RAPID COMMUNICATIONS IN MASS SPECTROMETRY, VOL.

10, 1415-1417 (1996)

A Preliminary Stable Isotope Study on a Potential

Radioactive Waste Repository Site in the Mecsek
Mountains, Southern Hungary
Attila Dernkny* and IstvBn Fbrizs
Laboratory for Geochemical Research, Hungarian Academy of Sciences, Budapest, Budaorsi bt 45, H-1112, Hungary

Zoltiin MBthC
Mecsek Ore Mining Co., Ptcs, Esztergiv L. lit 19, H-7633, Hungary.
SPONSOR REFEREE: Dr. Kiroly Vtkey, Central Research Institute for Chemistry, Hungarian Academy of Sciences, Budapest,
Hungary

A potential repository site for high-activity radioactive waste is investigated in the vicinity of a former uranium
mine in the Mecsek Mts. (S. Hungary). In order to evaluate the usefulness of the site, stable H, C and 0 isotope

compositions of shallow groundwaters, repository site waters, carbonate veins and fluid inclusions of the veins
have been measured. Shallow groundwaters have H and 0 isotope compositions identical to those of the present
day local precipitation water, whereas repository site waters show 6D and li1'0values characteristic of
Pleistocene meteoric waters. Based on S"C, 6"O and 6D (inclusion fluid) data, the calcite veins might have been
formed by movements of meteoric water originating from precipitation in a warmer climate of the geological
past. The results indicate that no significant infiltration of surface waters to the investigated repository site
occurs, but signs of migration of Pleistocene waters along the veins has been observed.

Making a decision on a planned radioactive waste repository requires knowledge as to whether the site is closed to
its environment. Since the repository in question is to be
built in the area of a former uranium mine at loo0 m depth
by opening a separate new shaft, its connection to surface
waters is the first issue to be studied. Another important
question is whether the rock complex is subject to the
circulation of fluids that could dissolve and carry material.
Such fluid movements are indicated by the presence of a
network of calcite (calcium carbonate) veins in the sedimentary rocks of the repository site. Thus, the repository
site area has been studied by numerous methods which
include porosity and impermeability measurement, age
determination (by tritium and 14Cdating) and determination
of metamorphic degree (by X-ray diffraction investigations). Among the methods used in this preliminary
investigation are stable isotope ratio determinations in
shallow groundwaters, repository site waters and calcite
veins, which have been carried out in order to provide a first
evaluation of solution migrations in the repository site. This
paper presents the stable isotope data and provides a model
for the formation and evolution of the calcite veins.
EXPERIMENTAL
Geological background

The geology of the area and the rock system in question has
been described in unpublished research reports not open to
the public, thus the main geological features are only briefly
discussed here. The rock system of the waste repository
belong to the so-called Boda Siltstone Formation that was
deposited in a salty lake environment during the middle
Permian over a depth of 700-900 m. The rock is a reddish
brown fine-grained siltstone with minor sandstone and

Author for correspondence.

CCC 0951 4 198/96/11] 415 4 3
0 1996 by John Wiley & Sons, Ltd.

carbonate intercalations. The siltstone consists mainly of

quartz, albite, illite, muscovite, chlorite, hematite and
carbonate minerals. Illite and chlorite crystallinity data
indicate rock formation conditions at the border of the
diagenesis-anchizone metamorphism. The siltstone is
frequently transected by veins that contain carbonates,
sulphates, feldspars, quartz and clay minerals, sulphide
minerals appear less frequently. The footwall rocks are
composed of lower-middle Permian sandstones and conglomerates. The hanging wall rocks are upper Permian
coloured sandstones. Unlike the Boda siltstone, that was
deposited in a lake, the footwall and hanging wall rocks are
of fluvial origin.
Analytical methods

Stable carbon and oxygen isotope compositions of calcites

were measured by the conventional phosphoric acid digestion method established by McCrea' on CO, (see also
procedure in Ref. 2). Stable oxygen and hydrogen isotope
compositions of water samples were determined by COzH,O isotope exchange3 and conversion of H,O with zinc
(Biogeochemical Labs., Indiana University, Bloomington,
IN, USA) at 480 "C to hydrogen gas,4respectively, followed
by isotope ratio measurement on CO, and H, respectively.
Inclusion waters were released from calcites by vacuum
crushing, and then the water obtained was treated as
described above. Special care was taken to maintain stable
hydrogen/zinc ratios during water conversion in order to
avoid the hydrogen isotope fractionation caused by hydrogen absorption by zinc upon c o ~ l i n g .13C/"C,
~ . ~ '80/'60
and
D/H ratios were determined in CO, and H, gases using a
Finnigan MAT (Bremen, Germany) delta S mass spectrometer. The raw data were corrected for ''0
The
data are expressed as conventional S values (S=[R,,,,,/
Rsrandard
- 1 J x 10o0, where Rsample
and Rsrmdard
are the isotope
ratios in the sample and in the standard, respectively) in %O
relative to the PDB (Pee Dee Belemnite) and SMOW
Received 14 July 1996
Accepted 22 Jury 1996

STABLE ISOTOPE STUDY ON RADIOACTIVE WASTE SITE

1416

(Standard Mean Ocean Water) international standards. The

reproducibilities of S13Cand 8'0 data from carbonates and
waters were better than f 0 . l%o. The average reproducibilities of 6D data of water samples and inclusion waters were
f l%o and f 3%0, respectively.

RESULTS AND DISCUSSIONS

All of the measured stable isotopic compositions are listed
in Table 1 and plotted in Figs 1-3. Since measurements
have been made on different materials, the results will be

Table 1. Stable isotope compositions of waters, total dissolved

carbonate, carbonates and their inclusion waters. All
data are in %O relative to PDB (SI3C) and SMOW
6D)
SD

8'80

- 76
- 68
- 69

- 11.0
- 11.0
-9.5
- 9.5

6C

6'80

waters

4238 mine water

4239 mine water
4241 shallow groundwater
4242 shallow groundwater

- 76

calcite veines

- 5.5
- 4.4
- 4.3

2
3
4
5
6
7
9
11
13
14
16
17
18
19
20
21

- 4.6

- 4.6

- 5.3
- 4.7
- 0.2
- 0.9
- 3.2
- 0.2
- 3.5
- 3.4
- 3.3
- 4.3

H20ppm

6D

1090
780
800
570
970
260
690
680
1330

- 79
- 71

2
3
4
5
6
7
18
19
21

- 65
- 73
-51
- 42
- 52
- 72

-120

'

-10

'

10

b"0 [SMOW,

20

30

"/,I (70C)

Figure 2. Stable hydrogen and oxygen isotope compositions of waters in

equilibrium with calcite veins, potential repository site, Mecsek Mts., S.
Hungary. The 8D values were directly measured in inclusion waters, the
S'*Ovalues calculated using the fractionation relationship of O'Neil el aP4
at 70 "C. the fields of water types are taken from S h e ~ p a r d . ' ~

presented in separate sections, then a model describing the

isotopic changes will be given at the end.
Waters

The stable H and 0 isotope compositions of water samples

clearly reflect the differences between sample origins and
form two compositional groups. Two samples (4241 and
4242) collected from shallow groundwater have SD and
S1'0 values ( - 68.5 +0.5%0 and - 9.5%0,respectively) that
are practically identical to the mean isotopic compositions
of the present day local precipitation.8 The other two
samples (4238 and 4239) collected at 1000 m depth in the
repository shaft have more negative SD and 8
'0 values
( - 76%0 and - 11%0, respectively) indicating that these
waters precipitated and subsequently infiltrated into the rock
system under different climate conditions that were cooler
by 3-5 "C, than present day temperatures,' most probably
during the Pleistocene.
The difference of the two collection localities is also
reflected in the 6I3C data for the total dissolved carbonate
(TDC). A shallow groundwater sample (4241) has a more
negative 613C value ( - 12.5%0) than those of samples
collected in the repository site ( - 7.6 and -7.0%0). The
more negative value is consistent with dissolution of
atmospheric CO, and its mixing with I3C-depletedorganicderived C 0 2produced in the soil as expected in the case of
shallow groundwaters.", I' The higher 6I3C values obtained
from repository site waters reflect the effect of rock/water
interaction, since these waters must have infiltrated relatively 13C-rich sedimentary carbonates on their way to the
deep site and consequently contain a dissolved component
for which S13C-O%~.'2

- 72

0 ,

- 7.0

- 12.5
nd

16.4
16.4
16.4
16.0
16.1
15.9
15.7
15.9
18.5
16.9
15.8
15.6
15.0
14.4
14.4
15.9

- 4.8

inclusion waten

PC

- 7.6

magmatic water

-20

-40
-50
-60
-70

**
-6

'

14

'

-80

I
15

16

17

18

19

6"O (SMOW, '/J

Figure 1. Stable isotope compositions of carbonate veins, potential
repository site, Mecsek Mts., S. Hungary.

-90
-6

-5

-4

-3

6I3C(PDB,
Figure 3. Correlation of stable hydrogen isotope compositions of inclusion waters and carbon isotope compositions of calcite veins.

STABLE ISOTOPE STUDY ON RADIOACTIVE WASTE SITE

Calcite veins
The C and 0 isotope compositions of calcite veins collected
within the repository site area show a scatter between - 5.5
and -0.2%0 and between 14.4 and 18.5%0, respectively
(Table 1 and Fig. 1). The S13Cdata reflect the values of the
solutions from which the carbonates were precipitated,
whereas the 8'0 data depend strongly on both fluid
composition and precipitation temperature. The C isotope
compositions suggest mixing of two carbon components,
one with a high SI3Cvalue and another that is more depleted
in I3C. The first component can certainly be identified as
dissolved sedimentary carbonate with S13C-W0,I2whereas
the second component might have originated from the
oxidation of organic material (with 6I3C in the range - 30
to -20%0) or from magmatic CO, (for which
6I3C - 7%0"). The distinction will be made on the basis of
0 and H isotope compositions.
Since the S1*0data of carbonates alone do not imply fluid
origin, fluid 8'0 compositions have been calculated using
the calcite-water oxygen-isotope fractionation relationship
of Friedman and 0'Neili3modified after O'Neil et all4 with
precipitation temperatures estimated by fluid inclusion
microthermometry (79- 124 "C, K. Torok, unpublished
results). The calculated 8'0 data are shown in Fig. 2 (see
discussion later).

Inclusion fluids
The calcite veins contain'260 to 1330 ppm H20, whose H
isotope compositions show correlation with the 6I3Cdata of
the host carbonates (Fig. 3). Since fluid inclusions represent
the solutions from which their host calcites were precipitated and since post-formational H isotope exchange
between inclusion fluid and host mineral could not take
place, their SD values directly reflect those of the original
solutions. Thus, the 6D values, plotted as a function of
calculated S1'O (fluid) values, provide a plot which enables
us to make a distinction between waters of different origin
(Fig. 2). This figure also shows the main water types." The
distribution of data points indicate mixing of meteoric
water, with 6D - 4Wo0 and 6"O - 5%0, and organic
water (i.e. water derived from the oxidation of organic
matter16). The isotopic compositions of the presumed
meteoric water are significantly higher than those of the
present day local precipitation, indicating that the waters
responsible for the formation of vein calcites derive from
precipitations during a warm climate prevailing prior to the
Pleistocene.
The next question is the source of the D-depleted
component. As has been shown in Fig. 3, the 6D values are
correlated with the SI3Cdata from calcites, thus the negative
SD shift could be related to the influence of organic matter
oxidation. This process might be inferred from Fig. 2, in
which the data points are scattered between the meteoric
water line (MWL) and the field of organic waters. On the
other hand, the lowest SI3C(calcite)value ( - 5.5%0) corresponds to 25% organic-derived carbon in the TDC, whereas
the lowest 6D value ( - 79%0)requires -50% organic water
in the fluid. Remarking that organic matter contains much
more C than H, the observed 6D and 6I3C shifts cannot be
attributed entirely to admixing of organic-derived fluid.
Another explanation can be found in the presence of
secondary fluid inclusions that became trapped in the
already crystallized calcite by cracking and subsequent
healing. In this way, the calcite would contain two
generations of fluid inclusions. The isotopic compositions

1417

characteristic for warm climates would correspond to the

primary generation, whereas the SD value of -79%0
indicates the influence of Pleistocene waters in the formation of secondary fluid inclusions. Since the Pleistocene
waters would bring I3C-depleted dissolved carbon (with
SI3C- - 7.3%0, see above), secondary carbonate precipitation from these solutions might modify the measured 613C
value of the bulk vein calcite. The reason why the assumed
secondary fluids do not plot on the meteoric water line
(MWL, Fig. 2) can be found in the different degrees of
interaction with "0-enriched sedimentary rocks.

CONCLUSIONS

SD and SI8O data indicate that the water collected at the

investigated potential radioactive waste repository site in
the Mecsek mountains is of Pleistocene meteoric water
origin that differs isotopically from the shallow groundwaters collected above the repository site. The shallow
groundwaters have isotopic compositions that are identical
to those of the present day local precipitation. On the basis
of stable C, 0 and H isotope compositions, the formation of
the network of calcite veins in the repository site is not
related to the shallow groundwaters or to the repository site
waters, but can be attributed to movements of meteoric
waters precipitated during a warm climate in the geological
past before the Pleistocene. The results indicate that
repository site waters have no appreciable amount of
surface water component. However, upward movements of
fluids cannot be excluded, and a future study with more
detailed sampling is needed. Limited migration of Pleistocene waters along calcite veins has been detected in the
rocks of the potential repository site.
Acknowledgments
The paper is published with the permission of the Mecsek Ore Mining Co.
The mass spectrometer laboratory was established and developed with the
financial support of the Hungarian Scientific Research Fund (OTKA 1154
and T 014968).

REFERENCES
1. J. M. McCrea, J . Chem. Phys. 18,849 (1950).
2. A. DemCny and I. F6rizs. Rapid Commun. Mass Spectrom. 5, 524
(1992).
3. S . Epstein and T. K. Mayeda, Geochim. Cosmochim. Acta 4, 213
(1953).
4. M. L. Coleman, T. J. Shepherd, J. J. Durham, J. E. Rouse and G. R.
Moore, Anal. Chem. 54,993 (1982).
5. A. Demtny, Chem. Geol. 121, 19 (1995).
6. H. Craig, Geochim. Cosrnochim. Acra 12, 133 (1957).
7. J. Santrock, S. A. Studley and J. M. Hayes, Anal. Chem. 57, 1444
(1985).
8. J. DePk. VITUKI Budapest, Research Report (1995).
9. International Atomic Energy Agency, Sraristical Treatment of Data on
Environmental Isoropes in Precipitation. IAEA, Vienna (1992).
10. W. M. Sackett and W. S. Moore, Chem. Geol. 1,323 (1966).
11. P. Fritz, J.-Ch. Fontes, S . K. Frape, D. Louvat, J.-L. Michelot and W.
Balderer, Geochim. Cosmochim. Acra 53, 1765 (1989).
12. J. Hoefs, Stable isotope geochemistry, Springer Verlag, pp. 140
(1980).
13. I. Friedman and J. R. ONeil, Dafa of Geochemisrp 61h, Geol. Sun?
Prof: Paper 440-KK (1977).
14. J. R. O'Neil, R. N. Clayton and T. K. Mayeda, J. Chem. Phys. 51,5547
( 1969).
15. S. M. F. Sheppard, in Stable isoropes in high temperature geological
processes, J. W. Valley (Ed.), H. P. Taylor, Jr. and J. R. O'Neil, Reviews
in Mineralogy 16, 165 (1986).
16. S. M. F. Sheppard and A. Charef, C.R . Acad. Sci. Paris, t. 302. se,: II
19, 1189 (1986).