Ann. Bot.

43 285-293 1979

On the Use of the Katharometer

for the Estimation of Carbon Dioxide
Concentrations in Soils
L. W. POEL
Department of Plant Biology, University of Birmingham, P.O. Box 363, Birmingham BIS 2TT

Accepted: 17 November 1977

ABSTRACT

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The method depends upon the difference in thermal conductivity between carbon dioxide and other
components of the soil atmosphere.
The circuit calibration and mode of operation of the instrument are fully described together with
an investigation of the effect of differences in ambient temperature.
Values of carbon dioxide concentration obtained in trials on culture and field soils are given. The values
lie within ranges reported by earlier workers using gas analysis of samples of soil air.

Key words: katharometer, CO2 concentration, soil atmosphere.

INTRODUCTION
In 1915, G. A. Shakespear, of the Department of Physics in the University of Birmingham,
was approached by the British Admiralty to devise a method of detecting dangerous
concentrations of hydrogen arising in hangars during the filling of airships. The
instrument that he produced, and to which he gave the name 'katharometer', depended
upon the difference in thermal conductivity between hydrogen and air. Over the years
the method was developed by the Cambridge Instrument Company Limited for the
estimation of a wide range of gases and found application in many diverse branches of
Science and Industry (Barron, 1951). In the sphere of plant metabolism, early forms of
the instrument were used in studies of the carbon dioxide exchange of leaves (Waller,
1926) and of plant respiration (Stiles and Leach, 1931; Leach, 1932). More recently, the
katharometer has been employed extensively as a detector in gas analysis by gas
chromatography.
Carbon dioxide concentrations in soils have almost always been estimated by gas
analysis of samples of the soil atmosphere obtained either by suction or by burying
a porous thimble and allowing its contents to attain equilibrium with the soil air (e.g.
Russell and Appleyard, 1915). Jensen, Van Gundy and Stolzy (1965) used a membrane-
covered glass electrode to record in situ the partial pressure of carbon dioxide in soil
cultures of tomato and found good agreement with gas chromatographic analysis of
withdrawn samples. However, one would anticipate that such an electrode would prove
too fragile for routine work in the field, a disadvantage that the rugged katharometer
described in the present article does not have.

0305-7364/79/030285 +10 $02.00/0 © 1979 Annals of Botany Company

286 Poel - Estimation of Carbon Dioxide Concentrations in Soils

PRINCIPLES AND GENERAL FEATURES

The katharometer consists of a cylindrical block of copper or brass in which two holes
are drilled longitudinally. One of these holes passes completely through the block whereas
the other does not. A fine platinum spiral or loop of approximately 10 Q resistance is
inserted into each hole. In some instruments, both leads from each spiral are insulated
from the block whereas in others, one lead is insulated and brought out, the second being
connected directly to the block so that the block itself forms part of the circuit. The
spirals constitute two adjacent arms of a Wheatstone bridge, the other two arms being
manganin resistors each of about 10 O.. The latter are not connected directly to each
other in the bridge but are linked by a circular slide-wire of manganin or constantan, thus
enabling balancing of the bridge to be carried out. This arrangement and other features
of the basic circuit are shown in Fig. 1.

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Heating current
resistance

katharometer block
FIG. 1. Basic katharometer bridge circuit.

If the variable resistance is adjusted to furnish only a small current in the bridge as
indicated by the milliammeter, if all the resistances in the bridge circuit are of precisely
the same value and, further, if all are at the same temperature, then the bridge will be 'in
balance', giving a reading of zero on the galvanometer. Suppose now that the current
from the battery is increased to such a level that the platinum spirals are heated. Their
resistance will fall but, if both spirals are in contact with the same gas mixture, the bridge
will remain in balance for the resistances of the spirals will still be equal although lower
than when cold. However, if the lower end of the katharometer block is brought into
contact with air enriched with carbon dioxide, then the two spirals will no longer be
exposed to the same gas mixture; the 'closed' spiral will be in contact with ordinary air
as before but the 'open' spiral will be accessible to carbon-dioxide-enriched air. Owing
to the high thermal conductivity of carbon dioxide, more heat will be lost from the open
spiral than from the closed one. Hence, the resistance of the former will increase in
proportion to the concentration of carbon dioxide and the bridge will drift out of balance
to a corresponding degree, with a lag of about 5 min for the attainment of equilibrium
 Poel - Estimation of Carbon Dioxide Concentrations in Soils 287
There are two ways to record quantitatively the effect of exposure of the open spiral
to a concentration of carbon dioxide above that in air. Either the out-of-balance current
can be read on the galvanometer or, if it is graduated with a scale of suitable divisions, the
slide-wire dial can be adjusted to restore balance, the number of divisions of rotation
required to achieve this being recorded. In either case, the instrument is calibrated against
gas mixtures of known carbon dioxide contents. An unknown concentration can then be
derived by interpolation on a calibration curve.

DESCRIPTION OF THE INSTRUMENT

Plate 1 shows the complete carbon dioxide analyser. The probe, now shrouded in
insulating materials against variations in external temperature, is the actual one depicted
in Stiles and Leach (1931, p. 469). Recent calibration of this instrument (Fig. 3) shows
that it has not deteriorated over the years.
The detailed circuit of the meter is shown in Fig. 2. Stiles and Leach (1931) calibrated
and operated their instruments on the out-of-balance bridge current principle. This called

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for a highly sensitive and hence delicate galvanometer. Clearly, such a galvanometer
cannot be employed in an instrument designed for use in the field. The Pye Unicam taut
suspension galvanometer installed in the present meter is insufficiently sensitive for
measuring out-of-balance bridge current nor for providing other than a very approximate
indication of null-point in a balanced bridge mode of operation. However, measurement
of the potential difference across the galvanometer substantially raises the effective sen-
sitivity of the meter. For this purpose, a Comark D.C. microvoltmeter (portable model)
is employed. This would be equally suitable for use in either mode of operation of the
bridge, but, since the null-point method depends not only on the sensitivity of the null
detector but also on that of the slide-wire adjustment, the potential drop across the
galvanometer corresponding to the out-of-balance current is measured.
It may be wondered why, as the potential difference across the Pye galvanometer is
being measured, the latter instrument is retained in the circuit since it could be replaced
for this purpose by an equivalent resistor. In practice, the galvanometer serves a valuable
function in indicating approximately the degree to which the bridge is put of balance,
so allowing the appropriate range of the microvoltmeter to be selected before switching on.
The lower end of the katharometer block is protected against direct contact with the
soil (and the consequent risk of soil reaching the open spiral) by a tubular brass shrouding.
To the upper end of the block, a length of copper tubing is attached and this contains
the fixed resistors of the bridge. As mentioned previously, all the external metal surfaces of
the probe are sleeved with insulating materials so as to minimize the influence of changes
in ambient temperature. The five-core cable is taped to the probe to avoid movement of
the cable being transmitted to the fixed resistors and their soldered joints; such movement
causes instability of readings. The cable terminates in a six-pin plug socket and at this
end also, there is provision for securing the cable to the side of the case to preclude
variation in contact resistance at the panel connexion arising from movement of the plug.
The katharometer used is operated at 102 mA, derived from a 2-4 V, 15 AH D.E.A.C.
Type 2/SD15 sealed nickel cadmium accumulator. In order to obtain this current within
the range of adjustment of the variable resistors Rl and R2 (coarse and fine adjustments
respectively) further resistance in the circuit is necessary and this is provided by a com-
bination of fixed resistors on the positive side of the battery. Because the instrument is
inherently highly sensitive to changes in heating current, the milliammeter is fitted with
a magnifying lens to aid precise setting of the current.
The resistance of the manganin slide-wire is low (0-1 Q) and this would limit the range
of carbon dioxide concentrations that could be handled by the instrument. Moreover, the
four resistances used in the construction of a katharometer probe are unlikely all to be
io BOT 43
288 Poel - Estimation of Carbon Dioxide Concentrations in Soils

Katharometer block
connections

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o
To microvoltmeter

FIG. 2. Detailed circuit of the soil carbon dioxide analyser.

of precisely the same value so that there may be a weighting in favour of the 'open
side' or the 'closed side'. Such imbalance would reduce the effective range of adjustment
of the slide-wire and may even be sufficient in magnitude to render the slide-wire control
totally ineffective. For these reasons, a chain of four resistances (made by hand from
constantan wire) is fitted. Each resistance is of approximately 0-1 Q. and they can be
added stepwise to either end of the slide-wire as necessary by means of the contact
selector S3 and the rotary changeover switch S4.
The Pye Unicam galvanometer is brought into circuit by opening the switch S2 which,
in the closed position, short-circuits the galvanometer and thus damps its movement for
protection during carriage of the meter. S5 is a rotary changeover switch, useful if either
a centre-zero microvoltmeter is not available or one wishes to utilize the greater range
 Poel - Estimation of Carbon Dioxide Concentrations in Soils 289
of a left-hand zero instrument. Since measurements are made at the microvolt level, it is
imperative that all switches be of low and reproducible contact resistance.

CALIBRATION
A glass chamber having inlet and outlet tubes was fitted to the probe and through this
carbon-dioxide-free air (derived from a small compressor via a soda lime tube) was
passed for 30 min after switching on the instrument, adjusting the heating current to
102 mA and bringing the galvanometer and microvoltmeter readings approximately to
zero deflexion. At the end of this period, a null reading on the microvoltmeter was set
precisely. The carbon-dioxide-free airstream was replaced by a series of known con-
centrations of carbon dioxide in air delivered by a gas-mixing assembly. For each carbon
dioxide concentration, the mixture was allowed to pass for 10 min followed by carbon-
dioxide-free air for 10 min. At the end of each of these 10 min periods the out-of-balance
potential difference was measured and, after recording the difference between the two
readings, the bridge was brought to balance again.

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All gas streams, whether carbon-dioxide-free or otherwise, were moistened since
a calibration based on dry gases would not be valid for the humid conditions prevailing
in the soil atmosphere. Water has a very high thermal conductivity (about seven times
that of carbon dioxide) and hence any instrument depending upon differential thermal
conductivity will be profoundly affected by variations in water content of the medium,
be it gaseous or solid, into which its probe is inserted. Indeed, this has furnished a method
for estimating in situ the water content of soils (De Jager and Charles-Edwards, 1969.)
However, the katharometer as used for soil carbon dioxide estimation is in contact not
with the liquid phase of the soil but with the soil atmosphere containing water vapour.
Although the water content of the soil may vary widely ' the air between the soil particles
is generally nearly saturated with water vapour' (Nobel, 1974, p. 388). Thus constancy of
water vapour content can probably be assumed for practical purposes, except perhaps
in dry, sandy soils. In passing, the carbon dioxide katharometer clearly cannot be used
in exceptionally wet soils since water would be liable to flood into the open chamber and
reach the platinum spiral.
The calibration curve obtained is shown in Fig. 3. Each point represents the mean of
not fewer than three completely separate determinations. Only in the case of ordinary
air, the carbon dioxide content of which is close to the resolution of the instrument, did
the standard deviation of replicates exceed 1 -74 per cent of the mean. The slope of the
curve indicates a sensitivity of 0-0258 per cent carbon dioxide per microvolt.
The above calibration was carried out under uniform conditions of ambient tempera-
ture in the laboratory. In the field, soil temperature and atmospheric temperature will
vary both individually and relative to each other. Stiles and Leach (1931) found that
temperature had an appreciable effect on the katharometer readings in their studies and
therefore a laboratory investigation of the temperature factor was conducted with the
present system.
An attachment for the supply of humidified carbon-dioxide-free air was constructed
(Plate 1). This comprised a coil of copper tubing and a cylindrical brass chamber in
series preceded by a soda lime tube, a U-tube containing moistened cotton wool and
a hand pump. The copper tubing and brass chamber were immersed in a water bath filled
with cold water. The attachment was fitted to the probe and the instrument having been
switched on and stabilized for 30 min, carbon-dioxide-free air at the temperature of the
water bath (12-5 °C, measured with a Comark digital thermometer) was pumped through
intermittently for sufficient time to achieve a steady null reading. By judicious manipu-
lation of the water bath thermostat, the temperature of the water bath was raised one or
two degrees at a time. At each temperature, air was pumped to the katharometer probe
290 Poel - Estimation of Carbon Dioxide Concentrations in Soils

300

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1 2 3 4 5 6 7
Carbon dioxide concentration
(% by volume)

FIG. 3. Calibration curve for the Stiles and Leach (Shakespear) katharometer.

Temperature (°C)
20 30

-20

FIG. 4. Effect of air temperature on katharometer readings. The bridge was balanced against
carbon-dioxide-free air pumped intermittently through a metal coil and cylinder immersed in
a water bath at 12-5 °C. Increasing imbalance as the water-bath temperature was raised is shown
as negative values, the effect of temperature being opposite in direction to that of carbon dioxide.
 Poel - Estimation of Carbon Dioxide Concentrations in Soils 291
and the out-of-balance potential difference recorded at equilibrium. The results are
plotted in Fig 4.
As shown by Stiles and Leach (1931), the effect of temperature is opposite in direction
to that of carbon dioxide and for this reason, the potential differences are shown in
Fig. 4 as negative values. From 12-5 to 25 °C, the relationship is a linear one and the slope
indicates a difference of 1-05/JV for a change of 1 °C which is equivalent to 0-0271 per
cent carbon dioxide. This is in good agreement with the value of 0-025 per cent quoted by
Stiles and Leach (1931) for the temperature range 17 °C to 25 °C. Above 25 °C the
influence of temperature progressively declines up to 40 °C, the highest temperature
reached in the investigation.
Clearly, temperature differences of no more than a few degrees could introduce
appreciable errors particularly at low levels of soil carbon dioxide. Such differences are
likely to occur between the soil atmosphere and the air above the soil which is used
(when freed of carbon dioxide) for setting the zero. The solution to this problem is to
bring the temperature of the carbon dioxide-free air reaching the probe as close as
possible to that of the soil. In achieving this, use is made of the metal coil and cylinder

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employed in the laboratory investigation described above. On arrival at a site, the
assembly is buried in the soil to the same depth as that to which the katharometer
probe will be inserted. Providing that pumping is gentle, the carbon-dioxide-free air will
be at or close to the soil temperature. Discrepancies in soil temperature between sites
and also at a given site on different occasions will often exist and are allowed for by
adjustment of the carbon dioxide concentration data to an arbitrarily chosen reference
temperature. Finally, many other components of the meter circuit are susceptible to
drifting resistance as a result of variation in external temperature. Accordingly, steps
must be taken when necessary to shield the entire system from direct insolation and
strong winds.

LABORATORY TRIAL
For this purpose, a quantity of soil taken from a field adjoining the Biology Building was
packed into a tall litre beaker and moistened. A number of barley grains was sown
superficially in the soil. The beaker was placed in an illuminated growth cabinet at 25 °C
for 1 week at which stage the leaves were about 7 cm long. The beaker was then taken
from the growth cabinet and time allowed for its contents to return to laboratory
temperature. A soil core was removed by means of a no. 18 cork borer, leaving a hole
6-5 cm deep for insertion of the katharometer probe. The data obtained are presented

TABLE 1. Analyses of carbon dioxide concentration in a soil culture of seedling barley

Potential difference across galvanometer (fiV)

Equivalent
Carbon percentage
dioxide-free (by volume)
Soil air Difference carbon dioxide
10 -5 15 0-25
6 -10 16 0-27
26 10 16 0-27
16 2 14 0-23
15 0 15 0-25
Mean 0-254
S.D. 0017

Heating current = 102 mA; readings taken after lOmin; microvoltmeter brought to zero after each
carbon dioxide-free air reading.
292 Poel - Estimation of Carbon Dioxide Concentrations in Soils
in Table 1. The level of carbon dioxide concentration indicated appears reasonable for
the conditions of the trial and the individual readings show a remarkable degree of
uniformity.
FIELD TRIAL
The area selected for preliminary testing of the instrument in the field lies to the north of
the Biology Building, extending from the Worcester and Birmingham Canal to the
boundary of the University Tennis Courts. From the overgrown towpath the land rises
gently to the crest of the canal embankment and then falls steeply (gradient 1 in 0-35)
to more or less level ground about 3 m below. On the canal embankment, characteristic
plant species are Rubus fruticosus, Urtica dioica, Festuca rubra. The vegetation of the
level area, cut over during the growing season, is coarse grassland of which the main
constituents are Agropyron repens, Agrostis tenuis, Holcus lanatus, Dactylis glomerata
and Plantago lanceolata. The soil throughout the area is a brown loam, much looser in
texture on the canal embankment than on the level part.
In October 1977 seven sites for estimation of soil carbon dioxide concentration were

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chosen, three located on the canal embankment and four on the level area. At each site,
three or in some instances four separate estimations were made. Soil temperature was
14 °C at all sites. As an analysis of variance revealed no significant difference between
the means for the sites on the canal embankment and likewise for those on the level
ground, the raw data for the sites in each area were pooled. The means for these pooled
data are presented in Table 2. The difference of means proved highly significant (by
Student's / test) at better thanP = 0001.

TABLE 2. Mean soil carbon dioxide concentrations on a canal embankment and

a level grassland area below

Canal
embankment Level area
No. of estimations 9 13
Mean (% by volume) 0-246 0-566
Range of values 010-0-38 0-29-100
Standard deviation 0105 0185

Since gaseous diffusion from the soil to the atmosphere is facilitated by a loose soil
texture, one would expect to find a lower equilibrium concentration of carbon dioxide
in the embankment soil than in that of the level grassland. That this was actually the case
in the trial inspires confidence in the instrument for use in field investigations, a confidence
which is strengthened by the fact that the carbon dioxide concentrations recorded fall
within ranges of values encountered by Russell and Appleyard (1915) in their classic
study of the soil atmosphere of Rothamsted fields.

ACKNOWLEDGEMENTS
The author is grateful to Miss V. B. A. Willington for carrying out the field trial, and to
Miss A. J. Cox for the photographic work.
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 POEL - Estimation of Carbon Dioxide Concentrations in Soils

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PLATE I

Ann. Bol. 43, 285-293, 1979 (Facing p. 293)

 Poel - Estimation of Carbon Dioxide Concentrations in Soils 293

LITERATURE CITED
BARRON, S. L., 1951. The Development of the Thermal Conductivity Method of Gas Analysis. Cambridge
Monograph No. 3. Cambridge Instrument Company Ltd, London.
DE JAGER, J. M. and CHARLES-EDWARDS, J., 1969. Thermal conductivity probe for soil-moisture deter-
minations. J. exp. Bot. 20, 46-51.
JENSEN, C. R., VAN GUNDY, S. D. and STOLZY, L. H. 1965. Recording CO2 in soil-root systems with
a potentiometric membrane electrode. Proc. Am. Soil Sci. Soc. 29, 631-3.
LEACH, W., 1932. Further experimental methods in connexion with the use of the katharometer for the
measurement of respiration. Ann. Bot. (Old Series) 46, 583-96.
NOBEL, P. S., 1974. Introduction to Biophysical Plant Physiology. W. H. Freeman, San Francisco.
RUSSELL, E. J. and APPLEYARD, A., 1915. The atmosphere of the soil: its composition and the causes of
variation. / . agric. Sci., Camb. 7, 1-48.
STILES, W. and LEACH, W., 1931. On the use of the katharometer for the measurement of respiration.
Ann. Bot. (Old Series) 45, 461-88.
WALLER, J. C , 1926. The katharometer as an instrument for measuring the output and intake of carbon
dioxide by leaves. New Phytol. 25, 109-18.

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E X P L A N A T I O N O F PLATE 1
The soil carbon dioxide analyser showing the bridge control unit, the katharometer probe, the battery,
the portable microvoltmeter and the carbon-dioxide-free air attachment.