Chemosphere: Global Change Science 1 (1999) 153±161

Atmospheric carbon monoxide Ôin situÕ monitoring by automatic

gas chromatography
V. Gros 1, B. Bonsang *, R. Sarda Esteve
LSCE, Orme des Merisiers, B^
at.709, CE Saclay, 91 191 Gif sur Yvette cedex, France

Received 15 April 1998; accepted 2 February 1999

Importance of this Paper. CO measurements in the background atmosphere of the southern hemisphere are mainly based
on weekly ¯asks' samples which allow the study of seasonal variations and long-term trends but do not give access to short-
term variations. The development of a fully automatic gas chromatograph described here, allows to perform 10-min step
measurements of CO which can be combined with monitoring of tracers or reactive compounds. This technique is used for
the study of background atmosphere such as at Amsterdam island in the remote Indian ocean or for measurements in the
more polluted atmosphere of the northern hemisphere.

Abstract

In order to develop Ôin situÕ automatic CO measurements, we adapted the method based upon the separation by gas
chromatography and the detection by hot mercuric oxide reduction, previously described in the literature. We applied
this method in order to alternate the injection at the atmospheric pressure of a standard and a sample, with each sample
calibrated against the preceding standard. A frequency of 5 min was chosen for each run, which implied a sample
measurement every 10 min. The evolution of the standards used in the routine experiments was regularly checked
against a primary standard provided by NOAA. First measurements, made at Amsterdam Island (37°S, 77°E) with this
procedure, showed quite a good agreement with other values observed in the remote Southern Hemisphere. Several tests
were then performed in order to determine some characteristics of the measurement. Thus, the standard deviation of the
mean CO mixing ratio, for 100 analyses of a single air sample containing approximately 200 ppbv CO, averaged ‹ 2%,
which determined the stability of the measurement. The reproducibility was found to be at most 2.5% and the overall
uncertainty of the measurement was estimated at 4%. Finally two intercomparison exercises between two similar in-
struments were performed at Amsterdam Island and they agreed within 4% and 5.5%, respectively, that is namely in the
range of the uncertainty of the analytical procedure. Ó 1999 Elsevier Science Ltd. All rights reserved.

Keywords: Carbon monoxide; Gas chromatography; Automatic Ôin situÕ measurement; Short-term variations; Remote
atmosphere

*
Corresponding author.
1
Present address: Max Planck Institute for Chemistry, Air Chemistry Division, Mainz, Germany. E-mail: vgros@mpch-
mainz.mpg.de (V. Gros)

1465-9972/99/$ ± see front matter Ó 1999 Elsevier Science Ltd. All rights reserved.
PII: S 1 4 6 5 - 9 9 7 2 ( 9 9 ) 0 0 0 1 0 - 0
154 V. Gros et al. / Chemosphere: Global Change Science 1 (1999) 153±161
1. Introduction
Carbon monoxide (CO) has been measured for
more than 50 years even if its key role in the
tropospheric chemistry, via its reaction with OH,
has only been recognized since the 1970s. From
solar spectroscopy to non-dispersive infrared gas
®lter correlation, several methods have been used
to measure CO and they are reviewed in (WMO,
1994). The CO measurement consisting of sepa-
ration by gas chromatography and detection by
hot mercuric oxide reduction is assumed to have a
very low limit detection (2 ppbv) and a good ac-
curacy (1% at 100 ppbv) (WMO, 1994). This
method has been described by Seiler et al. (1980)
and Novelli et al. (1991,1992) and can be used
either for in situ measurement or for CO analyses
based on ¯asks' sample collection. In situ mea-
surements are necessary for continuous monitor-
ing particularly in remote locations which are too
far away from the laboratory. Moreover, the sta-
bility of CO in ¯asks strongly depends on the
nature of the ¯asks and on the delay between in
situ sampling and analysis in the laboratory
(Novelli et al., 1992). In order to perform auto-
matic and in situ measurement, we adapted a GC
instrument in the laboratory. However, in order to
check and improve its performances in low pol-
luted conditions the instrument was operated at
Amsterdam Island (37°S, 77°E) in the Indian
Ocean.
2. Instrument description and analytical procedure
The instrument used, a RGA3 (Trace Analyti-
cal), allowed the separation and detection of CO
and H2 with a typical retention time of 1.5 min. for
CO. The carrier gas used was Nitrogen 5.0 (purity
of 99.999%) at a ¯ow rate of about 20 ml/min.
Temperature of the back¯ush column (1/8 in ´ 30
1/4 in unibeads 1S 60/80) and the analytical col-
umn (1/8 in ´ 30 1/4 in mole sieve 5A 60/80) was
95°C whereas temperature of the detector was
265°C.
The RGA3 analyzer was adapted for in situ
continuous monitoring of CO including calibra-
tion. A 4-port valve, option of the RGA3, allowed
us to make a stream selection between the stan-
dard and the sample and to select the frequency of
the calibration. It has been decided to inject the
sample alternately with a standard and to calibrate
each sample with the preceding standard. Two
kinds of standards, both in the range 100±200
ppbv, were used in our study. Primary standards
provided by NOAA (CO-in-air, standardized
against the CMDL/NOAA primary, gravimetric
scale (Novelli et al., 1991) were used to calibrate
secondary standards provided by Air-Liquide
(CO-in N2 ). In the automatic runs of the system,
the secondary standard is continually circulating
with a low ¯ow rate (under 10 ml/min) and
therefore is able to last over a year.
For sampling, a Reciprotor pump located
downstream the sample loop allowed the circula-
tion of ambient air in the system. For the standard,
we mounted a 6-port valve at the rear of the in-
strument. The four possible con®gurations of the
system ± sample load, sample injection, standard
load and standard injection ± are depicted in Fig. 1
(a±d).
In sample load position, sample ¯ows through
the sample loop while the carrier gas is back-
¯ushed in column 1 in order to remove the com-
ponents from the former injection which will not
be eluted. The correct timing of the 10-port valve
switching enables CO2 , NMHC to be back¯ushed.
The following step, sample injection, consists in
¯owing the carrier gas through the sample loop
which drags along the sample to column 1, column
2 and ®nally to the detector. During these two
steps the standard gas circulates at a low ¯ow rate
(less than 5 ml/min) controlled by a metering
valve. The two other steps, standard load and in-
jection, are based on the same principle, with the
standard circulating at atmospheric pressure in the
sample loop at a ¯ow rate of 5±10 ml/min.
In order to avoid measurement of the pressure
in the loop and subsequent calculations, the loop
must be loaded at the same pressure for standard
and sample. Loading the loop at ambient atmo-
spheric pressure appears to be the easiest way. In
the con®guration described above, the sample
pressure in the loop is lower than the ambient at-
mospheric pressure, resulting from a pressure drop
 V. Gros et al. / Chemosphere: Global Change Science 1 (1999) 153±161 155

Fig. 1. The 4 possible con®gurations of the system: a) sample load, b) sample inject, c) standard load, d) standard inject.

in the sampling and injection lines. In order to
avoid this problem, an electrovalve, controlled by
the software Borwin, was mounted between the 6-
port valve and the pump. This electrovalve isolates
the pump a few seconds before the sample injec-
tion and allows the pressure in the loop to equili-
brate with the external pressure. In this new
con®guration, we checked that the loop was
loaded at the same pressure for both sample and
standard within the accuracy of the pressure sen-
sor (i.e. 0.1 Torr). Several tests were conducted
over a period of 3 months in order to estimate the
pressure drop when the electrovalve was not used,
i.e. from March to December 1996 for Amsterdam
Island measurements. They consisted of the injec-
tion of the sample with and without the electro-
valve operating. The pressure drop was found to
be randomly distributed over the range 15±25% of
the ambient pressure which will result in a cor-
rective factor of 20 ‹ 5 %. In order to adjust more
precisely this corrective factor, we have made
comparisons with the data obtained at Crozet Is-
lands from ¯asks samples (Gros et al., this issue).
For these two sets of data the best ®t was obtained
156 V. Gros et al. / Chemosphere: Global Change Science 1 (1999) 153±161

for a corrective factor of 25% i.e. in the upper

range of our estimate. This factor (+ 25 %) was
applied to Amsterdam Island measurements from
March 1996 to December 1996. Besides the un-
certainty on the measurement calculated in section
3.5, the data obtained at Amsterdam Island for
1996 present an additional uncertainty due to this
problem of pressure drop and are estimated at
‹ 5%.
Data acquisition and instrument control were
made by `Borwin' gas chromatography software.
This software was used in order to follow the
chromatograms in real time and compute directly,
from the peak area of each sample and its pre-
ceding standard, the concentration of CO. This
software was also used to start the analytical
procedure of the RGA3 instrument, allowing to
choose the frequency of the measurement. Each
injection which alternates a standard and a sample
was made every 5 min. Consequently the fre-
quency of the measurement as well as of the
standard was ten min. An example of chromato-
gram for a standard and for a sample is given in
Fig. 2.

3. Characteristics of the measurement

3.1. Linearity

The linearity of the measurements was ®rst

studied over a wide range with injections of a
standard of 9.5 ppmv provided by the National
Institute of Standards and Technology (NIST) at
various pressures in the sampling loop. The re-
sponse of the detector was checked up to a pres-
sure of 760 Torr. As described in Fig. 3a a good
linearity can be observed (with a correlation co-
ecient of 0.99985) up to a pressure of 80 Torr
corresponding to 1 ppmv of CO at ambient at-
mospheric pressure. Afterwards, we studied more
speci®cally the linearity in the range of expected
concentrations in background air (i.e 50±500
ppbv). These tests were performed with another
source of standard (standard with 365 ppbv/air
provided by NOAA). As shown in Fig. 3b, a good
linearity was observed for the range 0±600 ppbv
with a correlation coecient of 0.99976. Even if
Fig. 2. An example of CO chromatogram for standard and
sample, respectively.
the linearity could change with time (Novelli et al.
1992), it is not expected to a€ect the range of in-
terest, i.e 0±200 ppbv, very close to the origin of
the response of the instrument.
3.2. Stability
The stability of the measurement was checked
by continuously ¯owing a secondary standard (Air
Liquide) during a time period of 5 h and recording
the peak area every 3 min (Fig. 4). The stability of
the measurement over this period is statistically
 V. Gros et al. / Chemosphere: Global Change Science 1 (1999) 153±161
Fig. 3. (a) Detector responses to injections of a standard of 9.5
ppmv at various pressures in the sampling loop. A good lin-
earity is observed for the concentration range 0±1 ppmv. (b)
Detector responses to injections of a standard of 365 ppbv at
various pressures in the sampling loop. A good linearity is
observed for the concentration range 0±600 ppbv.
Fig. 4. Recording of the peak area of the Air Liquide standard
during a time period of 5 h.
157
determined as the standard deviation of this
peak area and is about 2%. The variability of the
measurement includes several factors as variability
of the carrier gas ¯ow rate, of the ambient pres-
sure and of the eciency of the HgO to Hg con-
version. As the ambient pressure variability was
not signi®cant during the period of study (<0.2%),
the 2% variability observed is representative of the
stability of the measurement itself. Many other
similar tests were performed with very similar re-
sults.
3.3. Reproducibility
The reproducibility of the measurement was
checked by calibrating standards in the range of
50±200 ppbv against the primary standard
(NOAA). The reproducibility over about 100
measurements is statistically determined as the
relative standard deviation of the calculated stan-
dard concentration, and ranges from 1% to 2.5%
with generally highest values corresponding to the
lowest concentrations. Other calibrations regularly
performed showed a similar or better reproduc-
ibility and this value of 2.5% can therefore be
considered as the maximum analytical uncertainty
of the measurement.
3.4. Calibration
Evolution of the secondary standard is con-
trolled about every two months against the pri-
mary standard and its value is readjusted if
Fig. 5. Calibrations of the secondary standard (Air Liquide)
against the primary standard (NOAA) at Amsterdam Island.
158 V. Gros et al. / Chemosphere: Global Change Science 1 (1999) 153±161

 2  2  2
necessary. For example, variations of the standard DCAL DCNOAA DRAL;NOAA
ˆ ‡
Air Liquide used at Amsterdam Island since May CAL CNOAA RAL;NOAA
1997 is given in Fig. 5. Primary standard was
cylinder CA01995, CO-in-air with 151.5 ‹ 1.5 ppbv and ®nally
CO and was assumed to be stable with respect to  2  2  2
CO for periods of at least 1.5 year (Novelli et al., DCsample DCNOAA DRsample;AL
ˆ ‡
1991). The secondary standard does not seem to Csample CNOAA Rsample;AL
present any signi®cant drift but its value ¯uctuates  2
DRAL;NOAA
around 193.1 ‹ 4.5 ppbv which represents a 2.5% ‡ :
RAL;NOAA
variability. Therefore, the secondary standard
variability observed over one year is within the An uncertainty of 1% on the concentration of
analytical uncertainty of the measurement. Note the primary standard NOAA is provided by the
that the evolution observed can vary from one manufacturer (Novelli et al., 1991). The uncer-
secondary standard to another. tainty on the ratios Rsample ,AL and RAL;NOAA were
experimentally evaluated at 2.5%, as described in
section 3.3. Finally CO measurements are made
3.5. Overall uncertainty of the measurement with an overall uncertainty of about 4%.

As the CO concentration of a sample is deter-

mined as 3.6. Intercomparison of two analyzers
Asample
Csample ˆ CAL  ˆ CAL  Rsample;AL ;
AAL We performed at Amsterdam Island two series
where; Rsample;AL ˆ Asample =AAL of intercomparison between two identical RGA3
analyzers. Each analyzer was working indepen-
with dently with its own sample line and secondary
AAL standard. Only the primary standard was com-
CAL ˆ CNOAA  mon for both analyzers. The two intercompari-
ANOAA
sons were made in March 1997 and in November
ˆ CNOAA  RAL;NOAA ; 1997 with respective CO level of about 40 ppbv
and 60 ppbv. Fig. 6 a and b present the distri-
where butions of the di€erence between the analyzers.
RAL;NOAA ˆ AAL=ANOAA ; On an average, this di€erence (analyzer 1ÿ ana-
lyzer 2) was 1.59 ‹ 2.09 ppbv for the ®rst inter-
where Csample , CAL and CNOAA stand for the CO comparison and ÿ3.3 ‹ 2.0 ppbv for the second
concentration of the sample, the secondary stan- intercomparison. The secondary standard associ-
dard (Air Liquide) and the primary standard ated with the ®rst analyzer was changed between
(NOAA), respectively, Asample , AAL and ANOAA the two intercomparisons and this could explain
represent the CO peak area of the sample, the Air why analyzer 1 presented higher values in the ®rst
Liquide and NOAA standards, respectively. exercise and lower values in the second. Finally,
As the terms are independent and the corre- results between both analyzers agreed within 4%
sponding uncertainty is rather low (a few percent), for the ®rst run and 5.5 % for the second run.
the uncertainty on the measurement can be cal- The uncertainty on the primary standard being
culated as the same for both analyzers, it is not taken into
 2  2  2 account in the di€erence observed. Therefore, the
DCsample DCAL DRsample;AL uncertainty on each chain of measurement is less
ˆ ‡ ;
Csample CAL Rsample;AL than 4% and the di€erence observed between the
analyzers remains within the global uncertainty
with of 8%.
 V. Gros et al. / Chemosphere: Global Change Science 1 (1999) 153±161 159

were then aggregated into hourly and monthly

averages.
A ®rst set of measurements was performed be-
tween March and December 1996 at Amsterdam
Island. Since January 1997, an electrovalve, which
solved the problem of pressure drop, has been in-
stalled. A 8-day time series during September 1997
is given in Fig. 7a. CO background levels are about
55 ppbv, which is in good agreement with other
data published for this area. For example CO
monthly mean was 55 ppbv at Cape-Grim (Tas-
mania, 40.6°S, 144.68°E) in September 1995
(Steele et al., 1996). The increase of CO which can
be observed on 8th September results from trans-
port of continental air from Southern Africa (de-
tails in Gros et al., this issue).
This CO measurement system has been also
used for in-situ measurement in the Northern
Hemisphere during the two phases of the EC

Fig. 6. Intercomparison between CO analyzers at Amsterdam

Island (a) 10±19 March 1997 and (b) 10±14 November 1997.

4. Time series

Continuous measurements every 10 min implies

the management of a large amount of data and it
was necessary to apply a ®lter in order to suppress
the results out of range. A visual inspection of the
chromatograms have shown that every outlier data
was due to a wrong peak integration which was
often linked to electrical spikes and artefacts. At
Amsterdam Island, in 1996, the rejected data for
each month were less than 10% of the total, except
for June 1996 where about 12 % of the data were
removed. In 1997, this ®gure decreased to less than
1% of the total (except for April 1997 where it
increased to 2.5%), this signi®cant improvement Fig. 7. CO measurements at Amsterdam Island (a) and in
was probably due to the installation of the elec- Greece in comparison with black carbon (BC) measurements
trovalve previously described. The remaining data (personal communication) during the AEROBIC campaign (b).
160 V. Gros et al. / Chemosphere: Global Change Science 1 (1999) 153±161
campaign AEROBIC which took place in Portugal
(August 1996) and Greece (July±August 1997). A
time series is given for the second campaign in Fig.
7b in association with the measurement of black
carbon (T. Nunes and C. Alves, personal com-
munication). The very good agreement between
the variations of the two compounds which have
the same anthropogenic sources ascertains the
quality of our CO measurement.
5. Conclusion
We adapted the CO measurement based on
separation by gas chromatography and detection
by hot mercuric oxide reduction in order to per-
form continuous monitoring , with a step time of
10 min and to reach a very low detection limit
adapted to the ambient measurements in pure
marine atmosphere. One of the ®rst applications of
this technique was the continuous monitoring of
CO in a remote location (Amsterdam Island: 37°S,
77°E) where logistical problems occur. CO data
are now available in this location since March
1996. Measurements are made automatically every
10 min and are based on the alternate measure-
ment of the standard and of the sample, with a
simple injection procedure at ambient atmospheric
pressure. This technique requires very little man-
power, and needs only to replace the carrier gas
every two months, and the secondary standard
every year. Comparison of our measurements with
other observations in a remote area of the South-
ern Hemisphere shows a quite good agreement for
the monthly average. The high frequency of our
measurements allowed us to observe CO episodes
on a short time scale (see Gros et al., this issue).
This system was used during two ®eld cam-
paigns in Europe, where the CO level is of the
order of 200 ppbv, and the results presented very
good correlations with other anthropogenic trac-
ers such as black carbon.
Acknowledgements
We are grateful to the Institut Francßais pour la
Recherche et la Technologie Polaires (IFRTP), the
Territoire des Terres Australes et Antarctiques
Francßaises (TAAF) and the Institut Francßais de
Recherche pour lÕExploitation de la Mer (IF-
REMER) for ®nancial and logistical support of
the monitoring station at Amsterdam Island
(grant RACEA 146). This work was also sup-
ported by Centre National de la Recherche
Scienti®que (CNRS) and Commisariat a lÕEnergie
Atomique (CEA). Data for black carbon are from
courtesy of T. Nunes and C. Alves. The authors
are indebted to Pierre Nadeau and Beno^õt Pelczar
for technical assistance in measuring CO at Am-
sterdam Island. This is a LSCE contribution
no.227.
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Steele, L.P., Langenfelds, R.L., Lucarelli, M.P., Fraser, P.J.,
Cooper, L.N., Spencer, D.A., Chea, S., Broadhurst, K.,
1996. Atmospheric methane, carbon dioxide, carbon mon-
oxide, hydrogen, and nitrous oxide from Cape Grim ¯asks
air samples analysed by gas chromatography, in Baseline
Atmospheric Program Australia 1994±1995, R.J. Francey,
A.L. Dick and N. Derek (Eds.), Bureau of Meteorology and
CSIRO Division of Atmospheric Research, Melbourne,
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98, Boulder, 8±11, 1994.
Valerie Gros obtained her PhD from the University of Paris 7
in December 1998. She worked on the study of ozone (O3 )
and carbon monoxide (CO) variabilities in the marine boun-
dary layer of the southern hemisphere. She particularly stud-
ied the marine atmosphere of Amsterdam Island, Indian
ocean, with pointing out the key processes involved in the O3
and CO budgets over di€erent time scales. She has several
publications in international referred journals and conference
proceedings.
Bernard Bonsang has worked in the ®eld of atmospheric sci-
ences since 1972. He is Directeur de Recherche (CNRS) since
1993. He studied the oceanic source of reduced sulphur gases
and hydrocarbons. One part of his activities concerned also the
 V. Gros et al. / Chemosphere: Global Change Science 1 (1999) 153±161 161

evaluation of the production of carbon monoxide, methane and
NMHC's by biomass burning in the tropics, with particulate
emphasis on the tropospheric ozone budget. His main activities
are focused on the oxidizing capacity of the troposphere in the
frame of national and European projects and on a global scale
on long range transport of ozone and its precursors over the
oceans. He has been coordinator of EC projects dealing with
oxidation processes of VOC's. He is author of more than 60
publications in international referred journals and conference
proceedings.