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Permeation of atmospheric gases through polymer O-rings used in flasks for

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 JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 109, D04309, doi:10.1029/2003JD004073, 2004

Permeation of atmospheric gases through polymer

O--rings used in flasks for air sampling
P. Sturm,1 M. Leuenberger,1 C. Sirignano,2 R. E. M. Neubert,2 H. A. J. Meijer,2
R. Langenfelds,3,4 W. A. Brand,5 and Y. Tohjima6
Received 14 August 2003; revised 17 December 2003; accepted 22 December 2003; published 25 February 2004.

[1] Permeation of various gases through elastomeric O-ring seals can have important
effects on the integrity of atmospheric air samples collected in flasks and measured some
time later. Depending on the materials and geometry of flasks and valves and on
partial pressure differences between sample and surrounding air, the concentrations of
different components of air can be significantly altered during storage. The influence of
permeation is discussed for O2/N2, Ar/N2, CO2, d13C in CO2, and water vapor. Results of
sample storage tests for various flask and valve types and different storage conditions are
presented and are compared with theoretical calculations. Effects of permeation can be
reduced by maintaining short storage times and small partial pressure differences and by
using a new valve design that buffers exchange of gases with surrounding air or by using
less permeable materials (such as Kel-F) as sealing material. General awareness of
possible permeation effects helps to achieve more reliable measurements of atmospheric
composition with flask sampling techniques. INDEX TERMS: 0394 Atmospheric Composition
and Structure: Instruments and techniques; 1694 Global Change: Instruments and techniques; 1610 Global
Change: Atmosphere (0315, 0325); 1615 Global Change: Biogeochemical processes (4805); KEYWORDS:
permeation, air sampling, storage effects
Citation: Sturm, P., M. Leuenberger, C. Sirignano, R. E. M. Neubert, H. A. J. Meijer, R. Langenfelds, W. A. Brand, and Y. Tojhima
(2004), Permeation of atmospheric gases through polymer O-rings used in flasks for air sampling, J. Geophys. Res., 109, D04309,
doi:10.1029/2003JD004073.

1. Introduction al., 1998]. Measurements of the O2 concentration can

provide important constraints on the global carbon cycle
[2] Flask sampling of atmospheric air is an important tool
[Keeling et al., 1993]; however, they are challenging
in climate research to investigate atmospheric composition
because the variations occur only at the parts per million
changes on regional to global spatial scales and on time-
(ppm) level relative to the large 21% O2 content. Any small
scales from hours to decades. Especially for remote sites
disturbance of sample air can thus result in a similar or
and for airborne campaigns, often the only way to obtain
bigger signal compared with the real atmospheric variations.
measurements is to collect air in glass flasks in situ and to
[4] To reduce adsorption and desorption of gas molecules
analyze the samples later in a laboratory equipped with
on surfaces, the flasks most commonly used for O2 mea-
measuring instruments. This increases the risk of altering
surements are made of glass. There exist different valve
the composition of the air either during the sampling
designs; however, all flasks currently in use for this task are
procedure or during the storage prior to measurement. To
sealed by a polymer material, which is pressed against the
minimize such adverse effects, one must choose appropriate
glass surface of the valve. All polymers are subject to
filling procedures and flask materials.
permeation of gases, which therefore limits the effectiveness
[3] In the case of atmospheric O2 concentrations these gas
of the seal if partial pressure differences between sample
handling aspects prove to be particularly crucial [Keeling et
and surrounding air exist.
[5] Processes other than permeation may also influence
1
Climate and Environmental Physics, Physics Institute, University of the stability of the sample composition. For instance,
Bern, Bern, Switzerland. selective outgassing or physical adsorption of gases on
2
Centrum voor IsotopenOnderzoek, University of Groningen, Gronin- O-rings as well as oxidation of grease used to lubricate the
gen, Netherlands. O-rings can cause changes of the air composition. Keeling
3
Commonwealth Scientific and Industrial Research Organisation
Atmospheric Research, Aspendale, Australia.
et al. [1998] reported a depletion in the O2/N2 ratio
4
Institute of Antarctic and Southern Ocean Studies, University of and CO2 concentration in 5 L glass flasks fitted with
Tasmania, Hobart, Tasmania, Australia. Viton O-rings and filled to 1000 hPa pressure with 20 extra
5
Max Planck Institute for Biogeochemistry, Jena, Germany. O-rings inserted in the flasks. Flasks with no extra O-rings,
6
Atmospheric Environment Division, National Institute for Environ-
mental Studies, Tsukuba, Japan.
however, showed no significant drifts over 313 days in
accordance with the findings of Bender et al. [1996].
Copyright 2004 by the American Geophysical Union. [6] In this paper we report on the permeation process of
0148-0227/04/2003JD004073$09.00 different gases and various O-ring materials used for glass

D04309 1 of 9
D04309 STURM ET AL.: PERMEATION OF GASES THROUGH O-RINGS D04309

valves. Because of the sensitivity of high-precision O2/N2 The flux of diffusing species is given by Fick’s first law,
measurements to small interferences we focus particularly
J ¼ Drc: ð6Þ
on O2/N2. Additionally, water vapor, Ar/N2, CO2, and d13C
in CO2 are discussed. Section 2 summarizes theoretical The gas flux through the low-pressure surface of the wall
considerations on the permeation process and shows the can then be calculated from equations (5) and (6):
time dependence of the permeation rate for helium through
a Viton O-ring. Section 3 deals with changes of sample air Dðc1  c2 Þ
composition with increasing storage time and compares J ð x ¼ d; t Þ ¼
d
measured to calculated permeation rates. Tests with various

2D X1
Dn2 p2 t
O-ring materials and different storage conditions are pre- þ ½ð1Þn c1  c2 exp  : ð7Þ
d n¼1 d2
sented. In section 4 storage drift measurements and perme-
ation calculations of flasks sealed with new double O-ring
valves are discussed. Finally, section 5 summarizes our For large values of t one obtains the steady state flux
major findings.
Dðc1  c2 Þ DS ðp1  p2 Þ
J ð x ¼ d; t ! 1Þ ¼ ¼ : ð8Þ
d d
2. Permeation Process
2.1. Theory The product
[7] Permeation is commonly viewed as a three-step pro-
cess. First, gas dissolves into the solid’s surface; then it K ¼ DS ð9Þ
diffuses through the solid; and finally, it desorbs from it. The
time dependence of the permeation rate is determined by the is the permeation coefficient. It has, like the diffusion and
diffusion process because the solution and desorption occur solubility coefficient, a strong (approximately exponential-
on much shorter timescales than the diffusion through the like) dependence on temperature. Finally, the steady state
solid [Perkins, 1973]. The concentration c of the diffusing permeation flux F of a gas exposed with a partial pressure
species in the solid’s surface is given by Henry’s law, difference (p1  p2) to a membrane of thickness d and
surface area A is
c ¼ Sp; ð1Þ
Aðp1  p2 Þ
F ¼ AJ ð x ¼ d; t ! 1Þ ¼ K : ð10Þ
where S is the solubility coefficient and p is the gas d
pressure. Diffusion of the dissolved gas into the interior is 2.2. Measurement of Time-Dependent
governed by Fick’s second law, Permeation Rate
@c [8] Flasks used at the Physics Institute, University of
¼ Dr2 c; ð2Þ Bern, are each equipped with two high-vacuum valves
@t
(Louwers Hapert, Netherlands). The valves are opened
where D is the concentration-independent, isotropic diffu- and closed by moving a cylindrical plug in and out of a
sion coefficient. If we consider a planar membrane with a 9 mm ID valve tube (see Figure 1a). An O-ring sitting in a
large area-to-thickness ratio, equation (2) can be reduced to notch on the plug seals the flask volume from surrounding
a one-dimensional form air. The O-ring material is Viton (FKM 70-Copolymer-

2  compound 51414-GenuineViton1A).
@c @ c [9] Although the property of a large area-to-thickness ratio
¼D ; ð3Þ
@t @x2 is not true for an O-ring, the one-dimensional consideration
where x is the coordinate perpendicular to the membrane. of the permeation process is still justified for this valve type
Assuming that the membrane is initially free of gas and that because the sealing O-ring is mounted on and enclosed by
the concentrations of gas at the two surfaces are fixed at c1 impermeable cylindrical glass, which acts as a boundary
and c2, respectively, the initial and boundary conditions are in two dimensions. According to the size of the valves and
O-rings the effective thickness and exposed surface area of
an O-ring can be estimated. For our flasks the O-ring
cð x; t ¼ 0Þ ¼ 0 ð4aÞ
thickness and surface area are 1.7 mm and 20 mm2,
respectively, per valve. Unless otherwise specified, all cal-
cð x ¼ 0; t Þ ¼ c1 ð4bÞ
culations presented in this paper are based on these O-ring
dimensions.
cð x ¼ d; t Þ ¼ c2 ; ð4cÞ [10] To make sure that the changes in sample composition
we observe in these flasks are primarily due to permeation
where d denotes the membrane thickness. The solution of and are not a result of leaks, we conducted an experiment
equation (3) consistent with equations (4a), (4b), and (4c) is using these flasks and a helium leak detector. The previously
[Barrer, 1941] evacuated flasks had been filled to 950 hPa with helium, and
x the flux through the Viton O-ring valve was subsequently
cð x; t Þ ¼ c1 þ ðc2  c1 Þ measured by the leak detector. The temperature was 20C.
d

 Figure 2 shows the permeation flux as a function of time.
2X 1
c2 cos np  c1 npx Dn2 p2 t
þ sin exp  : ð5Þ Instead of a sharp signal increase as expected from a real
p n¼1 n d d2 leak, the leak detector’s helium signal slowly increased

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D04309 STURM ET AL.: PERMEATION OF GASES THROUGH O-RINGS D04309

laboratory in Bern (560 m asl) show a strong dependence of

the measured O2/N2 ratio on the storage time. This corre-
lation is attributed to permeation of gases through the Viton
O-rings of the flasks’ valves. In Figure 3, dO2/N2 measure-
ments from Jungfraujoch are plotted as a function of storage
time. The 0.5 L flasks were stored at room temperature and
at a mean ambient pressure of 950 hPa over a period of up
to 381 days. The mean sample pressure during the storage
time was 720 hPa. Ordinary least squares regression
yields a slope of 407 ± 11 per meg yr1. Hence, even after
a storage time of 100 days, the effect of permeation
clearly exceeded any real atmospheric signal. For example,
the seasonal cycle amplitude at this site is expected to be of
the order of 100 per meg [Keeling et al., 1993]. With
permeation coefficients KO2 = 1.1 1015 m2 s1 hPa1
15
and KN2 = 0.3 10 m s hPa1 for O2 and N2,
2 1

respectively, one would expect a slope of 379 per meg yr1,

very close to the measured value.
[14] On the basis of these results, laboratory experiments
were conducted to further test the stability of sample air
composition in these flasks. Four 0.5 L flasks were filled to
655 hPa with dry air from a high-pressure cylinder and were
Figure 1. Schematic diagram of different flask valves: stored at ambient pressure (950 hPa). The samples were
(a) valve with cylindrical shaft (Louwers Hapert, Nether- analyzed 4 times during the storage period of 299 days, in
lands), (b) valve with tapered shaft (Glass Expansion, which sample pressure decreased to 560 hPa. Figure 4
Melbourne, Australia), and (c) double O-ring valve with shows dO2/N2 deviations from the first measurement of
buffer volume. each flask sample. These measurements agree well with
predicted drift rates, indicating that the O-ring dimensions
and permeation coefficients used to calculate predicted dO2/
because of permeation. Steady state permeation was
N2 drift rates seem to be justified.
achieved in 40 min. The solid line in Figure 2 is a least
[15] Storage tests were also conducted by the Common-
squares fit of equation (7) to the measured data. The fitted
wealth Scientific and Industrial Research Organisation
parameters are the permeation and solubility coefficients K
(CSIRO) in their 0.5 L glass flasks fitted with different
and S, respectively. We obtain a solubility coefficient of
O-ring materials (Viton, perfluoroalkoxy (PFA), and poly-
SHe = 2.3 105 hPa1 and a permeation coefficient of
tetrafluoroethylene (PTFE)) and at a range of sample
KHe = 15.1 1015 m2 s1 hPa1, which is in agreement
pressures from 1000 to 2100 hPa. The results demonstrate
with the values listed in Table 1.
the dependence of permeation rates on O-ring material and
[11] Given the O-ring geometry and permeation coeffi-
partial pressure differences [Langenfelds, 2002]. Each
cients for different gases, we can estimate the influence of
CSIRO flask is fitted with two valves (Glass Expansion,
permeation on sample air composition for different sample
Melbourne, Australia), which differ from those manufac-
pressures and flask volumes. However, the uncertainty in
the O-ring dimensions and the large range of some
permeation coefficients shown in Table 1 restrict the
precision of such an estimate. The scatter of results in
Table 1 is probably mainly due to modifications in
polymer manufacturing over the last decades and the fact
that the polymers may vary between different manufac-
turers. The composition of a polymer can cause properties
to differ by orders of magnitude. It is therefore essential to
compare theoretical calculations with measured drifts in
sample air composition as a function of storage time.

3. Flask Storage Drift

3.1. Permeation Influence on O2/ N2
[12] We express changes in elemental and isotopic ratios Figure 2. Helium permeation through a Viton O-ring. An
as relative deviations from a reference gas. In the case of initially evacuated flask was filled with helium to 950 hPa.
O2/N2, variations are reported in units of per meg (where 1 The helium flux was then measured as a function of time
per meg = 0.001%) according to dO2/N2 = [(O2/N2)sample/ (circles). The O-ring has a thickness of 1.7 mm and an
(O2/N2)reference  1] 106. exposed surface area of 20 mm2. A least squares fit of
[13] Atmospheric flask samples taken in flasks at the equation (7) to the measured data (line) yields permeation
high-altitude station Jungfraujoch (3580 m above sea level and solubility coefficients of KHe = 15.1 1015 m2 s1
1 5 1
(asl), 46330N, 7590E) at ambient pressure and stored in the hPa and SHe = 2.3 10 hPa , respectively.

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D04309 STURM ET AL.: PERMEATION OF GASES THROUGH O-RINGS D04309

Table 1. Permeation Coefficients K for Various Polymer Materials and Gasesa

Material N2 O2 Ar CO2 H2 O He Temperature, C Sourceb
Viton 0.05 – 0.3 1.0 – 1.1 5.8 – 6.0 40 9 – 16 20 – 30 1
1.1 216 25 2
0.17 0.3 3.5 4.9 20 3
0.45 1.65 2.4 15.0 25 4
0.233 1.7 12.8 23 – 30 5
PTFEc 0.14 0.04 0.12 27 20 – 30 1
4.7 23.3 25 2
2.5 8.2 570 23 6
1.44 – 2.4 3.37 – 7.5 7.51 30.1 – 523 25 5
2.3 7.5 4.4 530 20 7
NBRd 0.2 – 2.0 0.7 – 6.0 5.7 – 48 760 5.2 – 6 20 – 30 1
0.177 – 1.89 0.72 – 6.15 5.63 7.4 – 8 20 – 25 5
Neoprene 0.8 – 1.2 3–4 19 – 20 1400 10 – 11 20 – 30 1
0.01 – 2 3.0 13.9 – 19.2 0.6 – 7.5 25 5
0.19 1.4 1.2 7.2 20 7
Polyurethane 0.4 – 1.1 1.1 – 3.6 10 – 30 260 – 9500 20 – 30 1
0.8 10.5 3.6 20 – 25 5
Silicone 76 – 460 460 – 2300 8000 20 – 30 1
75 – 210 195 – 450 450 1028 – 2280 238 – 263 room 5
128 286 156 20 3
e
PCTFE 0.004 – 0.3 0.02 – 0.7 0.04 – 1 20 – 30 1
0.22 25 6
a 15 2 1 1
The units are 10 m s hPa .
b
Sources are 1, Peacock [1980]; 2, Ma et al. [1995]; 3, Beckmann [1991]; 4, Laurenson and Dennis [1985]; 5, Parker Hannifin Corporation [2001]; 6,
O’Hanlon [1989]; and 7, Holland et al. [1974].
c
PTFE is polytetrafluoroethylene.
d
NBR is acrylonitrile butadiene copolymer.
e
PCTFE is polychlorotrifluoroethylene.

tured by Louwers Hapert in that the valve shafts are exchange during flask storage between CO2 and water
tapered and seals are formed by compression of the O-rings condensed on the flask walls [Gemery et al., 1996].
(Figure 1b). Figure 5 shows changes in dO2/N2 over storage Depending on the analysis technique, water vapor can also
times of up to 15 months in flask air samples filled to adversely affect the measurement itself. In particular, for
1500 hPa. The higher sample pressure compared with a precise O2/N2 measurements it is a prerequisite that the
mean ambient pressure of 1000 hPa led to dO2/N2 being analyzed sample air is dry. Therefore flask air samples are
depleted in these samples. All data points represent individ- usually dried at the time of sampling either by a chemical
ual flask samples analyzed on a single occasion. Lowest drift drying agent (e.g., anhydrous magnesium perchlorate,
rates of 61 per meg yr1 were observed with Viton O-rings. Mg(ClO4)2) or by a cryogenic cold trap. However, because
[16] To account for the geometric differences between of the large permeability coefficients of most polymers for
Glass Expansion (GE) and Louwers Hapert (LH) valves, we water vapor (Table 1), initially dry samples stored in the
measured helium permeation rates with a helium leak laboratory are intensely subject to water vapor permeation.
detector for both valve types fitted with Viton O-rings. This
experiment showed that GE valves have a lower helium
permeation rate than LH valves. Depending on the valve
and on how tightly the GE valve is closed, the steady state
permeation flux was a factor of 4 –10 smaller for GE valves
than for LH valves. This can be explained by the smaller
area of the O-ring that is exposed to the gas in the closed GE
valves. Because of the conical tip of the piston the O-ring is
compressed into the groove cut in this tip, and the gap
between the glass piston and the mating conical seat is
smaller than for LH valves. Assuming a 7 times smaller area
(3 mm2 instead of 20 mm2, d = 1.7 mm), one would expect
a dO2/N2 drift rate of 59 per meg yr1, which is consistent
with the observations.
[17] Figure 6 shows observed rates of drift as a function
of sample pressure. Drift rates are near zero at sample
pressures of 1000 hPa and increase approximately linearly Figure 3. Measurements of dO2/N2 as a function of
with sample pressure, providing compelling evidence that storage time. The samples are from Jungfraujoch and are
permeation is indeed the dominant modifying process. stored in 0.5 L flasks, filled at ambient pressure at 3580 m
above sea level and at a mean temperature of 7C. Mean
3.2. Permeation of Water Vapor sample pressure at room temperature is 720 hPa, and mean
[18] Variations of the amount of moisture in the sample ambient pressure is 950 hPa. Ordinary least squares
air can induce different artifacts, like oxygen isotope regression yields a slope of 407 ± 11 per meg yr1.

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D04309 STURM ET AL.: PERMEATION OF GASES THROUGH O-RINGS D04309

Figure 6. Rate of drift in dO2/N2 as a function of pressure

and O-ring material (symbols same as for Figure 5), as
Figure 4. Changes in dO2/N2 due to storage in 0.5 L determined by linear regression to data in Figure 5
flasks. Measurements of the flasks UBE-107 (circles), UBE- (corresponding to the sample pressure of 1500 hPa) and
108 (squares), UBE-113 (diamonds), and UBE-114 (plus data for other sample pressures (not shown). Error bars
signs), filled to 655 hPa and stored at 950 hPa, agree well denote the standard error of the regression for data sets with
with the calculated increase (solid line). Note that dO2/N2 more than two points.
does not increase linearly because of the pressure decrease
of the sample air after each decanting. flux is controlled by the humidity of the air at the flasks’
storage location. With an average ambient vapor pressure
Figure 7 shows the increasing amount of moisture as a of 14 hPa, which corresponds to 60% relative humidity
function of storage time for air samples in 0.5 and 2.5 L at 20C, one obtains from the observed drift rates a
flasks stored in the laboratory. Water vapor concentration permeation coefficient for water vapor through our Viton
was inferred by mass spectrometry from ion beam intensity O-rings (d = 1.7 mm and A = 20 mm2) of about KH2O =
at m/z 18, measured as a voltage V18. After subtraction 220 1015 m2 s1 hPa1, which is consistent with the
of the background signal, which is the m/z 18 intensity of a values listed in Table 1.
dry standard gas, V18 was converted into a pressure using [21] Thus permeation of water vapor may have adverse
the m/z intensity of N2 (V28) and a correction factor, which effects on trace gas measurements if sample air is not dried
accounts for the different ionization efficiencies of water at the time of analysis. The increasing water vapor concen-
vapor and N2. tration leads to dilution of trace gas concentrations in
[19] The 0.5 L flask air samples show an increase in sample air and might also lead to other storage- or analy-
moisture content of 3.87 ± 0.17 hPa yr1; the 2.5 L samples sis-related measurement artifacts for some species, includ-
are enriched by 0.79 ± 0.22 hPa yr1. The 2.5 L flasks are a ing dO2/N2.
factor of 4.9 ± 1.4 less influenced by water vapor 3.3. Permeation of Ar and CO2
corresponding to the 5 times larger volume of these flasks.
Both flask types had a sample pressure of 1000 hPa. [22] Changes in dAr/N2 and dCO2/N2 for the same sam-
[20] Since for initially dry samples the water vapor ples as in Figure 4 are shown as a function of storage time in
pressure difference between sample and surrounding air is Figure 8. The dAr/N2 values of these four samples show an
independent of sample pressure, the water vapor permeation increase of 399 ± 32 per meg after 299 days. Because of
larger mass-dependent fractionation processes at the time of

Figure 5. Changes in dO2/N2 due to storage in Common-

wealth Scientific and Industrial Research Organisation’s 0.5 Figure 7. Water vapor as a function of storage time for 0.5
L glass flasks fitted with Viton (circles, with linear L (circles) and 2.5 L flasks (plus signs). The steeper slope
regression represented by the line), perfluoroalkoxy (plus for the 0.5 L flasks (factor of 4.9 ± 1.4) reflects the
signs), and polytetrafluoroethylene (squares) O-rings. difference in flask volume.

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D04309 STURM ET AL.: PERMEATION OF GASES THROUGH O-RINGS D04309

people in the laboratory may cause diurnal CO2 concentra-

tion variations, it is difficult to accurately predict CO2
permeation fluxes. Under some circumstances, there may
be little or no change in the CO2 concentration of sample
air, for example, where a background air sample at a
pressure of 1200 hPa is stored in an environment with
CO2 enriched by 20% above background level.
[25] In terms of a mixing ratio the permeation of other
gases may also become important. The increasing amount
of CO2 in the samples of Figure 8 is diluted by the
simultaneous influx of water vapor. If the sample air is
not dried again at the time of analysis and assuming an
ambient water vapor pressure of 14 hPa and KH2O = 220
1015 m2 s1 hPa1, one would obtain a CO2 concentration
drift after 299 days of 0.2 ppm for the conditions as
outlined in Figure 8. If the sample air is dried prior to
measurement, the dCO2/N2 increase of 6% corresponds to a
CO2 concentration change of +2.4 ppm. Thus CO2 measure-
ments from flask samples are not only dependent on flask
volume and sample pressure but are also highly sensitive to
ambient CO 2 mixing ratios and analysis techniques.
Figure 8. Changes in dAr/N2 and dCO2/N2 plotted as a Changes in CO2 of the magnitude reported here are poten-
function of the storage time and as a change relative to the tially much larger than targets for CO2 intercomparability
first measurement for the same samples as in Figure 4: among laboratories of ±0.1 ppm in the Northern Hemi-
UBE-107 (circles), UBE-108 (squares), UBE-113 (dia- sphere or ±0.05 ppm in the Southern Hemisphere recom-
monds), and UBE-114 (plus signs). (top) The dAr/N2 values mended by the World Meteorological Organization [2003].
show an increase of 399 ± 32 per meg after 299 days. On [26] Effects of permeation will also influence the isotopic
the basis of KAr = 1.65 1015 m2 s1 hPa1 one would composition of CO2 in flask samples. It is likely that isotopic
expect an increase of 1071 per meg (line). (bottom) The fractionation is associated with the permeation process itself;
CO2/N2 ratios (in %) are enriched by 5.8 ± 0.3% after that is, the lighter isotopomeres are favored over the heavier
299 days. The initial CO2 concentrations were between ones, comparable, for example, with diffusion of CO2
401.6 and 406.9 ppm. The line is an estimate based on through air. Moreover, the influx of water vapor might lead
KCO2 = 6 1015 m2 s1 hPa1 and an assumed mean CO2 to 18O isotopic exchange between water and CO2.
concentration of 450 ppm of laboratory air. [27] Permeation can affect the isotopic composition, even
in the absence of permeation fractionation effects. Changes
analysis and the poorer overall precision of dAr/N2 measure- in d13C occur if flasks are stored in an environment enriched
ments, the storage drift is not as well resolved as for dO2/N2. by biogenic CO2, such as in a laboratory. Assuming an
The dAr/N2 drift rate is slightly smaller than that for dO2/N2. average enrichment of 80 ppm with d13C = 25% (versus
This is consistent with measurements from Langenfelds Vienna Peedee belemnite) compared with 8% for back-
[2002]. However, an estimate based on a permeation ground air, the drift rate for 0.5 L flasks with 600 hPa sample
coefficient of KAr = 1.65 1015 m2 s1 hPa1 (Table 1) pressure would be about 0.05% yr1. Thus changes in
gives an expected drift rate of 1070 per meg in 299 days for isotopic composition become potentially significant if sam-
these samples. The predicted and observed drift rates differ ples are stored for long periods in a CO2-rich environment.
by a factor of 2.7, suggesting that the value of KAr in Table 1 [28] In many laboratories it is the practice to store pure
is too large. CO2 samples for a limited period of time in test tubes sealed
[23] The initial CO2 concentrations of these samples were by an O-ring valve. On some occasions, for example, when
between 401.6 and 406.9 ppm. During the storage period of shipping such tubes to other laboratories, storage times can
299 days a dCO2/N2 change of 6% was observed (Figure 8, be up to several weeks, and permeation effects for these
bottom). This result can be explained with a CO2 permeation samples with their large CO2 gradient can become large.
coefficient of KCO2 = 6 1015 m2 s1 hPa1 (Table 1) and a These effects were already observed in the 1980s [Keeling
mean CO 2 concentration of ambient laboratory air of et al., 1989] but were not studied in detail at that time. New
450 ppm, i.e., 20% above a background atmospheric investigations, now with the aid of the permeation model
CO2 level of 370 ppm (solid line, Figure 8). presented here, are under way at the Centrum voor Iso-
[24] Unlike for O2, N2, and Ar, where concentration topenOnderzoek (CIO), Groningen, Netherlands. They will
changes in ambient air are negligible with respect to produce, among other things, d13C and d18O permeation
permeation, the mole fraction of CO2 in laboratory air can fractionation factors.
change substantially. Changes in sample CO2 concentration
are therefore highly dependent on the storage conditions.
The CO2 partial pressure difference and the permeation flux 4. Double O-Ring Valves
are likely to vary with storage location and also with time. [29] Tests with different O-ring materials and the data in
As the flask samples may be stored in a CO2-enriched Table 1 show that Viton has comparably low permeation
environment or a well-ventilated room or as the presence of coefficients. So far, it is the preferred material for O-rings in

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glass flasks used for O2/N2 measurement programs. A new

approach to further reduce permeation influences is a new
valve design, the so-called double O-ring valves. This
design was, to our knowledge, first discussed and used by
the National Institute for Environmental Studies, Tsukuba,
Japan. In contrast to conventional valves, where a single
O-ring seals the sample air from the atmosphere, the double
O-ring valves incorporate a second O-ring, which creates an
additional small buffer volume (Figure 1c). Initially, this
buffer volume also contains sample air, eliminating any net
permeation fluxes between flask and buffer volume. In first
order, permeation due to partial pressure gradients between
the sample and ambient air only leads to changes of air
composition in the buffer volume. Only these changes in the
Figure 10. Comparison of dO2/N2 drifts for 0.35 L flasks
buffer volume are eventually passed on to the flask volume
equipped with either two single O-ring (open symbols) or
through permeation. The larger the buffer volume is and the
two double O-ring (solid symbols) valves. The buffer
smaller the ambient/buffer permeation fluxes are, the more
volume of the double O-ring valves is 0.08 mL. Sample air
effective the double O-ring valve is in reducing modifica-
pressure is 1000 hPa, and ambient storage pressure was kept
tion of sample air composition. The construction of the
below 4 hPa for both flask types. The calculated changes for
double O-ring valve allows a sequential opening in order to
single and double O-ring flasks are represented by the
be able to evacuate the buffer volume prior to decanting
shaded and the solid line, respectively.
sample air into analytical inlet systems.
[30] The permeation influence with double O-ring valves
can be calculated by solving two coupled linear differential [31] A different experimental setup was used at the CIO,
equations for the partial pressures in the buffer and flask Groningen, for a comparison test between single and double
volume, respectively. In addition to calculations, different O-ring valves. All flasks had a volume of only 0.35 L and
flask storage tests with double O-ring valves were carried were filled with dry air to ambient pressure (1000 hPa).
out. Figure 9 shows a storage drift test performed at the Max During the storage time they were connected to a vacuum
Planck Institute for Biogeochemistry (MPI-BGC), Jena, line, which kept the pressure below 4 hPa in order to sustain
Germany. Here 1.4 L flasks equipped with two custom- a pressure gradient of 1000 hPa across the O-rings. The
made double O-ring valves (Louwers Hapert, Netherlands) flasks were fitted with two valves each (Louwers Hapert,
and filled with dry sample air to 2000 hPa were stored at Netherlands), either with single or double O-rings. The
ambient pressure and were measured several times during double O-ring stopcocks were produced at the workshop
200 days. The buffer volume of each valve is 0.6 mL. Six in Groningen. The buffer volume of these valves is
flasks show a change in dO2/N2 of 3 to 31 per meg after about 0.08 mL.
200 days storage in accordance with the calculated drift rate [32] The experiment was carried out twice, once with 16
(solid line in Figure 9). Three samples, however, are flasks stored over a period of 98 days and once with 8 flasks
depleted in dO2/N2 by 70 to 92 per meg, which is close stored over 66 days. Samples were measured after a range
to the expected change for single O-ring flasks of 116 per of storage times and in pairs at a time, in each case
meg. Possible explanations for this different behavior are including a single and a double O-ring flask. Each sample
different initial flask conditions, i.e., impurities in the flasks, was analyzed only once so that sample pressures were
or oxidation of grease used to lubricate the Viton O-rings. constant over the duration of the storage test.
[33] The results are plotted in Figure 10 as the deviation
from the mean of the measurements on the filling day. Solid
symbols represent individual samples from double O-ring
flasks, and open symbols represent samples from single
O-ring flasks. The single O-ring flasks show a change in
dO2/N2 of about 470 per meg after 98 days, which is in
good agreement with the predicted change for this test setup
(shaded line). The drift rate for the double O-ring flasks is
clearly lower. However, the calculated drift rate leads to a
depletion of 181 per meg (solid line), whereas the measure-
ments reveal a depletion of 280 per meg over 98 days
storage, which corresponds to an improvement factor of only
about 1.7 compared with the single O-ring flasks. Indepen-
dent of the O-ring dimensions, the permeation coefficients,
and the size of the buffer volume, one would expect the
Figure 9. Changes in dO2/N2 due to storage for nine 1.4 L double O-ring flasks to perform at least a factor of 2 better
flasks equipped with two double O-ring valves (symbols, with respect to permeation than the single O-ring flasks
dashed lines). The buffer volume of each valve is 0.6 mL, because the overall thickness of polymer for any gas to
and the sample air pressure is 2000 hPa. The solid line permeate is doubled with two O-rings. The reason why this
represents the expected drift rate. is not the case for the presented experiment is not yet

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storing flasks in a CO2-controlled environment is to store

them in a well-ventilated area where CO2 levels are always
close to background.
[38] The water vapor content increases for initially dried
samples if they are stored at ambient humidity. If water vapor
affects the analysis, the sample air therefore has to be dried
again prior to the measurement after long storage periods.
[39] The surface area and the thickness of the sealing
material vary with different valve types. Such geometric
differences can also result in significant differences in
permeation rates. Where samples must contain overpres-
Figure 11. Calculated ratio of single O-ring to double O-ring sure, e.g., for reasons concerning introduction of air samples
flask storage drifts (improvement factor) for dO 2 /N 2 to analytical instruments, the double O-ring valves can
and double O-ring flasks with a buffer volume of 0.6 mL per considerably reduce permeation influences, at least for
valve as a function of time. This improvement factor is nearly storage times of up to a few weeks. Other methods for
independent of flask volume and pressure gradients. reducing permeation effects are under investigation. One
approach involves using seals constructed from Kel-F
known. Part of the explanation might be the different (polychlorotrifluoroethylene (PCTFE)). Compared with
absolute pressure gradients across the two O-rings, which Viton, Kel-F has the advantage of lower permeation coef-
causes different plastic deformations of the two O-rings. ficients but the disadvantage of its greater hardness, making
[34] On the basis of theoretical considerations it is clear it more difficult to achieve reliable glass-polymer seals.
that the performance of double O-ring flasks compared with Tests with Kel-F-sealed glass flasks are currently being
single O-ring flasks becomes less efficient the longer the performed at the MPI-BGC, Jena, Germany.
storage period is. Double O-ring flasks with a buffer volume [40] Acknowledgments. This work was supported by the Swiss
of 0.6 mL per valve and O-ring dimensions of d = 1.7 mm National Science Foundation and the EC Projects MILECLIM, ALPCLIM,
and A = 20 mm2 lead to a substantial improvement in dO2/ and AEROCARB, an EC Project of the CARBOEUROPE cluster. We
N2 stability only for the first few weeks of storage. The thank P. Nyfeler for technical assistance and R. Francey and P. Steele for
helpful discussions. Valuable comments were provided by R. Keeling and
permeation influence compared with single O-ring flasks is an anonymous reviewer. We acknowledge the International Foundation
reduced after 1 month by a factor of 29 and after 1 year by a High Altitude Research Stations Jungfraujoch and Gornergrat (HFSJG),
factor of only 3.5 (Figure 11). The improvement factor is, to which made it possible to take flask samples at Jungfraujoch.
a good approximation, independent of flask volume and
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