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CO2 soil flux at Vulcano (Italy): Comparison between active and passive
methods

Article in Applied Geochemistry · January 2004

DOI: 10.1016/S0883-2927(03)00111-2

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 Applied Geochemistry 19 (2004) 73–88
www.elsevier.com/locate/apgeochem

CO2 soil flux at Vulcano (Italy): comparison between

active and passive methods
Maria Luisa Carapezzaa,*, Domenico Granierib
a
INGV—Sezione Roma1, Via di Vigna Murata 605, 00143 Rome, Italy
b
INGV—Osservatorio Vesuviano, Via Diocleziano, 323, 80128 Naples, Italy

Received 26 September 2002; accepted 9 May 2003

Editorial handling by H Ármannson

Abstract
Carbon dioxide soil flux has been used for many years to monitor Italian active volcanoes and both the active
Dynamic Concentration (DCM) and the passive Accumulation Chamber (ACM) methods are employed. These two
methods have been compared by means of 218 simultaneous flux measurements carried out in the La Fossa area of
Vulcano Island, where a large variation of CO2 soil release occurs. Results indicate that DCM overestimates CO2 flux and
is proportional to it only in high flux zones (flux higher than 100 gm
2 day
1). Using ACM fluxes and the Stefan–Maxwell
equation, the measured CO2/depth curves in the soil could be reproduced. In high flux points CO2 is transported
mostly by viscous flow up to a very shallow depth and then by diffusive flow, which is the dominant gas transport
mechanism in low flux points. Carbon dioxide soil flux values are controlled by proximity to active gas releasing frac-
tures, by changes in the barometric pressure and by variations in soil permeability.
# 2003 Elsevier Ltd. All rights reserved.

1. Introduction therefore be established. The knowledge of these areas is

Over the last years soil degassing, mainly of CO2, has
been increasingly employed for the study of gas release
in volcanic and geothermal areas (Bergfeld et al., 2001)
and for the recognition of volcano–tectonic structures
(Barberi and Carapezza, 1994; Giammanco et al., 1998).
Geochemical studies have shown that in both active and
quiescent volcanoes, gas is released not only from the
craters and fumaroles, but also from particular zones on
the flanks and even at the base of volcanoes. The con-
tribution of this soil degassing to the total gas output is
significant (Allard et al., 1991; Chiodini et al., 1998).
A deep origin (e.g. magmatic vs metamorphic) of the
released CO2 can be ascertained by isotopic analyses
and the nature of diffuse degassing structures can
* Corresponding author. Tel.: +39-06-5186-0420; fax: +39-
06-5186-0549.
E-mail address: carapezza@ingv.it (M.L. Carapezza).
0883-2927/03/$ - see front matter # 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0883-2927(03)00111-2
very important in active volcanoes, like Mt. Etna, where
high risk flank eruptions frequently occur and the geo-
chemical monitoring of degassing structures as potential
sites for opening of new eruptive fissures is a useful
complement to seismic and ground deformation mon-
itoring (Badalamenti et al., 1994a).
Also of great importance is the identification and
control of degassing structures in inhabited areas
around quiescent volcanoes, like the island of Vulcano
or Colli Albani, where high CO2 flux through the soil
can produce a dense gas layer on the ground with a
consequent lethal hazard, as indicated by episodes of
human and animal deaths in these zones (Baxter et al.,
1990; Badalamenti et al., 1991; Pizzino et al., 2002;
Carapezza et al., 2003).
Geochemical monitoring of anomalous soil degassing
on the flank of volcanoes may represent, together with
remote sensing methods such as COSPEC and FTIR
(Malinconico, 1987; Francis et al., 1998; Bruno et al.,
1999; Burton et al., 2001), an important surveillance
74 M.L. Carapezza, D. Granieri / Applied Geochemistry 19 (2004) 73–88
tool when an eruption is impending and the monitoring
of crater fumaroles becomes impossible.
All the cases mentioned require frequent measure-
ments of the CO2 flux or, better, continuous monitoring.
In Italy, two different methods to measure CO2 flux
have been developed and extensively used in volcano
monitoring: the accumulation chamber method (ACM)
(Chiodini et al., 1998) and the dynamic concentration
method (DCM) (Gurrieri and Valenza, 1988). Presently
there are 12 automatic stations monitoring CO2 flux on
Italian volcanoes: 4 (DCM) at Vulcano Porto, the other
8 (ACM) are placed at Stromboli (2), Vesuvius (2),
Campi Flegrei (2) and Etna (2). In addition, monthly, or
more frequently in case of crisis, field surveys are carried
out on sampling networks at Vulcano and Etna (with
DCM) (Badalamenti et al., 1988; Diliberto et al., 1993,
2002; Giammanco et al., 1998), and at Vesuvius, Campi
Flegrei and Cava dei Selci site on Colli Albani with
ACM (Chiodini et al., 2001; Carapezza et al., 2003). The
DCM was first utilised in Italy and data collection goes
back nearly 15 a (Badalamenti et al., 1988). It is still the
only method systematically used in soil gas monitoring
at Vulcano and on the Etna flanks, along with the 2 new
ACM stations installed in summer 2001. The ACM has
become progressively more popular for CO2 soil flux
measurements, both in Italy and elsewhere (see Bergfeld
et al., 2001).
In order to make a close comparison of these two
methods they were both simultaneously used in detailed
field surveys on the island of Vulcano, over a large soil
degassing area with a wide range of CO2 fluxes. The
field work was planned in order to investigate the dif-
ferences between the two methods and their limits and
advantages. An attempt is made to quantify a conver-
sion factor between the two data sets which may help in
obtaining comparable flux values that allow, in case of
volcanic unrest, interpretation of the different data sets.
In addition to 218 simultaneous field flux measure-
ments, soils were cored and analysed in the laboratory
to check for the effects of their permeability and grain
size on the CO2 flux. Carbon dioxide concentration gra-
dients in the soil were measured at some locations to
investigate the gas transport mechanism. Finally some
environmental parameters were simultaneously mea-
sured to check for their influence on the CO2 soil gas flux.
2. Geological and geochemical setting
Vulcano is the southernmost island of the Aeolian arc
that was formed by subduction of the African plate
beneath the European plate (Barberi et al., 1973; Gas-
parini et al., 1982; Patacca et al., 1990). The island is
entirely made of volcanic rocks, ranging in composition
from trachybasalts to shoshonites, latites, trachytes and
rhyolites (Keller, 1980; Ellam et al., 1988; De Astis et
al., 1997; Gioncada, 1997). It emerged from the sea
about 120 ka ago and consists of several eruptive centres
that migrated with time from SE to NW. There are two
active volcanic centres in the northern part of the island:
La Fossa and Vulcanello. The La Fossa cone was built
up in the last 6 ka whereas Vulcanello emerged from the
sea in 183 B.C. (Keller, 1980). Both had several histor-
ical eruptions, the most recent of which occurred at La
Fossa in 1888–1890 and gave name to the ‘‘vulcanian’’
explosive eruption type (Mercalli and Silvestri, 1891;
Walker, 1973). Since the end of the last eruption in
1890, the La Fossa cone has been in a quiescent state,
characterised by an intense fumarolic activity on the
rim, inside the crater and at the base of the volcanic
edifice (Baia di Levante beach).
The fluids discharged by the La Fossa crater fumar-
oles are the result of a mixing process between (a) a
magmatic phase released by a shallow magmatic body,
(b) a geothermal phase resulting from the vaporization of
a brine or of laterally infiltrated seawater and (c) a minor
surficial component of meteoric origin (Chiodini et al.,
1995; Nuccio et al., 1999; Tedesco and Scarsi, 1999).
During the last century, several episodes of unrest
occurred at the La Fossa that were not followed by
eruptions. The first occurred in 1916–1924 when the
temperature of the crater fumaroles progressively
increased from about 100 to 613  C (Sicardi, 1941). A
second increase of crater fumarole temperature and gas
output began in 1977. The temperature reached the
maximum value of 692  C in January 1993, then
decreased to 430  C in February 1996 and increased
again to over 500  C in the same year (Barberi et al.,
1991; Capasso et al., 1997). Since then, both gas output
and maximum temperature have decreased slightly to
the present value of 340–360  C. During the progressive
increase and expansion of the fumarolic activity no sig-
nificant geophysical anomalies were recorded, apart
from some short seismic swarms and minor inflation
and deflation episodes (Barberi et al., 1991; La Volpe et
al., 1997).
The unrest, therefore, mostly consisted of an increase
(with fluctuations) in the steam and gas output and
maximum temperature of the crater fumaroles. Chemi-
cal and isotopic evidence, especially during rapid chan-
ges, indicated an increasing input of hot magmatic
fluids. An increasing input of deep hot fluids into the
shallow groundwaters at the base of the volcano was
also observed (Chiodini et al., 1995; Tedesco, 1995;
Italiano et al., 1998; Nuccio et al., 1999; Capasso et al.,
1999, 2001). A magmatic component is indicated by the
high gas temperature, the nature of the compositional
variations and the high 3He/4He ratio (up to 6 times the
air ratio: R/Ra=6; Tedesco and Scarsi, 1999; Italiano
and Nuccio, 1997) a value falling in the compositional
range for the magmatic He of island arc volcanoes
(Craig et al., 1978; Welhan et al., 1988). Clinopyroxenes
 M.L. Carapezza, D. Granieri / Applied Geochemistry 19 (2004) 73–88 75

of the 1888–1890 eruption products have a significantly

lower R/Ra ratio (3.8; Magro, 1997) suggesting that the
present He is being released from a more primitive, and
possibly deeper, magma body than the 1888–1890
magma, which also shows crustal contamination
(Gioncada, 1997). The positive correlation between CO2
and He and the CO2 isotopic composition indicate that
CO2 also derives from magma degassing. The varia-
tions observed in fumarolic discharge during unrest
crises are attributed to variability in the vertical per-
meability induced by earthquakes and self-sealing
hydrothermal processes, that modify the mixing pro-
portion between the magmatic and the hydrothermal
gas components (Chiodini et al., 1992, 1995; Tedesco,
1995). Degassing at different depths by depressurisation
of a saturated magma has also been postulated (Nuccio
et al., 1999).
Soil gas measurements began at Vulcano as part of a
geothermal exploration project (Bertrami et al., 1984).
Carbon dioxide and He concentration anomalies were
found, and shown to be correlated with the main struc-
tural features of the island. In 1984 a systematic mon-
itoring of soil CO2 was initiated. The CO2 flux was
measured at least monthly by DCM on a network of 51
points at the base of the La Fossa cone and in the
inhabited area of Vulcano Porto (Badalamenti et al.,
1988) (Fig. 1). Since 1989, CO2 and He concentrations
at 50 cm depth were also measured monthly using the
same network (Carapezza and Diliberto, 1993; Car-
apezza, 1994, 1996; Diliberto and Gurrieri, 1994;
D’Alessandro and Parello, 1997). Results revealed the
Fig. 1. Location of the CO2 soil flux measurement points.
existence of zones, particularly at the southern base of
Dashed areas indicate the fumarolic fields of the La Fossa cra-
the La Fossa cone (Palizzi zone) and at Baia di ter and Baia di Levante. Coordinates are in UTM 33- ED 50.
Levante (Fig. 1), with strong soil emission of CO2 and Digital Elevetion Model of Vulcano Island by Pareschi et al.
He rich gas, chemically and isotopically similar to the (1999).
gas of the nearest fumaroles (crater and Baia di
Levante) and showing synchronous variations with
them. In 1988 the ACM was first employed at the La soil CO2 flux measurements. In 1994 the authors carried
Fossa (Baubron et al., 1990) and the existence of out a detailed comparative study of the ACM and DCM
strong soil CO2 and He degassing areas with magmatic techniques at this site.
inprint was confirmed.
In the early 1990s, the temperature and gas output
from the La Fossa crater fumaroles increased so strongly 3. Techniques for the measurement of CO2 soil flux
that it became dangerous to sample the fumaroles. As an
alternative, soil gas sampling at the base of the volcano, Many CO2 soil flux measurement techniques have
with particular attention paid to monitoring the CO2 been applied for geological and agricultural aims and
flux, was intensified. Continuous automatic stations include both direct and indirect methods (e.g. Reiners,
using DCM were installed at the base of the La Fossa 1968; Kucera and Kirkham, 1971; Kanemasu et al.,
cone (Badalamenti et al., 1994b) for recording the CO2 1974; Parkinson, 1981). Direct methods are called either
soil flux. active or passive, whether or not a flux of air is used to
These studies have shown a wide variation of CO2 extract gas from the soil. In the present study, the
flux from the soil around the La Fossa cone, ranging authors have utilised the active ‘‘dynamic concen-
from 0.2 to 2900 gm
2 day
1 (Chiodini et al., 1998), i.e. tration’’ (DCM) and the passive ‘‘accumulation cham-
from values typical of vegetated soil to those of actively ber’’ (ACM) methods. The measurement of CO2
degassing volcanic zones. This area therefore appeared concentration profiles in the soil, in some of the loca-
to be an ideal site to test the different techniques for tions where CO2 flux by DCM and ACM had been
76 M.L. Carapezza, D. Granieri / Applied Geochemistry 19 (2004) 73–88
measured, allows an estimate of the prevailing gas
transport regime (Evans et al., 2001).
The DCM (Gurrieri and Valenza, 1988) is an ‘‘active’’
method shown schematically in Fig. 2. The gas is
extracted from the soil at about 50 cm depth by means
of a pump. The aspiration flow of the pump is constant
and if CO2 flux from the soil is lower than that of the
pump, some outside air enters the system, mixes with
the soil gas and the mixture is brought to the analyser.
This should maintain unaltered the natural flow condi-
tions around the measuring site. Once pumping, the DC
measurement is obtained when the CO2 concentration
of the analysed gas–air mixture reaches a constant
value. According to Gurrieri and Valenza (1988) the
dynamic concentration is directly proportional to CO2
flux by the following relationship:

t ¼ M CD ð1Þ
where
t is the CO2 flux (in cm/s), CD is the measured
CO2 dynamic concentration (expressed in mole fraction)
and M is a factor depending on the experimental device
(geometry and length of the probe; flow rate of the
Fig. 2. Device for the measurement of the CO2 dynamic con-
centration (modified after Gurrieri and Valenza, 1988). The 50
cm long and 1.3 cm wide steel tube (a), laterally perforated in
the lowest 15–20 cm, is rammed into the ground. A small Cu
probe (b) is inserted into it and a rubber plug (c) seals the sys-
tem. The soil gas inside the tube is connected to the atmosphere
through a second small tube inserted into the plug (d). The gas
is brought to an IR spectrometer analyser (IRS) by a pump (e).
pump) and on soil permeability. For the loose pyro-
clastic-alluvium Vulcano soil, a constant M value of
3.8*10
2 cm/s was adopted assuming a constant poros-
ity coefficient (P=0.34) and a constant soil permeability
(24 darcy) (Gurrieri and Valenza, 1988; Badalamenti et
al., 1988). It will be shown that this assumption is
incorrect, as the Vulcano soil permeability varies by
over one order of magnitude and the need to estimate
the factor M at each measurement point appears to be a
strong limitation to the use of DCM.
Witkamp and Frank (1969) have shown that the CO2
flux tends to be overestimated when DCM is used and
according to Kanemasu et al. (1974) and Falcone (1994)
results are strongly affected by the physical modifi-
cations induced by pumping under different flux
regimes. In the opinion of Tonani and Miele (1991)
DCM would be proportional to flux for high CO2 flux
values (510
3 cm/s or 1690 gm
2 day
1) only.
The ACM (see Fig. 3 for technical details) is a direct,
passive method based on the measurement of the initial
CO2 concentration increase inside a chamber of known
volume, placed on the soil. This increase is directly pro-
portional to the CO2 flux (Tonani and Miele, 1991). The
method is based on the mass balance of the gas in the
volume of the chamber:
HdcðtÞ=dt ¼
t ð1
cðtÞÞ ð2Þ
Fig. 3. The accumulation chamber for CO2 soil flux measure-
ment (modified after Chiodini et al., 1998). The 10 cm high and
40 cm diameter circular chamber is placed on the ground. The
soil gas is pumped to an IR spectrometer after the removal of
water vapour by a filter filled with Mg(ClO4)2 and it is then
reinjected into the chamber. The spectrometer signal is
acquired by the AD converter and transmitted to the palmtop
computer.
 M.L. Carapezza, D. Granieri / Applied Geochemistry 19 (2004) 73–88
where H is the height of the AC, dc(t)/dt is the increase
of CO2 concentration with time within the chamber,
t
is the total CO2 flux entering from the soil into the
chamber, c(t) is the CO2 concentration at time t.
Integration of (2) gives:
ðt
=HÞ
cðtÞ ¼ 1
e ð20 Þ
and assuming that ct=0=0
dc=dt ¼
t=H ð3Þ
In the field, the gas–air mixture within the ACM is
continuously analysed by an IR spectrometer and the
concentrations are recorded on a palmtop computer,
where the concentration/time curve may be seen. A
program gives the flux value (in cm/s or ppmV/s) once
the operator has selected the portion of the curve for the
initial concentration gradient calculation. The ACM
does not require any specific assumption and flux can be
measured without knowing the soil characteristics. The
method has been tested by several authors under con-
trolled laboratory conditions. Chiodini et al. (1998)
measured values within 15% of the imposed flux,
whereas Evans et al. (2001) recognized a systematic
underestimation of the flux (average of
12.5%), over
an imposed flux range of 200–12,000 gm
2 day
1.
In a field ACM reproducibility test carried out at two
points with high and low CO2 flux and consisting
respectively of 20 and 12 consecutive measurements on
the same site, the authors found an uncertainty of 12%
(high flux, avg=997 gm
2 day
1) and of 24% (low flux,
avg=5.7 gm
2 day
1).
4. Field work
The field work was carried out in July–mid September
1994. Measurement points were distributed over a 2.2
km2 area, at Vulcano Porto and at the base of the La
Fossa cone (Fig. 1). It consisted of 218 simultaneous
measurements of CO2 soil flux by DCM and ACM and
particularly of:
A survey on 47 points of the permanent network
currently used for monthly measurements of the CO2
flux by the DCM (Badalamenti et al., 1988; Diliberto
et al., 1993 and 2002) (Fig. 1);
Ten surveys on 11 selected points at the base of the La
Fossa cone to monitor the flux variation with time (9 of
the permanent network and 2, 4M and C4, newly iden-
tified in the highly degassing Palizzi zone) and several
additional measurements on the Palizzi zone points;
Two surveys to investigate short time and small scale
lateral variations.
On the network, DCM flux was measured in the per-
manent probes whereas the ACM equipment was placed
77
on the ground with its center at 30–70 cm distance from
the DCM probe. At the other points DCM flux was
measured by placing the probe at the centre of the sur-
face covered by the ACM chamber.
At 45 points on the permanent grid a soil core was
drilled to about 50 cm depth (to 100 cm depth in 5 high
flux points, with a recovery of 72–83 cm). All the cores
were collected in the proximity (less than 50 cm dis-
tance) of the measurement points, and analysed in the
laboratory for the physical characteristics of the soil.
5. Laboratory analysis of soil samples
In order to not disturb the soil samples, permeability
was measured directly using the Al casing of the 45
cores, whose length varied from 33.5 to 59 cm, but was
of about 50 cm in most samples. Water permeability
was measured by a variable load permeameter, after
saturation in water. Results are shown in Table 1 and in
the histogram of Fig. 4.
The variation is very wide (0.1–59.9 darcy). Large
differences are found also for cores drilled only a few
dozens of meters apart, indicating important lateral
variations in the Vulcano soil characteristics even on a
small scale. In all the 5 longer cores, the permeability of
the layers below 50 cm depth (22–33 cm thick, depend-
ing on recovery) was found to be much lower than in the
upper 50 cm. It is therefore clear that a constant per-
meability value cannot be assumed to convert DC into
flux values as used by Gurrieri and Valenza (1988),
Badalamenti et al. (1988) and Diliberto et al. (1993 and
2002).
Grain size analysis was made on 25 soil cores. In the 5
longest cores, analysis was carried out separately above
and below 50 cm, so that a total of 30 grain size analyses
were carried out, representative of 25 different CO2 flux
measurement points.
Fig. 4. Frequency histogram of Vulcano soil permeability
measured in 50 cm cores. Asterisk indicates the value (24 darcy)
used by Gurrieri and Valenza (1988) for the conversion of the
CO2 dynamic concentration into flux.
78 M.L. Carapezza, D. Granieri / Applied Geochemistry 19 (2004) 73–88

Table 1
Soil permeability and average and variation range of ACM and DCM CO2 soil fluxesab

Point K DCM DCM c ACM Meas. Point K DCM DCM c ACM Meas.
No. Darcy No.c No. Darcy Avg. No.c
Min Max Avg. Avg Min Max Avg. Min Max Avg. Min Max Avg.

2 2.8 71 167 99 12 16 85 49 14 29 5.5 10 2 4 1

3 34.2 276 610 394 562 32 95 54 13 30 7.5 13 4 5 1
4 17.1 1048 6135 2811 2003 122 624 276 23 32 3.7 13 2 3 1
4M 30.4 6118 27,547 16,709 21,165 465 2265 1252 20 33 6.4 42 11 19 1
C4 32.4 1555 20,111 6405 8620 238 1301 780 12 34 4.6 13 2 1 1
6 8.1 19 55 35 12 1 14 7 12 35 6.0 42 10 32 1
7 15.0 132 82 21 1 36 6.0 42 10 24 1
8 8.0 13 64 25 8 10 21 16 13 38 4.2 64 11 18 1
9 55.3 13 48 23 54 3 16 8 11 39 4.2 71 12 29 1
10 3.0 51 135 81 10 8 33 20 12 40 12.8 39 21 23 1
12 4.6 87 161 119 23 37 96 75 12 41 8.3 10 3 9 1
14bis 59.9 257 641 47 1 41bis 2.0 35 3 14 1
15 41.4 61 225 143 246 13 51 32 2 42 1.9 10 1 8 1
16 6.0 32 51 42 10 4 22 13 2 44 26.7 276 307 23 1
17 55.0 32 74 15 1 45 16.8 19 13 12 1
19 2.6 71 8 94 1 46 20.4 103 151 127 108 64 85 74 2
20 17.7 51 38 82 1 47 14.2 83 50 20 1
21 2.6 35 4 18 1 $0 12.7 10 13 11 7 2 11 6 2
22 0.1 13 0 18 1 81 6.7 48 13 35 1
23 6.0 19 5 21 1 82 35.6 51 76 33 1
24 2.6 3 0 4 1 83 11.4 22 31 27 13 14 17 15 2
25 7.4 19 6 3 1 84 13.0 58 31 19 1
26 2.5 6 1 4 1 85 8.0 19 6 14 1
27 16.2 19 13 15 1 86 8.0 13 295 135 45 10 75 34 10
28 5.5 35 8 15 1
a
Flux values are in gm
2 day
1
b
DCM c=corrected values
c
Meas. No.=Number of measurements.

Samples are all made up of loose volcaniclastic sedi-
ments. According to the Wentworth (1922) classification
all samples fall into the sand field: 3 fine sands,17 med-
ium size sands, 8 coarse sands and 2 very coarse sands.
Soil samples have an average grain diameter ranging
from
0.8 to 2.37 phi (avg=1.04; =1.61). Sorting
ranges from 0.9 to 2.57 phi (avg=1.74; =0.5); 2 sam-
ples are moderately sorted, 15 poorly sorted and 13 very
poorly sorted. Skewness ranges from
0.38 to 0.48
(avg=
0.03 and =0.18) with nearly symmetrical dis-
tributions for most samples.
The textural characteristics of the analysed samples
were used to evaluate their permeability using the fol-
lowing relation (Krumbein and Monk, 1951):
2 ð
1:31 
Þ
Kt ¼ Co ðDm Þ e
where Kt is the intrinsic permeability in darcy, Co is a
constant (760 darcy/mm2), Dm is the average dimension
of the grains (mm) and 
is the sorting in phi units.
Kt values calculated by Eq. (4) were compared with
the measured permeability values (K), neglecting the
samples without grain size uniformity (i.e. presence of
cm-sized pebbles). The two sets of data show a good
correlation (r2=0.796), with Kt usually higher than K
(only in one case it is lower and in 6 cases the values are
very similar). These differences can be explained with
reference to the fact that Kt depends on a factor (Co)
which likely differs from soil to soil. For this reason, in
the following discussion the measured K values will be
considered.
The intrinsic (water) permeability measured in the soil
samples can be used to estimate the apparent (gas) per-
meability by means of the Klinkenberg equation (see
Eq. 16 in Appendix). Thorstenson and Pollock
(1989a, b) estimated the Klinkenberg parameter for air
(bair) using the following relation with the intrinsic per-
meability (K):
bair ¼ 0:11K
0:39 ð5Þ
2 2
where bair is expressed in N/m and K in m .
For a generic gaseous species i, the Klinkenberg
ð4Þ
parameter bi can be calculated from:
bi ¼ ðMi =Mair Þ1=2 ðair =i Þ bair ð6Þ
where Mi
Mair, and air
i are the molecular weights
and the viscosities respectively of i and air.
Using Eq. (5) and the measured intrinsic permeability
values, Eq. (6) can be used for CO2. Results are shown
in Table 2. Average CO2 flowing pressures have then
been calculated for a set of variable initial pressures.
Using these data and applying Eq. (16) (see Appendix)
the graphs of Fig. 5 can be obtained. In agreement with
 M.L. Carapezza, D. Granieri / Applied Geochemistry 19 (2004) 73–88 79

Table 2 much higher than the intrinsic one and very

Klinkenberg parameter (b) for CO2 in the measured intrinsic difficult ‘‘on site’’ measurements of gas P
permeability range should be made in order to convert K into Kg;
The measured K values used for the conversion
Permeability bAir bCO2
(darcy) (Pa) (atm)
of DC into CO2 flux therefore represent the
‘‘minimum’’ permeability for CO2 of the system,
0.1 12923.873 0.1901 whose real value depends on the unknown
1 5264.931 0.0775 average P of the flowing CO2.
5 2810.570 0.0413
10 2144.829 0.0316
15 1831.121 0.0269
6. Results and discussion
20 1636.783 0.0241
25 1500.362 0.0221
30 1397.383 0.0206 6.1. Comparison between ACM and DCM flux values
35 1315.849 0.0194
40 1249.077 0.0184 Carbon dioxide soil flux values simultaneously mea-
45 1192.998 0.0176 sured by ACM and DCM are reported in Table 1,
50 1144.971 0.0168 together with the (water) permeability (K value) mea-
55 1103.192 0.0162 sured in the nearest soil core. DCM fluxes calculated
60 1066.384 0.0157 using the constant M conversion factor of Gurrieri and
65 1033.609 0.0152 Valenza (1988) (see Eq. 1) are compared, in the same
70 1004.164 0.0148
table, with values obtained by introducing a correction
factor (K/24) accounting for the measured permeability.
As previously discussed, the soil gas permeability is cer-
the Klinkenberg equation, the permeabilities for gas are tainly higher than the water permeability, but it cannot
always higher than those for liquid, and for increasing be estimated if the average pressure of flowing CO2 is
values of the average flowing gas pressure, this differ- not known. Diliberto et al. (2002), presenting 10 a of
ence tends to zero (see Eq. 18 in Appendix). DCM CO2 flux measurements at Vulcano, report that
The following conclusions are reached: no change in the M converting factor has been experi-
mentally observed using a sand with permeability of 32
In most laboratory measurements, gas flux darcy instead of the (24 darcy) sand of the initial Gur-
pressure is 1 bar or higher. Such a pressure gives rieri and Valenza (1988) experiment. Unfortunately the
apparent permeability values close to those of papers do not report how permeability was measured,
intrinsic (water) permeability; or if they refer to water or CO2 permeability, and which
In natural conditions average flowing pressure was the imposed average CO2 flowing pressure. It is
may be very low (Natale et al., 2000; Evans et al., clear from the K values in Table 1 that in most cases
2001) and therefore the apparent permeability is corrected DCM fluxes are lower than uncorrected ones,

Fig. 5. Gas permeability (Kg) as a function of the intrinsic permeability K for different CO2 pressures at depth. The 0.001 curve has to
be read on the right axis, all the others on the left one.
80 M.L. Carapezza, D. Granieri / Applied Geochemistry 19 (2004) 73–88

because the measured K values are lower than the con-
stant permeability (24 darcy) assumed for the calcula-
tion of uncorrected fluxes. Consequently uncorrected
DCM fluxes are almost always higher than the ACM
fluxes measured at the same site (Fig. 6a). However,
many corrected DCM fluxes in low permeability med-
ium–low flux zones (Log ACM flux < 2) are lower than
the corresponding ACM flux values (Fig. 6b). Such
behaviour may either reflect the different soil perme-
ability of the surface layer compared with 50 cm depth
(where DCM measurements are made); or result from
severe CO2 distribution disturbance caused by pumping
in low permeability soils. As there is no reason to use a
single soil permeability value to compute DCM fluxes,
in the following corrected DCM values will be referred
to.
In the Log–Log diagram for the whole data set
(Fig. 6) a relatively good linear correlation is found
between ACM and DCM fluxes (r2 of 0.86 and 0.74, for
uncorrected and corrected DCM values, respectively).
This correlation is influenced by the wide variation field
and it is clear from Fig. 6 that data can be subdivided
into a high flux group and a medium-low flux group
with a separating threshold at a Log ACM flux value

Fig. 6. Comparison of the CO2 soil flux Log values obtained by the ACM with uncorrected (A) and corrected (B) Log flux values
obtained by the DCM at the same points. Straight line is x=y Eq.
 M.L. Carapezza, D. Granieri / Applied Geochemistry 19 (2004) 73–88 81

of 2. All values in the high flux group refer to measure-
ments carried out in the Palizzi zone at the southern
base of the La Fossa cone (points n. 4, 4M, and C4;
Fig. 1 and Table 1). All the remaining points belong to
the medium–low flux group. In the high CO2 flux group
(Fig. 7a) DCM values are on average one order of
magnitude higher than ACM fluxes but the two sets of
data are relatively well correlated (r2=0.74). No corre-
lation exists between ACM and DCM data in the med-
ium–low flux group (Fig. 7b).
It is clear from Table 1 that although high flux values
correspond to soils with a medium–high permeability
(17–32 darcy), there is no correlation between soil per-
meability and CO2 flux. There are low permeability ( < 5
darcy) soils (e.g. points 2, 10, 12, 19) with a CO2 flux
higher than that measured in other soils which have a
permeability one order of magnitude higher (e.g. points
9, 17, 82). This indicates that although obviously soil
permeability affects the CO2 flux at the surface, this
depends also, and to a relevant extent, on the quantity
of CO2 that is locally released from the deep source.
From a geological viewpoint low permeability-medium
flux sites are thus as interesting as high permeability-
high flux sites, since both indicate a significant CO2
degassing at depth and the presence of gas releasing
cracks.
A strong variation of flux with time is observed at all
points where measurements have been repeated 10 or
more times in a time span of 2 weeks (see Table 1). Both
DCM and ACM fluxes vary by a factor of 2–6, with iso-
lated peaks up to 22.7 (DCM) and 14 (ACM). The var-
iations can be only partly explained by barometric

Fig. 7. Log–Log diagram of ACM and corrected DCM CO2 soil fluxes for high (A) and medium-low values (B). Straight line is x=y Eq.
82 M.L. Carapezza, D. Granieri / Applied Geochemistry 19 (2004) 73–88
pressure changes (see Section 6.3) and largely reflect
changes in the regime of deep degassing of the La Fossa
volcanic system.
In conclusion both DCM and ACM identify the same
high CO2 flux sites where Log fluxes (gm
2 day
1) are
respectively higher than 2 (ACM) and 3 (DCM)
(Fig. 7a). In the medium–low flux zone point dispersion
is large and for the same Log ACM flux a range of Log
DCM flux values over 1.5 order of magnitude can be
observed and vice-versa (Fig. 7b). In low flux zones, gas
transport is mostly by diffusion driven by the [CO2]
gradient (see Section 7). The different response of DCM
and ACM could be explained considering that ACM
chambers may have a blocking effect that lowers the
[CO2] gradient, whereas DCM pumping favours the
diffusion of CO2 within the soil.
6.2. Small scale and short time variation in CO2 flux
In the Palizzi area, between the two highly emissive
points 4 and 4M (Fig. 1), 14 ACM and DCM CO2 flux
measurements with 1 m spacing were carried out in 56
min at constant atmospheric pressure, over an area of
only 7 m2. ACM fluxes varied from 68 to 1960 gm
2
day
1 (avg 473;  541); DCM fluxes from 1010 to 21,130
gm
2 day
1 (avg 6760;  5920). The ACM and DCM
values are well correlated (r2=0.77), the second being over
one order of magnitude higher than the first. In the same
zone 24 ACM flux measurements were made in 1 h, moving
the chamber so that the covered surfaces were adjacent
to each other (40 cm distance between the accumulation
chamber centers in two successive measurements). The
following results were obtained (gm
2 day
1):
min ¼ 169 max ¼ 507 average ¼ 287  ¼ 86:
Results suggest that the surface release of CO2 is
confined to microcracks that are much narrower than
the ACM-chamber (40 cm diameter). These data con-
firm the large variability of CO2 soil flux even on a very
small scale and from an apparently homogenous soil.
Values differ over one order of magnitude at 4 m dis-
tance and by a factor of 3–4 at only 40 cm distance.
Estimates of total CO2 soil output are therefore affected
Table 3
Variation of CO2 flux within 24 h
Point Accumulation chamber (gm
2 day
1)
Min Max Avg s Min
4 225 385 309 48
4M 1205 2434 2035 390
C4 1104 1960 1542 288
by a large uncertainty even with a dense distribution of
measurement points.
ACM and DCM CO2 fluxes were measured every 2 h
for 24 h, at 3 high flux points in the Palizzi zone (4, 4M,
C4; Fig. 1). DCM flux was measured on the permanent
probes and ACM flux always in the same site at a dis-
tance from the DCM probe of 40, 30 and 32 cm respec-
tively. Results are shown in Table 3. Random variations
were observed (16–19% for ACM; 10–12% for DCM)
that probably reflect the methods’ uncertainties. No
correlation exists between the two sets of data at any
point, with DCM fluxes much higher, as usual, than
ACM ones. No correlation exists either with the simul-
taneously recorded environmental parameters. This
indicates that, at least in this case, the possible effects
due to variations in barometric pressure (1005–1008
mbar), air temperature (24.5–35.0  C) and air relative
humidity (35.0–63.7%) are lower than the measurement
uncertainty.
6.3. Influence of environmental parameters
Soil gas flux and concentration are affected by envir-
onmental conditions (atmospheric T, P and humidity,
soil T and moisture, wind speed) (e.g. Reimer, 1980;
Hinkle, 1994). The field work was carried out in dry
summer months with stable weather, so only variations
of atmospheric pressure (atm-P) have to be considered.
In high flux zones like Palizzi CO2 is transported mainly
by viscous flow, that is governed by the gas pressure
gradient (see Eq. 11 and following in Appendix). It is
therefore logical that in such zones atmospheric pressure
affects soil gas fluxes, and in fact a negative correlation
is found between the two parameters (Table 4). The
pressure effects are surprisingly somewhat higher on the
DCM flux, based on gas extraction from 50 cm depth,
than on the ACM flux which is measured at the soil sur-
face. Clearly atmospheric pressure changes also affect CO2
at 50 cm depth (see Table 4). No correlation between
atmospheric pressure and DCM flux is observed for the
whole set of data at point 4M, but the expected negative
correlation is found if the values are divided into two
groups corresponding to lower (4 Mb) and higher (4 Ma)
pressure respectively (Table 4). Chiodini et al. (1998) also
Dynamic concentration corr. (gm
2 day
1)
Max Avg s
2914 4359 3801 397
17,299 27,902 23,980 2977
1490 2647 2081 388
 M.L. Carapezza, D. Granieri / Applied Geochemistry 19 (2004) 73–88 83

Table 4 DCM CO2 soil fluxes were simultaneously measured

Relationship between CO2 soil flux and atmospheric pressure (Table 5). The shape of the CO2-depth curves depends
on the flux. Three representative profiles are shown in
Point Avg DCM flux— ACM flux— CO2a—
Fig. 8. The profile changes from nearly linear at point 8
ACM flux Atm P Atm P Atm P
(gm
2 day
1) (r2) (r2) (r2)
(CO2 flux=18 gm
2 day
1) to moderately curved at
point 4 (CO2 flux=473 gm
2 day
1) to highly curved at
4 287
0.76
0.30
0.69 point 4M (CO2 flux=1893 gm
2 day
1). The CO2 pro-
4M 1546
0.08
0.43
0.27 file shapes in the Vulcano natural sandy soil are very
4M a 1798
0.73
0.44 similar to those found by Gurrieri and Valenza (1988)
4M b 1326
0.65
0.50 and Evans et al. (2001) in laboratory tests using homo-
C4 1177
0.53
0.49 no data
genous sand and a range of imposed CO2 fluxes. Gur-
a
Concentration of CO2 measured at 50 cm depth. rieri and Valenza (1988) noted that the change in the
profile shape from curved to linear represents the tran-
sition from mainly viscous to mainly diffusive CO2 flux.
observed at Palizzi in 1994 a variation of the P-flux Evans et al. (2001) showed that the total viscous flow of
relation with time. Both the authors’ data and those of gas (a mixture of CO2 and air) does not change close to
Chiodini et al. (1998) indicate that CO2 soil flux for the the soil surface, where CO2 transport becomes diffusive.
same point varies by a factor 4–5 with atmospheric In other words a viscous CO2 flow at depth becomes a
pressure variations of 5–9 mbar. Variations in the flux viscous flow of mainly air near the soil surface and the
by 3–4 times are however also observed for the same pressure gradient persists up to the soil surface.
atmospheric pressure value, indicating that factors The evaluation of the relative contribution of the dif-
others than atmospheric pressure (probably related to the fusive and viscous components of the CO2 flux is diffi-
gas source at depth) govern the rate of the CO2 output. cult, mostly because the pressure gradient in the soil is
Under severe weather conditions CO2 flux values are not known (see the review in Appendix of the funda-
perturbated by rapid changes in the atmospheric pres- mental laws governing gas transport in porous media).
sure and by the high soil moisture and wind velocity It is known (Thorstenson and Pollock, 1989b; Evans et
(Hinkle, 1994). Therefore data must be corrected for the al., 2001) that small pressure gradients of only a few Pa
influence of environmental parameters in order to can generate viscous fluxes that overwhelm diffusive
obtain reliable information on the CO2 release from fluxes. Following the examples provided by Thorstenson
depth. DCM and ACM automatic stations can even and Pollock (1989b) the authors used the Stefan–Max-
operate under a thick snow cover which, however, well equation and the measured CO2 flux in order to
modifies the CO2 concentration in the soils and hence calculate the CO2 distribution with depth and compare
the flux (Badalamenti et al., 1994a; Gerlach et al., 2001). the values obtained with those measured in the field. In
order to do this it must be assumed that the numerical
effect of the Knudsen diffusivity and the total pressure
7. CO2 concentration profiles and gas transport gradients in the constitutive equation are negligible,
mechanism in the Vulcano soil whereas the Klinkenberg parameter may be estimated
by Eq. (6). Input data and results are shown in Fig. 8.
Carbon dioxide concentration profiles were obtained The computed CO2 values fit the measured ones well
at 3 points (4, 4M and 8; Fig. 1) by analysing the gas with the exception of the deepest part at point 4M. Here
extracted from 50, 75 and 100 cm depth (also from 25 the gas composition is almost pure CO2, transport is
cm at 4M) using a probe inserted into the soil with 3 (4 dominated by viscous flux and thus the Stefan–Maxwell
in 4M) small channels (4 mm diameter). The ACM and equation is no longer adequate to describe the system.

Table 5
Variation of CO2 concentration with depth compared with ACM and DCM soil fluxes

Point Range of CO2 concentration at various depths (vol%) Range of Range of Measur.
No. ACM flux DCMc flux No.a
25 cm 50 cm 75 cm 100 cm (gm
2 day
1) (gm
2 day
1)

4 21.6–50.9 30.8–67.9 38.2–76.9 155–624 747–4371 32

4M 42.4–90.1 54.1–96.1 68.3–100 68.3–100 465–1983 7985–34850 16
8 0.4–1.5 0.6–3.0 1.2–4.6 1.2–4.6 10–21 10
a
Data refer to the number of simultaneous measurements of all parameters.
84 M.L. Carapezza, D. Granieri / Applied Geochemistry 19 (2004) 73–88

Fig. 8. CO2 measured at different depths in the soil of points 4, 4M and 8 (large full symbols). Dashed lines are the CO2/depth profiles
computed with the Stefan–Maxwell equation. In all cases DO2
CO2=DN2-CO2=1.64e–5 m2/s. For each point the values of ACM flux
(F in gm
2 day
1), atmospheric pressure (P in mbar) and temperature (T in  C) and of nt are indicated.

Note that at the low flux point 8 the measured CO2
gradient is perfectly reproduced by assuming that the
soil is permeated by air down to a depth of 30 cm.
Using the DGM (Dusty Gas Model see Eq. 9 in
Appendix) Evans et al. (2001) were able to calculate the
ratio of various flux components (diffusive vs viscous) to
total molar flux and showed that the percentage of CO2
transported by viscous flux is at any depth approxi-
mately equal to its concentration at that depth. Such a
relation holds for medium to coarse dry soils at low
elevations where abiogenic CO2 flux predominates over
soil respiration flux. This is certainly the case in the
Palizzi zone, and from Fig. 8 it can be inferred that at
point 4M, where the highest surface flux is recorded,
CO2 transported by viscous flow is nearly 100% at 100
cm depth, and still over 80% at 25 cm depth. The per-
centage of CO2 transported by viscous flow decreases as
the measured surface flux decreases. It is still high (75%)
at 100 cm depth at point 4, whereas it is only a few
percent at the same depth at the low flux point 8, where
CO2 transport is mainly by diffusion.
Using the DCM (corrected) flux instead of the ACM
ones in the Stefan–Maxwell equation, there is no way of
reproducing the CO2 gradient measured at point 4M,
whereas an unrealistic porosity value (0.80) has to be
assumed at point 4. This confirms that the DCM over-
stimates CO2 flux. Although there are no CO2 values for
depths lower than 25 (point 4M) and 50 cm (point 4) the
profile shapes confirm the indication by Evans et al.
(2001) that CO2 transport which is mainly viscous at
depth becomes diffusive close to the surface.
8. Conclusions
Carbon dioxide soil flux values measured with the
DCM are frequently over one order of magnitude
higher than those measured with the ACM. In high flux
zones they are relatively well correlated whereas no
correlation exists in medium-low flux zones (AC flux
< 100 gm
2 day
1). In high flux zones the prevailing gas
transport mechanism is by viscous flow, and the CO2 in
the soil at any depth is approximately equal to the per-
centage of CO2 transported by viscous flow (Evans et
al., 2001). This can explain the good correlation found
between DCM and ACM fluxes in high flux zones, as
DCM values are related to CO2 at 50 cm depth, and
hence to the efficiency of gas transport toward the sur-
face. In low flux zones the gas is instead transported
mainly by diffusion and the relation CO2-total flux does
not hold anymore. In these zones the DCM pumping
creates a pronounced dilution effect that results in a
forced in-diffusion of CO2 at the base of the probe.
These results confirm that DCM overestimates CO2 flux
and that DCM is proportional to flux only for high flux
values, in agreement with the finding of Witcamp and
Frank (1969) and Tonani and Miele (1991). An indica-
tion that ACM fluxes correspond to real soil fluxes
better than DCM ones comes from the CO2 curves
measured at some high flux points. These in fact are well
reproduced using the Stefan–Maxwell equation and the
measured ACM fluxes, but cannot be reproduced using
the DCM flux values. Although DCM is based on gas
extraction from 50 cm depth and ACM from surface
 M.L. Carapezza, D. Granieri / Applied Geochemistry 19 (2004) 73–88
measurements of CO2 increase within a chamber, baro-
metric pressure has the same relevant influence on both
DCM and ACM fluxes, that vary by a factor of 4–5
with variations of atmospheric pressure of 5–9 mbar.
This simply indicates that atmospheric pressure varia-
tions affect the CO2 at 50 cm depth as well as the surface
CO2 flux and there is some evidence for this from the
CO2 measurements in the soil.
Comparison between the two sets of data is difficult
because of the lack of data on the soil permeability for
CO2 that is required to convert DCM into flux at each
measurement point. The data show that the (water)
permeability is highly variable even in apparently
homogeneous soils like the ones of Vulcano. However
CO2 soil permeability cannot be evaluated as the aver-
age CO2 flowing pressure is not known. This appears to
be a strong limitation for DCM because of the difficulty
of carrying out reliable in situ soil gas permeability
measurements, which are not needed for ACM.
Automatic continuous stations of either DCM
(Badalamenti et al., 1994b) and ACM (Rogie et al.,
1998) have proved to be reliable and a long term com-
parison between them is under way at Stromboli.
Large variability of CO2 soil flux is observed even on
a very small scale (up to over one order of magnitude in
points with a spacing of only a few meters). For the
purpose of volcano surveillance it is therefore con-
venient either to use continuous recording stations or to
establish a permanent network to be periodically reoc-
cupied for the measurement of CO2 flux, as it is cur-
rently done at some high flux Italian volcanoes. In any
case the control of CO2 soil flux is by now confirmed as
a powerful tool for investigating and monitoring volca-
nic, seismic and geothermal areas.
Acknowledgements
This work was supported by the National Volcanic
Group of Italy (GNV). The review of Dr. Niels
Oskarsson provided several useful suggestions.
Appendix. Gas transport in natural porous media
Fick’s first law is generally used to describe the diffu-
sion of a binary gaseous system. Under isothermal and
isobaric conditions, neglecting external forces (gravity,
electrical field, etc.), the diffusive F D i flux can be
expressed by:
FD
i ¼
nDrx ð7Þ
ij i cule–molecule collisions.
where n is the total mole fraction; Dij the binary diffu-
sion coefficient of species i in j; xi the mole fraction of
component i.
85
If the two species i and j have different molecular
weights (Mi >Mj), an initial flux of j toward i occurs.
This generates an infinitesimal increase of pressure in
the region occupied by the i species and as a con-
sequence a viscous flux of i versus j arises. In a free sys-
tem, without walls, the pressure increase is immediately
dissipated and the system remains in a steady state.
Diffusion through natural soil requires, however, a
more complex model accounting for two important
additional factors.
The coefficient Dij has to be corrected for the porosity
(n) and tortuosity (t) of the soil (Penman, 1940). The
corrective factor is called diffusibility (Qm) and modifies
the term Dij in Deij:
Deij ¼ Qm Dij ð8Þ
Abu-El-Shar’s and Abriola (1997) found a value of
Qm=0.435n for sands similar to the Vulcano soils. For
porosity typical of sands (0.30–0.40), Deij is much smaller
than Dij (0.13–0.17).
A second difficulty arises from the physical structure
of soil, which can be described as a multitude of wide-
spread channels, constituting a system with walls. In this
case the gas moving through the capillary cannot dis-
sipate the increment of pressure and the viscous flux is
not negligible. To account for this, Mason et al. (1967)
proposed the Dusty Gas Model (DGM) which considers
the soil–gas system as a multi-component gaseous mix-
ture where soil grains are assimilated to stagnant gas
giant molecules. For an isothermal and isobaric system
of n components, the DGM general equation, expressed
in terms of diffusive molar fluxes, is given by (Thor-
stenson and Pollock, 1989a, b):
     D
X xi ND j
xj NDi DGM N rPi
DGM
e
i kDGM ¼
j¼1j6¼i
D ij D i RT ð9Þ
i ¼ 1; :::;
where xi and xj are the mole fraction of gases i and j, ND i
e ND e
j are the total molar diffusive flux, Dij represents the
effective binary diffusion coefficient of species i in j given
by Eq. (8) and Dki is the Knudsen diffusivity. Note that
Eq. (9) is referred to an isobaric system (Ptot =cost) and
the term related to the viscous flux is still not considered.
The Knudsen diffusivity arises from collisions
between moving gaseous molecules and soil particles.
From a physical point of view the second term on the
left of Eq. (9) represents the momentum transferred
from gaseous species to the soil grains. The first term on
the left represents the momentum lost through mole-
Two extreme cases are possible:
(a) Di k >> Di e
(b) Di k <<Di e.
86 M.L. Carapezza, D. Granieri / Applied Geochemistry 19 (2004) 73–88

In case (a) the Knudsen diffusivity is negligible and or in the form:

Eq. (9) reduces to the Stefan–Maxwell equation (Thor-  k
T Di  P
stenson and Pollock, 1989a, b). This condition occurs N ¼
þK rP ð13cÞ
P RT
with high soil permeability and/or high gas pressure.
In case (b) the major contribution is given by mole-
cule–particle collisions. This occurs when the pore dia- Eq. (13c) suggests that the total molar flux can be
meter is small with respect to the gas molecule size and/ seen as a viscous flux governed by Darcy’s law (Eq. 12)
or for low gas pressure. where the intrinsic permeability (K) is replaced by
Under non-isobaric condition, the Pi term of Eq. (9) apparent, or gas phase, permeability (Kg):
becomes:
D ki 
rPi ¼ Prxi þ xi rP ð10Þ Kg ¼
þK ð14Þ
P
where P represents the total pressure of the system; the
term rP is the pressure gradient and suggests the and the total molar flux becomes:
appearance of a viscous flux.

The viscous flux is expressed by Darcy’s law : T P
N ¼
Kg rP ð15Þ
RT
K
q ¼ rP ð11Þ

Equation (14) shows that the gas (apparent) perme-
where q is the volumetric flux, K is the intrinsic perme- ability is higher than the liquid (intrinsic) permeability
ability e  is the dynamic viscosity of the gas. for a slipping effect impressed on the gas molecules
For an ideal gas Eq. (11) can be written as: along the porous medium walls. This phenomenon is
P K known as the Klinkenberg effect or ‘‘slip flux’’.
NV ¼
rP ð12Þ The original relation (Klinkenberg, 1941) is:
RT  
bi
where Nv is the molar viscous flux. Considering that the Kg ¼ K 1 þ
ð16Þ
total flux is given by the sum of viscous and diffusive P
fluxes (NTi=Ndi+xiNv), Eq. (9) becomes: where Kg and K are the gas and liquid permeability, bi is
    the Klinkenberg parameter which depends on the kind of
X xi NTj
xj N Ti DGM N T  gas, on the characteristics of the solid medium, on tem-
DGM

i kDGM perature and pressure and P is the gas average pressure.
j¼1 j6¼i
Deij Di
Eq. (16) is equal to Eq. (14) if the following relation
  ð13Þ is considered (Thorstenson and Pollock, 1989a and
Prxi kP xi rP
¼ þ 1þ k i ¼ 1; :::; 1989b):
RT Di  RT
Dik ¼ K bi =i ð17Þ
that is the DGM general equation under isothermal
conditions (Thorstenson and Pollock, 1989a, b). An increase of P determines a Kg decrease until it
For a single component gas phase, the molecular dif- approaches the liquid permeability:
fusivity vanishes, the molar fraction is equal to 1, and lim Kg ¼ K: ð18Þ
Eq. (13) reduces to:

P !1

KP rP rP References
NT ¼ NV þ ND ¼

DK
i : ð13aÞ
i RT RT
Abu-El-Shar’s, W., Abriola, L.M., 1997. Experimental assess-
Note that, even in the absence of a gas concentration ment of gas transport mechanisms in natural porous media:
gradient, a diffusive flux can exist as a consequence of parameter evaluation. Water Resour. Res. 33–4, 505–516.
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P., Robe, M.C., Maurenas, J.M., Faivre-Pierret, R., Martin,
The terms KP/i and DK i represent, respectively, the
D., Sabroux, J.C., Zettwoog, P., 1991. Eruptive and diffuse
viscous and diffusive component in the total flux equa-
emission of CO2 from Mount Etna. Nature 351, 387–391.
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Eq. (13a) can be written as follows (Mason and Mal- Ground CO2 output in the island of Vulcano during the
inauskas, 1983): period 1984–1988: gas hazard and volcanic activity surveil-
 lance implications. Rend. Soc. It. Mineral. Petrol., Car-
Dki PK
NT ¼
þ rP ð13bÞ apezza Mem. Vol 43, 893–899.
RT RT
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