The Science of the Total Environment, 45 (1985) 343--350 343

Elsevier Science Publishers B.V., A m s t e r d a m - - P r i n t e d in The Netherlands

MEASUREMENTOF THE EMANATIONOF RADON-222 FROMDANISH SOILS

A. Damkjmr and U. Korsbech

Department of Electrophysics, The Technical University of Denmark, Building 322,
DK-2800 Lyngby, Denmark

ABSTRACT
The radon-222 emanation from 70 samples of Danish s o i l s , subsoils, and sedi-
mentary rocks has been measured.
Two methods have been employed. The f i r s t one is to follow the growth of the
radon concentration in a radon-tight sample container by transferring small a i r
samples to a s c i n t i l l a t i o n flask detection system. The second one is to measure
the equilibrium gamma-activities of lead-214 and bismuth-214 in the sample when
the sample container is open and, subsequently, when i t is closed.
Based on the measured emanation rates the samples are grouped in three
classes: l ) less than 5 at~ms-s@c-l.kg- I , 2) from 5 to IO atoms.sec-l.kg - l , and
3) more than I0 atoms.sec-i.kg TM. In c l a s s 3 ) s~me diatomitic clays have shown
emanation rates as large as IO0 atoms.sec-l.kg -~.

INTRODUCTION
The effective dose equivalent to the Danish population from radon-222 and
i t s daughters is estimated to be the same as that from the external gamma radia-
tions, i . e . about 0.4 mSv per year ( r e f . l ) .
However, the natural radiation burden from radon and i t s daughters is not
well known, since the f i r s t Danish survey of indoor radon levels has just re-
cently been i n i t i a t e d .
Preliminary studies (ref.2) of the radon levels indicate that a small per-
centage of the houses has average radon-222 concentrations above 200 Bq.m-3.
Radon levels of that size cannot be accounted for by exhalation from building
materials alone. Hence, the major source of radon-222 in the "high level houses"
is believed to be the ground beneath the houses. A similar conclusion has been
reached for indoor radon in Sweden (ref.3).
The Danish surface geology is characterized mainly by glacial deposits, i . e .
moraine clay or sand and d i l u v i a l clay, s i l t or sand. Thus for most Danish
buildings a possible radon inflow w i l l originate from those types of deposits.
Below the glacial deposits are found Tertiary sediments or chalk of Maastricht-
ian age. In some l o c a l i t i e s the glacial deposits are missing, or have a thick-
ness of less than 2 m. In those l o c a l i t i e s the older sediments w i l l influence
or determine the radon flow into the buildings. F i n a l l y , a minor part of Denmark
is covered with post-glacial soft-deposits, i . e . peat, g y t t j a , and unconsolidat-

0048-9697/85/$03.30 © 1985 Elsevier Science Publishers B.V.

344

ed sand, s i l t or clay.
A geology s i m i l a r to the Danish is found in the northern part of Germany and
Poland, in Holland, and in the southeastern part of England.
I t has been the aim of the present work to investigate the techniques f o r
measurements of the radon emanation from soil samples, and to establish a p r e l i -
minary characterization of the Danish surface deposits as sources of radon-222.

THEORY
The exhalation of radon, i . e . the release of radon from the surface of a
sample, is the r e s u l t of a two-step process ( r e f . 4 ) . F i r s t , the radon atoms,
which by t h e i r r e c o i l energy leave the mineral grains, must be slowed down and
stopped in the pore space. This emanation process is enhanced by the presence
of water in the pore space. Second, the radon atoms must d i f f u s e to the surface
of the sample in order to escape. This process is also influenced by the pres-
ence of water, since an increasing amount of water in the pore space w i l l dimi-
nish the d i f f u s i o n length f o r radon ( r e f . 5 ) .
Consider a sample of a porous material enclosed in a "radon-tight" container.
The sample f i l l s the container to the height ~, which leaves a confined a i r v o l -
ume VD above the sample. The steady state solution of the d i f f u s i o n equation
r e a d i l y y i e l d s the radon a c t i v i t y concentration AS (Bq.m-3) in VD f o r the equi-
librium situation (ref.6)

RMt ~ VD
AS = i B= r , B , (I)
VD( + ~)
where R = radon emanation rate (atoms per sec per kg dry mass); Mt = dry mass of
the sample (kg); VD = volume of a i r above the sample (m3); ~ = height of the
sample (m); VB = volume of the sample (m3); L = d i f f u s i o n length of radon in the
sample (m); and ~ = porosity of the sample.
Equation ( I ) can be s i m p l i f i e d by the approximation B/tghB = I , i f the d i f f u -
sion length L is large compared to the sample dimension ~. In that case, the
emanation can be determined by the measurement of AS:

VD 1
R = AS Wt
t (I + ~) (2)

AS can be measured when the e q u i l i b r i u m is reached. However, i t is f a s t e r to

determine AS from the growth curve of the a c t i v i t y concentration in the contain-
er. Caution must be exerted in the l a t t e r case, since t h i s is not a steady state
s i t u a t i o n . The exhalation rate from the sample into the a i r volume VD decreases
from the free exhalation rate EF at the time of closure to the bound exhalation
rate EB, when the e q u i l i b r i u m is attained.
The r a t i o between the two is given by:
 345

EF tghB
--: 1 + (3)
EB ~B

Samuelsson ( r e f . 7 ) has calculated the exhalation rate E(t) as a f u n c t i o n of

time. E(t) drops o f f sharply from EF and approaches EB asymptotically. The "re-
shaping time" is introduced as the time t s f o r which E(ts) - EB = O.05(EF-EB).
The order of magnitude of t s depends on B and is found to be 1 day f o r B = 0.5
and 1 hour f o r B = 0 . I .
As an approximation, the exhalation rate can therefore be considered constant
s h o r t l y a f t e r the closure, i f L is large compared to ~ and i f ~ >> I . With t h i s
approximation the growth curve f o r the a c t i v i t y concentration is given by:

A(t) = AS(I - e - x t ) (4)

where ~ is the e f f e c t i v e decay constant, i . e . ~ = ~ R n f o r a " r a d o n - t i g h t " c o n t a i n e r .

Based on t h i s approximation, AS , and hence the emanation rate R, can be de-
termined from measurements of A(t) during the growth period.

EXPERIMENTAL PROCEDURES
F i r s t method
The sample container used f o r the a c t i v i t y growth measurements is a 5.8 l i t r e
c y l i n d r i c a l steel vessel supplied with two valves f o r the c i r c u l a t i o n of a i r
samples.
The radon detector system consists of an a i r f i l t e r , a pump, and the s c i n t i l -
l a t i o n f l a s k which was always at atmospheric pressure. A i r samples were trans-
ferred to the s c i n t i l l a t i o n f l a s k by connecting the sample container and the de-
t e c t o r system in a closed c i r c u i t . The a i r was then c i r c u l a t e d u n t i l the a c t i v i -
ty concentration was homogenized. F i n a l l y , the s c i n t i l l a t i o n f l a s k was discon-
nected and counted f o r 300 min. or more. A waiting period of 15 min. was i n t r o -
duced before the counting in order to avoid 220Rn. This procedure involves a
c a l c u l a t i o n of the 4
:22 Rn-daughter c o n t r i b u t i o n . A minimum of 2 and a maximum of
4 a i r samples were measured f o r each s o i l sample during a period of I0 days.
The a i r sampling introduces a small d i l u t i o n of the a c t i v i t y concentrations.
This d i l u t i o n can be accounted f o r i f ~ is known. Thus the data treatment is an
i t e r a t i v e procedure: With ~ = ~Rn as the s t a r t i n g p o i n t , the corrected a c t i v i t y
concentrations are calculated. Expression (4) is then f i t t e d to the corrected
a c t i v i t y concentrations with ~ and As as the f i t t i n g parameters. This process is
repeated with the new value of ~ u n t i l the l i m i t i n g value of ~ is found. I f t h i s
value is reasonably close to the decay constant f o r 222Rn, and i f the reduced ×2
f o r the f i t is acceptable, the emanation is f i n a l l y determined from AS and equa-
t i o n (2).
346

Second method
This method is based on the measurement of the equilibrium gamma a c t i v i t i e s
of 214pb and 214Bi both of which are daughters of 222Rn. The sample is placed
in a container made of brass f o i l - a Marinelli beaker - which f i t s around a
Ge(Li) gamma ray detector. First a measurement with the container open is per-
formed. Before and during the measurement, 222Rn atoms exhaled from the sample
is assumed to leave the conatiner through a hole in the outer part of the Mari-
n e l l i beaker. Then the container is closed, and within two weeks a near-equili-
brium between 226Ra and 222Rn and daughters is reached, and the gamma a c t i v i t i e s
of 214pb and 214Bi are measured again.
The difference between the two a c t i v i t i e s is due to the leaking radon before
and during the f i r s t measurement in the open container. This difference is used
for a calculation of the radon leakage.
The assumption that L is large compared to the sample dimension is essential
for both methods. Typical sample heights for the f i r s t method were ~ ! 6 cm,
while the Marinelli beaker used for the second method has a typical dimension
of 13 cm. This should be compared to the diffusion length for radon which p r i -
marily depends on the porosity and the water content of the sample. Empirical
relations for soil material yield a diffusion length L > 20 cm for samples which
are not saturated with water (ref.5). Hence, for this type of samples, the
approximations of the methods should be applicable.
Samples with a water content close to the saturation have also been measured.
In these cases the sample dimension was kept smaller than the standard value,
or the sample was granulated in order to ensure a large effective diffusion
length.

RESULTS AND DISCUSSION

The determination of the effective decay constant ~ in the f i r s t method serv-
es as a leak control of the sample containers. Out of 80 measurements based on
the f i r s t method, only 8 measurements ( a l l performed with a preliminary version
of the sample container) showed ~-values s i g n i f i c a n t l y larger than ~Rn" These 8
cases were interpreted as "container leaks" and were rejected on that ground.
The effect of a small diffusion length was investigated for 4 samples of
compact clays (LYB l , KRO 14, STR A, and STR 2, see table l and 2). Using the
f i r s t method with a sample height of 4.5 cm, the emanation rate was measured as
a function of the water content. The emanation rates were found to increase with
the water content up to about 17 per cent ( i . e . water content per wet mass of
the sample). This effect is due to the increased retainment in the pore volume
of recoiling radon atoms. Above 17 per cent water the apparent emanation rate
decreases. This is interpreted as the result of a decreasing diffusion length
for radon.
 347

The results of the measurements are presented in Table 1 and 2. Table 1 in-
cludes all glacial deposit samples, i.e. both moraine deposits and diluvial de-
posits. Table 2 concern all other types of samples. For each sample is shown
the 226Ra content (Bq/kg), the emanation rate (atoms.s-l.kg-l), the emanation
ratio (fraction of "produced" radon atoms that is emanated), and the water con-
tent. Each sample is given a short lithological description.
The emanation rates of the samples varies from less than l atom.s-l.kg -l for
bryozoan limestone to more than lO0 atoms.s'l.kg -l for some clay samples. The
samples can be divided into 3 classes based on their emanation rate. The f i r s t
class comprises samples with an emanation rate of less than 5 atoms.s-l.kg - l ,
and in this class are found most samples of diluvial sand, s i l t , and gravel.
Also most samples of moraine sand belong to this class, as do all samples of
limestone and chalk.
Class 2 samples have an emanation rate between 5 and lO atoms.s-l.kg - l .
Most samples of moraine clay belong to this class regardless of their content
of sand, s i l t , gravel, moisture, and carbonates. A closer examination t e l l s ,
however, that the lowest emanation rate is found for the most sandy and stony
samples of moraine clay, and the highest emanation rate is found for the most
clayey samples. Class 2 also includes samples of diluvial clay.
Most of the samples of Tertiary marine clays belong to Class 3 with an ema-
nation rate of more than lO atoms.s-l.kg - l . The highest emanation rates are mea-
sured for the samples MOR 70 and MOR 71, which consist of a porous black Paleo-
cene clay with organic matter and diatoms. The measured emanation rates are in
the range 74-130 atoms.s-l-kg- l . The radium content of the samples is high too.
The samples MOR 69 and MOR 72 with an emanation rate of ll-15 atoms.s-l.kg -l
have been taken from the same deposit only half a meter above and below the
samples MOR 70 and MOR 71. Thus very strong local variations of the radon ema-
nation can be found in a deposit, which seen from a lithological point of view
is rather homogeneous.
A similar - but less strong - local variation has been seen in a deposit of
mo-clay, which is a porous marine diatomite with a low content of clay particl-
es.
Tertiary marine clays are found close to the surface at several localities
in Jylland and may influence the radon content of the air in the houses built
there.
In the group "miscellaneous" (Table 2) are seen 3 samples of peat soil.
Their 226Ra content differs very much as does their radon emanation. Probably
the 226Ra content of peat soils is very dependent on local geochemical condi-
tions. 226Ra is a daughter of 230Th which i t s e l f is a daughter of 234U. Uranium
is easily dissolved by water during oxidizing conditions and is precipitated
during reducing conditions. In peat soils the chemical environment in general
348

TABLE 1
Emanation of radon-222 from samples of glacial deposits

Radium Emanation Emanation Moisture

Sample name and description content atoms/ ratio weight t
Bq/kg (kg.s) per cent
Moraine clay
HAV lO, s l i g h t calcerous • 42 5.8-II 0.14-0.26 22
HUN l , s i l t y and sandy• 30 3.8-5.6 0.18 15
KLI l , with sand and gravel 28 5.8 0.21 9
MAD l , s i l t y and calcerous 27 7.5 0.28 16
MAD 2, with sand and gravel • 26 4.3-4.7 0.16-0.18 14
MAD 6, sandy, s i l t y , calcareous • 27 5.8-7.0 0.21-0.25 15
MAD 8, s l i g h t sandy and s i l t y • 37 8.7-II 0.23-0.29 13
MAD lO, s l i g h t sandy• 29 5.2-9.3 0.18-0.32 18
NEB 184, very sandy, stony 22 2.4 O.ll 3
NEB 185, s l i g h t sandy, stony 31 4.5 0.14 lO
TIK l , s l i g h t sandy, calcerous 26 7.2 0.28 lO
TIK 2, very sandy 25 9.8 0.39 3

Moraine sand
FUR 181, s l i g h t clayey 16 2.6 0.16 6
NEB 25, sand with gravel 16 l .5 0.09 4
SOS B, clayey, calcerous 29 7.5 0.25 13

Diluvial clay
KRO 2, very s l i g h t s i l t y • 32 lO.5-11 0.25-0.27 15
KRO 4 & 13, with traces of mica~ 30-34 5.2-6.2 0.15-0.20 18-27
KRO lO, traces of plant residues 37 8.1 0.22 18
KRO 14, with organic matter ~ 33 7.6 0.23 23
STR l , 2 & A, s l i g h t s i l t y • 28-29 3.4-5.8 0.12-0.20 23-25

Diluvial sand, s i l t , and gravel

FAR l , 2 & A, s i l t with clay • 19-21 2.8-3.6 0.13-0.18 II
HAL 2, s i l t with clay 24 6.2 0.26 19
HAL 6, sand 7 0.6 0.09 0
HAV l & 2, sand and wood residues ~ 9 2.4-2.5 0.27 21-24
HIM 13 & 14, gravel and sand ll-13 1.5-I.9 O.ll-O.17 0-4
HOV I I , s i l t , s l i g h t clayey 21 4.0 0.32 8
MAD 7, s i l t , sandy 13 3.4 0.27 5
VAS 2, sand, very fine 16 2.4 0.14 2
VAS 8, gravel and sand II 1.7 0.16 4

•Sample measured by both methods.

tMost of the moisture contents shown in the table correspond to the original
in situ moisture content.
 349

TABLE 2
Emanation of radon-222 from samples of non-glacial deposits

Radium Emanation Emanation Moisture

Sample name and description content atoms/ ratio weight t
Bq/kg (kg.s) per cent
Tertiary marine clays
ERS l , porous, black 41 19 0.47 49
FUR 121, sticky and plastic 18 I0.6 0.61 37
FUR 182, sticky and plastic 73 16 0.22 33
FUR 187, not plastic 18 9.9 0.55 35
LYB l & 6, micaceous, black* 52-53 9.5-12.3 0.19-0.23 20-24
MOR 69 & 72, with organic matter 39-60 ll-15 0.21-0.29 49-50
MOR 70 & 71, with organic matter* 250-300 7 4 - 1 3 0 0.31-0.54 45-48
SKI l , s l i g h t micaceous 39 9.9 0.25 27
SPA 3 & lO, s i l t y , organic matter 43-62 6.2-I0.4 0.I0-0.24 23-26
STA 50 & 51, micaceous, s i l t y 31-35 7.3-8.4 0.23-0.24 13-17

Moclay, a t e r t i a r y marine diatomite

FUR 122 67 ll.2 0o16 29
MOR 222, 231 & 237 35-56 9-22 0.25-0.39 36-48
SKA l * 70 ll-14 0.16-0.20 46
STO 177" 120 16-17 0.14-0.15 25

Limestone and chalk

ASS lO, coccolitic chalk 9 l .l 0.12 16
NEB 145 & 146, calcarenite 13-19 0.3-0.4 0.02-0.03 0-8
STE 3, bryozoan limestone 2.8 < 0.5 < 0.17 7

Miscellaneous
ALU l , alum shale 630 16 0.03 2
KRO 5, non-marine diatomite* 28 15.6-23.5 0.56-0.83 70
KRO 6, peat with sand and clay 38 lO.O 0.26 61
NEB 302, peat 7 l.l 0.17 65
NIV 3, peat 66 8 0.12 55
SKE l , Tertiary a l l u v i a l clay 42 9.5 0.22 3
TUN I I , sand with heavy minerals 850 52 0.06 0

*Sample measured by both methods.

tMost of the moisture contents shown in the table correspond to the original
in situ moisture content.
350

is reducing, and water with a content of uranium seeping through the s o i l w i l l

p r e c i p i t a t e the uranium. During the decay of uranium a content of radium is
slowly b u i l t up. Due to the long h a l f l i v e s of 230Th and 234U an e q u i l i b r i u m
between 234U and 226Ra is not reached u n t i l a m i l l i o n years l a t e r .
The Tables 1 and 2 include samples that have been measured by method I ,
samples that have been measured by method 2, and samples that have been measur-
ed by both methods. The l a s t group forms a basis f o r a comparison between the
two methods. In general the two methods have given the same results w i t h i n the
accuracy of the measurement, which is about +/- 20 per cent. However, f o r some
moist dense clayey samples the second method has given emanation rates of only
55-70 per cent of the emanation rates found by the f i r s t method. I t is assumed
that the difference is due to the larger sample dimension f o r the second method,
i . e . the condition that L is larger than the sample dimension has not been met.
In these cases the measured emanation rates may be too low.

CONCLUSION
As a r e s u l t of the present work a preliminary radon emanation catalogue of
common Danish s o i l s has been established.
The expected main trends of c o r r e l a t i o n between the emanation rates and the
226Ra content, the grain s i z e , the water content, and the porosity have been
confirmed.
A few geological deposits with high radon emanation rates have been found.
Houses with a high level of indoor radon could possibly be found in areas with
t h i s type of surface geology.

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