HEAVY METAL VARIATION IN THE SOILS ASSOCIATED WITH THE

BALAN MINING PERIMETER

AS Ramona Balint
Geological Survey of Romania
1, Caransebes St., Sector 1, RO-012271, Bucuresti - 32, Romania
e-mail: balint.ramona@yahoo.com

ABSTRACT
Balan perimeter is one of the most representative mining zones of the Eastern
Carpathians, well known for its copper ores, represented mainly by massive and/or
disseminated pyrite and chalcopyrite concordantly interlayered with low grade Cambrian
metamorphites of the Tulghes Group.
The chemical study of these accumulations highlighted the presence of elements (Cu,
Pb, Zn, Ni, Co, Mn) which, by geochemical characteristics and behaviour, can be
included in the category of heavy metals and which, by build-up and/or migration in the
surface water network and soils, can become pollution factors.
The present study has the objective of investigating the accumulation and migration
patterns of the mentioned elements in soils.
Key words: heavy metals, soils, aqueous solutions, pollution.

Introduction
The existence of mining exploitations in a certain area always has a negative impact on
the quality of the environment and, therefore, on human communities. Because of this
issue, mining perimeters must be permanently examined and monitored, in order to
prevent and diminish harmful effects and to improve environmental conditions.
It is well known that there has been an intense mining activity in the Eastern Carpathians
which, in most cases, has not made the object of a plan to prevent, eventually identify
and monitor pollutants. This situation has led to the development of necessary studies
that would highlight the areas where mining processes disturb the physico-chemical
balance of the soil, which takes the shape of increased elemental concentrations,
especially of heavy metals.
Therefore, the aim of this work is to identify the pollutant factors from the mining
perimeter of Balan and to mark out the areas where heavy metal content in soils exceeds
normal limits.
The distribution area of these elements reflects the layout of the exploration-exploitation
works in the Balan mining area.
It was observed that: (i) the elemental distribution is relatively uniform throughout the
entire perimeter, taking into account the remarkable number and location of the mining
works, the dumping sites and the settling pond and (ii) the maximum concentration
zones are outlined in the emplacement area of some tunnels and/or their associated
dumping sites.

1
Mineralogy and geochemistry of the copper ore from Balan
Balan ore, located on the eastern rim of the crystalline-Mesozoic area of the Eastern
Carpathians (Kräutner, Bindea, 1995) consists of fine pyrite-chalcopyrite dissemination,
as well as massive ore disposed as bands or small lenses (cm-dm) in the Cambrian
metamorphites of Tulghes Group (Kräutner, Popa, 1969); subordinately, sphalerite and
galenite have been identified, and only locally, cubanite and other Cu-Zn-Pb-Fe mineral
associations, as well as native bismuth, gold and silver have been observed (Petrulian, et
al, 1971).
In Balan ore, the presence of some heavy metals (Cu, Pb, Zn, Ni, Co), as well as Mn, has
been emphasized by analytical chemical investigations (table 1).

Table 1. Variation of some heavy metals (mg/kg) in the pyrite and chalcopyrite ore from
the mining area of Balan (Kräutner, et al, 1992).

Cu Pb Zn Ni Co Mn
Pyrite 50–30.000 25–30.000 10–24.000 3–650 100–1.600 10–1.030
Chalcopyrite 60–30.000 160-29.000 <10–200 <10–600 <10–1.100

Identification of pollution factors from the mining area of Balan

In order to identify the pollution factors, some field activities have been developed. They
consisted of observations on mining dumps, galleries and sludge beds, with the purpose
of pointing out their preservation state: stability of slopes, granulometry and weathering
products of petrographical and ore components.
These investigations highlighted:
- a precarious preservation of mining dumps, very seldom not stabilized or fixed only
with rods fences, and/or vegetation (coniferous, birch trees). Frequently, the mining
dumps present deep erosional marks on their slopes, created by rainwater flowing along
the slopes.
- the presence of pyrite and chalcopyrite ores mixed with tailings of mining dumps.
Their weathering under atmospheric conditions causes the enrichment in heavy metals of
surface and infiltration waters.
- the usage of mining dumps and/or tailings to repair local roads or to build the right
slope of the accumulation lake, which determines an extended pollution, outside the
mine’s working area.
- insecure galleries, some of them presenting incipient or total collapse phenomena.
- an intensive pollution of the Olt valley in the vicinity of the preparation plant, where
the color of the river’s water is brownish–yellow and the presence of Fe-oxide-
hydroxide deposits was observed.
- no preservation of Lunca Mare sludge bed, that could be an important pollution source,
taken into account its high content in heavy metals and its very fine constituent particles,
which can be taken by wind and carried out, thus affecting a wider area.

2
Methodology for sampling and analytical investigations
In order to emphasize the content of some heavy metals, their accumulation and
migration in the Balan mining area, 52 soil samples were collected from the soil surface,
each weighing about 250 g and air dried.
The samples were investigated as powder and aqueous solution using modern analytical
equipments, XRF (MINIPAL-4 spectrometer) and AAS, graphite technique (ZEEnit-700
spectrophotometer) after a previous specific preparation.
The sample preparation for XRF investigations consisted of sieving and grinding the
soils, weighing 4 g, heating them until constant temperature (105 oC), and pressing. For
AAS investigations using graphite technique, 2 g of soil were mixed with 10 mL
bidistilled water, stirred around 15 minutes, settled for about 30 minutes and finally
filtered.
After heating the soils at 105 oC, it was determined that the mass of the samples
decreased with 0,0041 – 0,1716 g, which represented volatile compounds.
Our own XRF and AAS procedures and certified reference materials were used. The
analytical data was processed using Winsurf, Ocad, and Excel software.

Heavy metal evaluation in the soils of Balan mining perimeter

According to analytical investigations, obtained concentrations of heavy metals are
frequently higher than the nationally admitted values (table 2) and sometimes can exceed
the intervention threshold (Order no. 756/1997 issued by the Ministry of Waters, Forests
and Environmental Protection of Romania). Heavy metal amounts in aqueous solutions
have normal values, except copper, which, in many cases, surpasses maximum admitted
concentration in wastewaters ejected into natural water resources, with which we
compared our solutions. (Decision no. 188/2002 issued by the Ministry of Environment
and Water Management of Romania).

Table 2. Alert threshold for sensitive terrains (Order no. 756/1997) and maximum
admitted concentrations of heavy metals in waters ejected into natural receivers
(Decision no. 188/2002), in mg/kg.

Cu Pb Zn Ni Co Mn
Soil 100 50 300 75 30 1500
Wastewater 0,1 0,2 0,5 0,5 1,0 1,0

Heavy metal concentrations obtained for the samples taken from Balan are presented in
table 3. Cobalt has values that usually exceeds the alert limit, while the amount of
manganese is approaching normal values, with only a few exceptions. The rest of the
studied elements frequently have a higher content than admitted concentrations.
The highest pollutant is copper, due to its accumulation in some areas and its obvious
mobility in aqueous solution, which leads to an increased bioavailability and potential
contamination of groundwater.

3
Table 3. Total content (*) and concentration in aqueous solutions (**) of Mn, Pb, Zn,
Ni, Cu and Co in the soils of Balan mining perimeter (mg/kg).

Values exceed normal concentration in soils.

Values exceed alert levels for soils.
Values exceed intervention levels for soils.

4
 Values exceed maximum admitted concentration in wastewaters.
Heavy metal correlation
The following diagrams represent total content of the studied heavy metals in soils from
Balan perimeter. The correlation charts highlight the reduced dispersion degree of the
samples as well as the positive linear trend between most of the elements. The
correlation coefficients have been calculated for every combination, as well as between
total content and aqueous solution concentrations. In solutions, the highest coefficients
were found between lead and zinc – 0.96, copper and zinc – 0.93 and cobalt and zinc –
0.95, while in powder, the best fitting was found between copper and lead (fig. 4), with a
coefficient of 0.83 and between copper and nickel (fig. 5), with 0.97. The high
correlation coefficients for these metals may suggest the possible substitution between
them, as well as a similarity in mobility and behaviour.
Zn-Pb Zn-Cu

300 7000
250 6000
200 5000
Zn-Pb 4000 Zn-Cu
Pb

150
Cu

3000
100
2000
50
1000
0 0
0 500 1000 1500 0 500 1000 1500
Zn Zn

Fig. 1 Zn-Pb correlation chart. Fig. 2 Zn-Cu correlation chart.

Co-Zn Cu-Pb

1200 300
1000 250
800 Co-Zn 200
Cu-Pb
Zn

Pb

600 150
400 100
200 50
0 0
0 10 20 30 40 0 2000 4000 6000 8000
Co Cu

Fig. 3 Co-Zn correlation chart. Fig. 4 Cu-Pb correlation chart.

C u-Ni Mn-Pb

600
300
500
250
400 200
Cu-Ni Mn-Pb
300
Pb
Ni

150
200 100
100 50
0 0
0 2000 4000 6000 8000 0 1000 2000 3000
Cu Mn

Fig. 5 Cu-Ni correlation chart. Fig. 6 Co-Zn correlation chart.

5
Heavy metal distribution in Balan area
The zonal distribution of heavy metals pointed out some maximum concentration zones
around galleries and dumping sites. Sample 39, which has high contents of every
studied element, is an exception, as there is no record of mining works in the area.
Under these conditions, their presence is easily presumable, but from unknown reasons
(lack of documentation, integration in the layout of the landscape or the development of
Balan town), these works have not been mentioned.
A direct correlation between areas with high concentration in soils and in aqueous
solutions is emphasized, pointing out the migration capacity of the elements taken into
account and, therefore, the extension of the polluted zone outside the vicinity of mining
works.
Although considered an element with low mobility, due to its bonding with organic
matter and clay materials (Mulligan et al, 2001), copper is found in aqueous solutions of
soils from Balan with concentrations between 0,004 and 6,634 ppm. The fact that the
highest amounts outline the town of Balan (Fig 7 and 8) is of great concern, because of
the availability of copper to plants and of the possibility of bioaccumulation in the
human body.
M e d ia s p .
M e d ia s p .

C o v e c i P e t e r C o v e c i P e t e r
S a r a t uS r i i H . S a r a t uS r i i H .
1 2 1 9 . 9a r 1a t u1r 3 0 6 . 0 5 F i e r u l b 1 2 1 9 . 9a r 1a t u 1r 3 0 6 . 0 5 F i e r u l b
ii b . ii b .
. 5 2 . 5 2
5 3 5 3
D l . S o p a r l e lo r D l . S o p a r le l o r
1 0 3ulb7 . 2 . 1 0 3ul b7 . 2 .
lt in
d d
p .S
an
5 1 p .S
an
5 1 l t in
Pa Pa
5 0 H a g h i m a s u l M a r e P . 5 0 H a g h im a s u l M a r e P .
4 9 4 9
1 7 9 3 . 5 1 7 9 3 . 5
O lt
O lt

5 4 S c a u n u l u i I I H . 5 4 S c a u n u l u i I I H .
gul
gul

p .F a
p .F a

S m o c h i n u 1l u 2 i 3 H 2 . . 9 2 S m o c h i n u 1l u 2 i 3 H 2 . . 9 2
1 3 1 4 . 9 1 5 5 1 3 1 4 . 9 1 5 5
D l . S c a u n u l u i D l . S c a u n u l u i
3 0 3 0
S i p o s b . 3 11 1 9 7 . 8 S i p o s b . 3 11 1 9 7 . 8
2 93 2 2 93 2
2 6 2 6
p . R u to c
p . R u to c

2 8 3 3 P ia t r a U n i c a 2 8 3 3 P i a t r a U n ic a
b.
b.

au
au

R u t o c e lo r
b. R u t o c e lo r
b.
rg
g
V ir

caun caun
Vi

1 1 7 2 . 3 3 4 S H a s m a s u l M a r e 1 1 7 2 . 3 3 4 S H a s m a s u l M a r e
ci b.
ci b.

P ia t r a S c 3 r 6i s 3a 5 1 7 0 8 . 2 3 P i a t r a S c 3 r 6i s 3a 5 1 7 0 8 . 2 3
C ova
C ova

1 3 7 6 . 7 5 1 3 7 6 . 7 5
3 7 3 7
4 5
M i
ne
ib B A L A N 4 5
Mi
ne
ib B A L A N
A ra m
. 3 8 A ra
. 3 8
a p. 3 9 m a p. 3 9
4 7 4 7
4 0 4 0
v.
v.

F a g u l C e t a t ii F a g u l C e t a t ii
S im in a
S im in a
Fa

Fa
gu

gu

1 1 2 1 . 9 5 1 1 2 1 . 9 5
lM

lM
V a ra c

V a ra c

4 1 4 2 4 3 4 1 4 2 4 3
u re

u re
s b

s
b.
b.

b.
.

2 0 4 4 1 Ga 2 0 4 4 1 Ga
2 1 lc 2 1 l
1 0 2 4 u t v. . 2 1 0 2 4 c u t v. . 2
1 9 G a l c u t 1 9 G a lc u t
2 2 4 3 2 2 4 3
L E G E N D L E G E N D
.

2 5 2 5
M ic a v

M ic a v

1 8 6 1 8 6
S a m p l e S a m p l e
v.

v.

7 O lt a R o z a H . 7 O l t a R o z a H .
a re
a re
Lunca

Lunca

1 7 1 7
B o r e B o r e
a M
a M

1 6 F5a g u l C i o 1 6 F5a g u l C i
nc
nc

8 b a n u lu i v
. 8 o b a n u lu
i v.
Lu

Lu

G a ll e r y S e d lo
ca v. G a ll e r y S e d lo
ca v.

S h a f t 1 4 5 6 S h a f t 1 4 5 6
1 5 1 5
1 3 1 2 9 5 7 C u r t a v . 1 3 1 2 9 5 7 C u r t a v .
S a n d o
1 0
m in i c S a n d o0 m in i c
1 1 5 8 1 1 1 5 8

Fig. 7 Distribution map of copper in the Fig. 8 Distribution map of copper in

soils of Balan (ppm). soil aqueous solution of Balan (ppm).

Lead is a very toxic and persistent element (Barnea, Caciu, 1979) which easily
accumulates in organisms, causing various health problems. As in the case of copper,
lead is also concentrated in the area of Balan town (fig. 9 and 10), making it dangerous
to consume food grown on these soils, water from the river or from water shafts.

6
 M e d ia s p .

M e d ia s p .
C o v e c i P e t e r C o v e c i P e t e r
S a r a t uS r i i H . S a r a t uS r i i H .
1 2 1 9 . 9a r 1a t u1r 3 0 6 . 0 5 F i e r u l 1 2 1 9 . 9a r 1a t u1r 3 0 6 . 0 5 F i e r u l b
ii b b. ii b .
. 5 2 . 5 2
5 3 5 3
D l. S o p a r l e l o r D l . S o p a r l e l o r
1 0 3 u l b .7 . 2 1 0 3 u l b .7 . 2
d d
p .S
an
5 1 lt in p .S
an
5 1 lt in
Pa Pa
5 0 H a g h i m a s u l M a r e P . 5 0 H a g h i m a s u l M a r e P .
4 9 4 9
1 7 9 3 . 5 1 7 9 3 . 5

O lt

O lt
5 4 S c a u n u l u i I I H . 5 4 S c a u n u l u i I I H .

gul

gul
p .F a

p .F a
S m o c h i n u 1l u 2 i 3 H 2 . . 9 2 S m o c h i n u 1l u 2 i 3 H 2 . . 9 2
1 3 1 4 . 9 1 5 5 1 3 1 4 . 9 1 5 5
D l . S c a u n u l u i D l . S c a u n u l u i
3 0 3 0
S ip o s b . 3 11 1 9 7 . 8 S i p o s b . 3 11 1 9 7 . 8
2 93 2 2 93 2
2 6 2 6
p . R u to c

p . R u to c
2 8 3 3 P i a t r a U n i c a 2 8 3 3 P ia t r a U n ic a
b.

b.
u

u
R u t o c r b. R u t o c r b.

ga
ga

n e lo n e lo

V ir
V ir

1 1 7 2 . 3 3 4 S cau H a s m a s u l M a r e 1 1 7 2 . 3 3 4 Scau H a s m a s u l M a r e

ci b.
ci b.
P i a t r a S c 3 r 6i s 3a 5 1 7 0 8 . 2 3 P ia t r a S c 3 r 6i s 3a 5 1 7 0 8 . 2 3

C ova
C ova
1 3 7 6 . 7 5 1 3 7 6 . 7 5
3 7 3 7
4 5
Mi
ne
i B A L A N 4 5
M i
ne
i B A L A N
A ra
b. 3 8 A ram
b. 3 8
m a
p. 3 9 a p. 3 9
4 7 4 7
4 0 4 0

v.
v.
F a g u l C e t a t ii F a g u l C e t a t i i

S im in a
S im in a

Fa
Fa

gu
1 1 2 1 . 9 5
gu

1 1 2 1 . 9 5

lM
lM

V a ra c
V a ra c

4 1 4 2 4 3 4 1 4 2 4 3

u re
u re

s b
s b

b.
b.

.
.

2 0 4 4 1 Ga 2 0 2 1 4 4 1 Ga
2 1 lc l
1 0 2 4 u t v. . 2 1 0 2 4 c u t v. . 2
1 9 G a l c u t 1 9 G a lc u t
4 3 2 2 4 3
2 2
L E G E N D L E G E N D

.
.

2 5

M ic a v
2 5
M ic a v

1 8 6 1 8 6
S a m p le S a m p le

v.
v.

7 O l t a R o z a H . 7 O l t a R o z a H .

a re
L un ca
a re
Lunca

1 7 1 7
B o r e B o r e

a M
F5a g u l C i
a M

1 6 F5a g u l C i 1 6

nc
8
nc

8 o b a n u lu
iv.
o b a n u lu
i v.

Lu
G a l le r y
Lu

G a ll e r y S e d lo
ca v.
S e d lo
ca v.

S h a f t 1 4 5 6 S h a f t 1 4 5 6
1 5 1 5

1 3 1 2 9 5 7 C u r t a v . 1 3 1 2 9 5 7 C u r t a v .
S a n d o0 m in ic S a n d 1 0
o m in ic
1 1 1 5 8 1 1 5 8

Fig. 9 Distribution map of lead in the Fig. 10 Distribution map of lead in soil
soils of Balan (ppm). aqueous solutions of Balan (ppm).

Lead, copper and zinc, as well as the other studied metals have another high
concentration area, upstream, more obviously outlined in the distribution maps of soil
aqueous solutions around sample no. 49, where many galleries were identified.
M e d ia s p .

M e d ia s p .

C o v e c i P e t e r C o v e c i P e t e r
S a r a t uS r i i H . S a r a t uS r i i H .
1 2 1 9 . 9a r 1a t u1r 3 0 6 . 0 5 F i e r u l b 1 2 1 9 . 9a r 1a t u1r 3 0 6 . 0 5 F i e r u l b
ii b . ii b .
. 5 2 . 5 2
5 3 5 3
D l . S o p a r l e l o r D l. S o p a r le l o r
1 0 3 ul b7 . 2 . 1 0 3ulb7 . 2 .
d d
p .S
an
5 1 l t in p .S
an
5 1 l t in
Pa Pa
5 0 H a g h im a s u l M a r e P . 5 0 H a g h im a s u l M a r e P .
4 9 4 9
1 7 9 3 . 5 1 7 9 3 . 5
l O lt

O lt

5 4 S c a u n u lu i I I H . 5 4 S c a u n u l u i I I H .
gul
gu
p .F a

p .F a

S m o c h i n u 1l u 2 i 3 H 2 . . 9 2 S m o c h i n u l1 u 2 i 3 H 2 . . 9 2
1 3 1 4 . 9 1 5 5 1 3 1 4 . 9 1 5 5
D l . S c a u n u l u i D l . S c a u n u l u i
3 0 3 0
S i p o s b . 3 11 1 9 7 . 8 S i p o s b . 3 11 1 9 7 . 8
2 93 2 2 93 2
2 6 2 6
p . R u to c

p . R u to c

2 8 3 3 P ia t r a U n ic a 2 8 3 3 P i a t r a U n i c a
b.

b.
au

au

R u t o c r b. R u t o c r b.
rg

rg

n e lo n e lo
Vi

Vi

1 1 7 2 . 3 3 4 Scau H a s m a s u l M a r e 1 1 7 2 . 3 3 4 S cau H a s m a s u l M a r e
ci b .

ci b.

P i a t r a S c 3 r 6i s 3a 5 1 7 0 8 . 2 3 P i a t r a S c 3 r 6i s 3a 5 1 7 0 8 . 2 3
C ova

C ova

1 3 7 6 . 7 5 1 3 7 6 . 7 5
3 7 3 7
4 5
Mi
ne
ib B A L A N 4 5
Mi
ne
ib B A L A N
A ra
. 3 8 A ra
. 3 8
m a p. 3 9 m a
p. 3 9
4 7 4 7
4 0 4 0
.

v.
S im in a v

F a g u l C e t a t i i F a g u l C e t a t ii
S im in a
Fa
Fa

gu

1 1 2 1 . 9 5
gu

1 1 2 1 . 9 5
lM
lM

V a ra c
V a ra c

4 1 4 2 4 3 4 1 4 2 4 3
u re
u re

s b
s b

b.
b.

.
.

2 0 4 4 1 Ga 2 0 2 1 4 4 1 Ga
2 1 lc l
1 0 2 4 u t v. . 2 1 0 2 4 c u t .v . 2
1 9 G a l c u t 1 9 G a lc u t
2 2 4 3 2 2 4 3
L E G E N D L E G E N D
.
.

2 5 2 5
M ic a v
M ic a v

1 8 6 1 8 6
S a m p le S a m p le
v.
v.

7 O l t a R o z a H . 7 O l t a R o z a H .
a re
a re

Lunca
Lunca

1 7 1 7
B o r e B o r e
a M
a M

1 6 F5a g u l C i 1 6 F5a g u l C i
nc

8
nc

8 o b a n u lu
i v.
o b a n u lu
i v.
Lu
Lu

G a ll e r y S e d lo
ca v. G a ll e r y S e d lo
ca v.

S h a f t 1 4 5 6 S h a f t 1 4 5 6
1 5 1 5

1 3 1 2 9 5 7 C u r t a v . 1 3 1 2 9 5 7 C u r t a v .
S a n d o m in i c S a n d 1
o0 m in ic
1 1 1 0 5 8 1 1 5 8

Fig. 11 Distribution map of zinc in the Fig. 12 Distribution map of zinc in soil
soils of Balan (ppm). aqueous solutions of Balan (ppm).
Conclusions
Soil investigation in the area of Balan has pointed out the presence of heavy metals with
significant concentrations, which frequently surpass normal values, admitted by
Romanian laws.
Zonal distribution of heavy metals outlines concentration areas downstream Olt river or
in the localities of Balan and Sandominic, which indicates the possible existence and
migration of heavy metals towards inhabited areas.
The extension of heavy metal influence and, therefore, of pollution in Balan mining
perimeter is caused not only by natural phenomena (leaching and natural transportation
because of underground water), but also by anthropic activities: using dumped material
to repair local roads in the area, precarious preservation of mining dumps, galleries and
Lunca Mare settling pond and absence of protection means for river Olt.

Acknowledgements
This research paper would not have been possible without the support of the
GEOECOLAB team from the Geological Survey of Romania. The author wishes to
express her gratitude to her supervisor, Dr. Lucia Robu who was abundantly helpful and
offered invaluable assistance, support and guidance.

References
Barnea M., Caciu Al. (1979) – Ecologie umana, Editura Medicala, Bucuresti.
Decision no. 188/2002 issued by the Ministry of Environment and Water Management
of Romania.
Kräutner H.G., Udrescu C., Gaftoi G. (1992) – Sulfur isotopes and trace elements in
copper ores and pyritic schists from Balan (East Carpathians), Rom. J. Mineral
Deposits, p. 1-29, Bucuresti.
Kräutner H.G., Bindea G. (1995) – The Ditrău alcaline intrusive complex and its
geological environment. Rom J. Of Mineralogy, vol.77, Supplement nr.3, Bucureşti.
Kräutner H.G., Popa Gh. (1969) – Studii geologice preliminare asupra zăcământului
Bălan. Raport. Arhiva I.G.R., Bucureşti.
Mulligan C.N., Yong R.N., Gibbs B.F. (2001) – Remediation technologies for metal-
contaminated soils and groundwater: an evaluation, Engineering Geology, vol 60, p.
193-207.
Order no. 756/1997 issued by the Ministry of Waters, Forests and Environmental
Protection of Romania.
Petrulian N., Steclaci L., Orloveanu Fl. (1971) – Studiul mineralogic al minereului de la
Balan St. Cer. Geol. Geogr., Geol., XVI, 2, p. 343-353, Bucuresti.