction, which
prefers a lower temperature (RXN 1); mechanism II
is an endothermic and dissociative reaction, where a
higher temperature will accelerate the reaction (RXN
2) (Da, 1999).
AB + e → AB− RXN 1
VOL. 27
AB + e → A• + B− RXN 2
With the performance of CO2 and N2 O under dif-
ferent ECD temperatures (as shown in Fig. 2), it
seems that the inherent response mechanisms of CO2
and N2 O in the ECD cell were different. The electron
capture mechanism of CO2 should belong to mecha-
nism I (RXN 1); CO2 colliding with electrons in the
ECD cell will emit heat. Therefore, a higher temper-
ature is a disadvantage for CO2 electron capture, and
thus the sensitivity of the ECD for CO2 decreases with
an increase in temperature. In contrast, N2 O should
belong to mechanism II (RXN 2), i.e. a dissociative
reaction, which absorbs heat when reacting with elec-
trons in the cell; the sensitivity will be greatly en-
hanced by an increase in detector temperature.
4.2 Possible explanation of the N2 O bias
caused by the presence of CO2
When N2 is applied as a carrier gas, CO2 and N2 O
in the air samples may generate the following reactions
(Da, 1999; Ševčı́k, 1977):
N2 + β → N+ 
2 +β +e RXN 3
N2 + β → N∗2 + β  RXN 4
N2 + e → N∗2 + e RXN 5
CO2 + β → CO+ 2 +β

+e RXN 6
CO2 + e → CO2 − RXN 7
−
N2 O + e → N2 + O RXN 8

Where β represents primary electrons; β represents
slow primary electrons; e is a secondary electron; N+ 2,
CO+ 2 , CO −
2 , and O −
are ionic nitrogen, carbon diox-
ide and oxygen, respectively; N∗2 is the super-excited,
long-lived state of nitrogen; and e is a slow secondary
electron.
Here, RXN 6 is an ionization reaction producing
electrons; furthermore, it is endothermic. RXN 7 gives
the CO2 electron capture process (mechanism I) and is
an exothermic reaction. The electron capture process
of N2 O is also an endothermic reaction (mechanism
II, RXN 8). When the ECD temperature is low, it
encourages RXN 7 and limits RXN 6 and RXN 8, so
the reaction of CO2 capturing electrons dominates the
ECD cell, and the behavior of CO2 in the cell performs
as negative ion production. It reduces the baseline cur-
rent and forms a negative peak, which is reversed to
positive by the signal recorder for easy observation. As
for N2 O, there are two reasons for its low sensitivity.
On the one hand, the low detector temperature limits
N2 O electron capture; on the other, CO2 competes for
and takes more electrons. The electron density is not
affected by RXN 6 because low temperature does not
benefit the reaction. The two compounds can both be
NO. 6 WANG ET AL.
detected at this temperature and do not disturb each
other, though the precision and sensitivity are worse.
With the detector temperature increasing, RXN 7
falls into decline and RXN 6 and RXN 8 become more
and more active. Gradually, the dominating reaction
of CO2 transfers from RXN 7 to RXN 6, and the whole
act of CO2 in the ECD cell changes from electron cap-
ture to electron production. Thus, with an increase in
ECD temperature, the signal of CO2 becomes weaker
and weaker. When the detector temperature is high
enough, RXN 6 and RXN 7 maintain the balance and
no net CO− 2 exists; the CO2 positive peak disappears
(see Fig. 2). As the detector temperature continues to
increase, RXN 6 totally dominates the reactions and
CO2 acts as a positive ion source; it enlarges the cur-
rent and forms a positive peak that appears negative
on the chromatogram.
For N2 O, on the one hand the temperature increase
encourages electron capture and the decline of RXN 7
provides more available electrons, which enhances the
sensitivity of N2 O (see Figs. 3a–3d). On the other
hand, RXN 6 plays an important role when the ECD
temperature is high (e.g. 330◦ C); it produces more
electrons and enhances the electron density in the ECD
cell, and the more CO2 , the greater the electron den-
sity. As a result, N2 O can capture more electrons than
free of CO2 . Thus, the response signal of N2 O appears
to increase with the CO2 content (see Fig. 1). How-
ever, the response of N2 O depends on the quantity
of N2 O and the electron density in the cell. When
enough CO2 is present, the ECD becomes saturated
with electrons and the response of N2 O is only de-
termined by N2 O content; therefore, it remains stable
and no longer increases with CO2 concentration (see
Figs. 1 and 4). This is why adding enough CO2 into
the ECD can enhance the sensitivity of N2 O and the
response is no longer disturbed by the content of CO2
in the gas samples.
β + CH4 → β  + CH+
4 +e RXN 9
Similarly, when highly abundant CH4 is introduced
into the ECD, a reaction like RXN 9 occurs (Ševčı́k,
1997). CH4 is not an electronegative compound and
no electron capture occurs. The ionization potential
of CH4 (12.6 eV) is lower than that of CO2 (13.7 eV),
which facilitates the reactions with β and electrons,
and provides slower electrons. Thus, when Ar-CH4 is
applied as a carrier gas or introduced into the ECD
as a make-up gas, the CH4 may supply abundant slow
electrons in the ECD pool; the response of N2 O only
depends on the content of Ar-CH4 in the gas samples,
and the influence of CO2 in the samples can be elim-
inated. The authors also tested the effect of adding
CH4 as a make-up gas when N2 was used as a carrier
1329
gas, and similar results were obtained. With the above
principle, GC methods that introduce slow-down me-
dia such as CH4 and CO2 into the ECD can supply
sufficient electrons and eliminate the CO2 -induced in-
fluence; it also greatly increases the sensitivity and
stability of the ECD for N2 O analysis.
Accurate measurement of concentration is the ba-
sis for determining emission sources and sinks of N2 O.
However, many laboratories are unaware that their
analyses of N2 O are incorrect. An estimated one-
third of all published measurements have overesti-
mated N2 O fluxes from terrestrial or aquatic systems
when using the DN method. Some researchers use
pre-columns filled with ascarite to remove CO2 before
analysis; this is not recommended by the present au-
thors because the efficiency of ascarite decreases as the
number of samples increase. On the other hand, labo-
ratory experiments show that the initial use of ascarite
also absorbs small amounts of N2 O.
5. Conclusions
The results of this study show that the detection
of N2 O by GC-ECD using only N2 as a carrier gas
was defective. The existence of CO2 in air samples
or in the ECD cell greatly enhanced the response of
N2 O, which produced an overestimation of the N2 O
concentration. The relationship between the N2 O sig-
nal and the CO2 content could be described by the
Michaelis-Menten equation. The bias between the ap-
parent N2 O concentration and the actual result in-
creased with ECD temperature and CO2 content. Ac-
cording to the performance of CO2 and N2 O at differ-
ent ECD temperatures, it was hypothesized that the
mechanism of electron capture was responsible. The
electron capture mechanism of CO2 should belong to
mechanism I, an exothermic and non-dissociative re-
action; and the electron capture mechanism of N2 O
should belong to mechanism II, an endothermic and
dissociative reaction.
Comparisons between the three methods have
shown that the DN method overestimated the N2 O
concentration at high ECD temperatures; it was defec-
tive in determining the N2 O concentration. N2 O con-
centrations measured by the AM and DN-CO2 meth-
ods were close to actual values; the bias caused by the
presence of CO2 could be eliminated by these meth-
ods, and there was no significant difference between
them. New GC carrier gas types with make-up gases
that can remove the CO2 -induced influence, such as
the DN-CO2 and DN-CH4 methods, are recommended
for the accurate measurement of N2 O,.
Acknowledgements. This study was supported by
the Knowledge Innovation Program of the Chinese
1330 A NEW CARRIER GAS TYPE
Academy of Sciences (Grant No. KZCX2-YW-204) and
the National Basic Research Program of China (No.
2007CB407303).
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