Int. J. Mol. Sci. 2008, 9, 434-453 [600710]

Int. J. Mol. Sci. 2008, 9, 434-453
International Journal of
Molecular Sciences
ISSN 1422-0067
© 2008 by MDPI
www.mdpi.org/ijms/
Full Research Paper
Analysis of Soil Heavy Metal Pollution and Pattern in Central
Transylvania
Ioan Suciu 1, Constantin Cosma 1, Mihai Todic ă 1, Sorana D. Bolboacă 2,* and Lorentz Jäntschi 3
1 Babes Bolyai University, Faculty of Physics, 1st M. Kogalniceanu, 400084 Cluj-Napoca, Romania
E-mails: [anonimizat]; [anonimizat]; [anonimizat]
2 “Iuliu Ha țieganu” University of Medicine and Pharmacy Cluj-Napoca, 6 Louis Pasteur, 400349
Cluj-Napoca, Romania. E-mail: [anonimizat]
3 Technical University of Cluj-Napoca, 103-105 Muncii Bvd, 400641 Cluj-Napoca, Romania
E-mail: [anonimizat]
* Author to whom correspondence should be addressed.
Received: 28 January 2008; in revised form: 29 March 2008 / Accepted: 31 March 2008 /
Published: 2 April 2008

Abstract: The concentration of five soil heavy metals (Pb, Co, Cr, Cu, Hg) was measured in
forty sampling sites in central Transylvania, Romania, regions known as centres of pollution
due to the chemical and metallurgical activ ities. The soil samples were collected from
locations where the ground is not sliding and the probability of alluvial deposits is small.
The concentration of heavy metals was measured by using the Inductively Coupled Plasma Spectrometry method. Data were verified by us ing the Neutron Activation Analysis method.
In some locations, the concentration for th e investigated heavy metals exceeds the
concentration admitted by the Romanian guideline. The highest concentration of lead (1521.8 ppm) and copper (1197.6 ppm) was found in Zlatna. The highest concentration of
chromium was found in Târn ăveni (1080 ppm). The maximum admitted concentrations in
the sensitive areas revealed to be exceed from five to forty times.
Keywords: Soil pollutant, Heavy metals (Co, Cr, Cu, Pb, Hg), Central Transylvania.
List of abbreviations: NAA = Neutron Activation Analys is; ICP = Inductively Coupled
Plasma Spectrometry; RSV = Reference Value in the Sensitive Area; ALS = Alert Level in
the Sensitive Area; RVLS = Reference Value in the Less Sensitive Area; ALLS = Alert
Level in the Less Sensitive Area; AIT = Area Intervention Threshold.

Int. J. Mol. Sci. 2008, 9 435

1. Introduction
Heavy metal contamination of soil results from anthropogenic such as mining [1], smelting
procedures [2] and agriculture [3] as well as natu ral activities. Chemical and metallurgical industries
are the most important sources of heavy metals in the environment [4].
The metals are classified as “heavy metals” if in th eir standard state they have a specific gravity of
more than 5 g/cm3. There are known sixty heavy metals. Heavy metals get accumulated in time in soils
and plants and could have a negative influe nce on physiological activities of plants (e.g.
photosynthesis, gaseous exchange, and nutrient ab sorption), determining the reductions in plant
growth, dry matter accumulation and yield [5,6]. In small concentrations, the traces of the heavy
metals in plants or animals are not toxic [7]. Lead, cadmium and mercury are exceptions; they are
toxic even in very low concentrations [8].
Every 1000 kg of “normal soil” contains 200 g chromium, 80 g nickel, 16 g lead, 0.5 g mercury
and 0.2 g cadmium, theoretically [9]. Monitoring the endangerment of soil with heavy metals is of interest due to their influence on groundwater and surface water [10,11,12] and also on plants
[13,14,15], animals and humans [16,17,18].
The main goal of the present research was to assess the heavy metals distribution in some
Transylvanian areas, known as mining, chemical or metallurgy industry centres. The comparison of the
soil heavy metal concentrations with the maximu m value admitted by the Romanian guideline [19,20]
has also been made.
2. Experimental Section
2.1. Studied Areas
Four areas near to the Romanian towns known as important pollution centres (Târn ăveni area –
Mureș County, Copș a Mică – Sibiu County, Zlatna – Alba Count y, and Câmpia Turzii – Cluj County)
were choose to be included into the study (Figure 1, from Google Earth
1).
The main characteristics of the pollution centres included into analysis were as follows:
o Tărnâveni, situated on the Târnava Mica River, an important chemical industry centre. To date, the
acetylene is the only product of the chemical indus try, but the previous activities must also be
considered. Nitrogen S.A. factory was built in 1916 and the main chemical produced were
mercury, gold, bismuth, barium salts, copper su lphate, sodium and potassium dichromate,
sulphuric acid. The soil structure in the area is [21]: brown and black earth, pseudoredzinic soils,
and hayfield black earth, regosoils, clay soils and alluvial soils (the last areas types were not
included into analysis). These types of soil ha d medium or reduced pollution vulnerability, which
allows to obtained accurate long-term soil pollution information [22].
o Copșa Mică, situated on the Târnava Mare River, the most polluted area in the Sibiu County, was
classified as an environmental disaster area2. The town is best known in Europe for its status (in
the 1990s) as one of the most polluted in Europe2. The S.C. Sometra S.A., a non-ferrous
metallurgical factory, is the main industry re sponsible by the pollution. The emissions coming
from the others economic agents from the industrial platform of Media ș city (S.C. Emailul, S.C.
Vitrometan, and S.C. Geromed) is add to the pollution in this area.

Int. J. Mol. Sci. 2008, 9 436

Figure 1. Geographic areas included into the study.
o Zlatna, a west Carpathians mining region, particularly known due to its old polymetallic ores
processing enterprises. Zlatna town is known as of the top 10 pollution ‘hot spots’ in Romania [23]. The primary and secondary metallic sulphi des are concentrated by floating technology, and
metals are extracted trough smelting procedures. Th e town is also a chemical centre preparing
different mineral salts. The soil structures in the area consist of cambiosoils, luvisoils and
regosoils, with high and moderate vulnerability to the pollution. Due to the pollutant industries in
Zlatna, the mean annual atmospheri c emissions were of 150 450 tones SO
2 and 3498 tones dust
laden with Pb, Zn, Cu, Cd, Sb, Bi and As in 1993 [24]. These values were of 41 000 tones SO 2 and
2715 tones dust (Pb: 44%, Zn: 26%, Cu: 21%) on res earch reported by Clepan in 1999 [25]. It is
known that Zlatna soil (around the industrial complex) is loaded with Pb, Cu, Zn and Cd at content
levels exceeding up the maximum allowable limits [26].
o Câmpia Turzii, situated on the inferior course of the Arie ș River, in the proximity of the Turda city,
in an area where the brown soils prevail. The I ndustria Sârmei S.A. is the main economic agent
(one of the biggest metallurgical units in Roma nia, manufacturing 41% of the production of wire
drawing with a low concentration of carbon). Ot her two important contributors are CERCOM S.A.
(ceramic products), and Chemical Inde pendent Group S.A. (chemical industry).
To date, there are no surveys referring to the pollu tion generated in the city’s neighbouring area of
above cities and areas even if it is known that are important polluting centre.
2.2. Sampling
Nine locations (see Table 1) were investigated on each region included into the study.

Int. J. Mol. Sci. 2008, 9 437

Table 1. Regions and locations: characteristics.
Zone Location Latitude
(North) Longitude (East) Elevation1 N (km) E (km)
Târnăveni
Ref:
46°17' N 24°15' E 1 46°20'13.94" 24°16'13.01" 403 5.988 1.563
2 46°19'13.09" 24°21'29.84" 332 4.109 8.345 3 46°19'41.91" 24°17'31.27" 281 4.999 3.238 4 46°20'02.78" 24°19'49.96" 287 5.644 6.207 5 46°17'48.50" 24°20'02.00" 326 1.498 6.465 6 46°19'18.16" 24°18'17.72" 294 4.266 4.233 7 46°17'34.68" 24°18'13.16" 325 1.071 4.135 8 46°17'10.77" 24°15'29.50" 330 0.333 0.632 9 46°18'02.94" 24°15'00.72" 322 1.943 0.015
Copșa Mică
Ref: 46°06' N 24°15' E 1 46°08'16.05" 24°17'37.87" 286 4.201 3.391
2 46°07'32.26" 24°20'16.10" 349 2.849 6.789 3 46°06'38.43" 24°14'04.82" 317 1.187 1.185 4 46°08'22.61" 24°15'21.76" 377 4.403 0.467 5 46°09'34.44" 24°15'08.67" 474 6.621 0.186 6 46°09'03.63" 24°18'18.41" 363 5.670 4.262 7 46°08'25.32" 24°20'06.61" 327 4.487 6.586 8 46°06'59.27" 24°21'34.77" 383 1.830 8.479 9 46°07'30.31" 24°18'16.87" 322 2.788 4.229
Zlatna Ref: 46°06' N 23°08' E 1 46°06'32.83" 23°14'01.57" 421 1.014 7.766
2 46°08'08.66" 23°12'45.21" 515 3.973 6.126 3 46°09'03.60" 23°09'19.42" 674 5.669 1.706 4 46°07'53.77" 23°08'42.37" 782 3.513 0.910 5 46°07'03.28" 23°15'14.32" 553 1.954 9.329 6 46°10'09.39" 23°11'09.13" 656 7.700 4.062 7 46°09'35.07" 23°13'46.11" 882 6.641 7.434 8 46°07'53.57" 23°14'13.97" 607 3.507 8.032 9 46°07'19.33" 23°11'09.90" 599 2.449 4.079
Câmpia Turzii Ref: 46°31' N 23°50' E 1 46°32'06.28" 23°54'59.37" 403 2.047 6.381
2 46°33'00.87" 23°53'18.69" 332 3.732 4.235 3 46°33'16.77" 23°52'53.84" 281 4.223 3.706 4 46°33'15.08" 23°50'27.53" 287 4.171 0.587 5 46°34'13.25" 23°50'55.82" 326 5.967 1.190 6 46°33'29.86" 23°52'18.40" 294 4.627 2.950 7 46°33'35.13" 23°55'33.63" 325 4.790 7.112 8 46°31'59.73" 23°50'51.47" 330 1.844 1.097 9 46°32'21.87" 23°52'38.98" 322 2.528 3.389

Int. J. Mol. Sci. 2008, 9 438

The location from where the soil samples were collected accomplished the following criteria:
o The absence of both ground sliding and existence of alluvial
o Samples of soil from the area situated near to the industrial platform (~ 2 km) [27]
o Samples of soil from the area situated at a distance up to 10 km from the industrial platform [27]
The steps applied for sampling was as follow:
o Step 1: Holes with an area of 40×50 cm were dug
o Step 2: Soil samples were took from depths of 5 cm, 15 cm and 25 cm
o Step 3: The soil samples were put in polyethylen e containers previously treated with a molar
solution of hydrochloric acid and rinsed with distilled water [28]. Whenever was possible the
determinations were made with up to 1ppb accuracy [29].
o Step 4: The samples were sifted and homogenized after drying. They were labelled and separated,
being prepared for analysis. Portions of samples were prepared to determine the concentration by
NAA (Neutron Activation Analysis) and ICP spectrometry (Inductively Coupled Plasma
Spectrometry). The determinations were made at the Institute for Nuclear Research Pite ști (NAA)
and at the EXPROGAZ Media ș (ICP).
o Step 5: NAA (Neutron Activation Analysis) determin ation. Samples of 70 mg were used for this
determination. These were irradiated in the pneum atic mail of the TRIGA reactor. The irradiation
time was from 1.5 up to 2 hours. The following data were collected: (1) the flow of the thermal neutrons (E < 0.5 eV) = 4.7·10
12 n/cm2/s; (2) the cadmium ratio: RCd = 1.8; (3) the thermal
flow/epithermal flow ratio ≈ 10. The measuring of the activ ity has been made with a γ spectrometer
chain of high resolution with an HpGe detector having a relative efficiency of 20%. The time of
measurement ranged within 3000s and 12000s. The m easurements started after the cooling of Na24,
isotope whose halving time is 15 hours. The con centration was determined by means of the KO
method with a Zr monitor; a method whose detection limits varies between 3 and 5 ppm. The obtained data were processed with the GENIE 2000 software
3 and the results were compared with
the values on standard samples (SRM) [30] (see Table 2).
Table 2. Romanian guideline on the admitted concentrations of the heavy metals in soil [19].
Element RVS (ppm) ALS (ppm) RVLS (ppm) ALLS (ppm) AIT (ppm)
Co 15 30 50 100 250
Cr 30 100 300 300 600
Cu 20 100 200 250 500
Hg 0.1 1 2 4 10
Pb 20 50 100 250 1000
RSV = Reference value in the sensitive area
ALS = Alert level in the sensitive area RVLS = Reference value in the less sensitive area ALLS = Alert level in the less sensitive area AIT = Area intervention threshold

o Step 6: ICP (Inductively Coupled Plasma Spectrome try) determination. On the samples of 250 mg
was added 3 ml of HNO 3 65% and 3 ml of HF 40% for these determinations. The obtained mixture
was introduced in a microwave oven and disintegra ted. After the digestion, it was introduced in a
glass bubble and completed with distilled water up to 50 ml. The solution was placed in a plasma

Int. J. Mol. Sci. 2008, 9 439

jet by means of a peristaltic pump, with 8 rolls and 3 channels. The maximum speed of 200
rotations/minute controlled by the computer was applied. An ultrasonic Cross-flow Babington IRIS ADVANTAGE spectrometer and an Echell-type cro ss-dispersion spectrograph was used, covering
a spectra interval of 178 – 800 nm. The system resolution ranged from < 0.01 nm to < 200 nm to <
0.03 to 600 nm. The CID 38196 mm
2 detector with 262144 grouped individual detectors into a
512×512 matrix, cooled with a two-step heat cha nger allowing on integration with a random access
was used. The source of plasma rousing with th e frequency of 27.12 MHz, controlled by the crystal
can supply a power of 750-1750 W, in 6 steps, controlled by the computer. The obtained data were processed in a first stage with the Thermo s SPEC/CID soft. The library of 20000 lines, all-
accessible in at least one order/degree of diffracti on, gives the possibility to obtain the image of the
whole spectra and a complete iden tification of the peaks. The detection limits ranged from 1ppm to
1 ppb, as follows: Cu, Co, Hg < 1 ppb, Hg < 10 ppb.
The same researcher in all locations extracted th e soil samples. The same person made the IPC and
NAA determinations. Due to the limited financial res ources there was not possible to carry out more
than one determination for a given depth and a give location. Thus, the uncertainty of measurements [31,32] was not possible to be determined.
3. Results and Discussion
One hundred and eight soil samples from a total surface of 4800 km
2 were collected and analyzed.
The results are presented according with the name of the studied areas.
3.1. Târnăveni area
The concentration of four heavy metals (Co, Cr, Cu, and Hg) was identified and quantified by using
ICP and/or NAA in 9 locations situated in Târn ăveni region (Table 3). The lead was the heavy metal
not identified in Târn ăveni area.
The surface plot representations of identified metals are presented in Figure 2 – 4.

10

Colour Range (ppm)
0-7
7-14
14-21
21-28
28-35
35-42
42-49
49-56
Reference (0,0):
46°17' N 24°15' E Distances: km 0
0 10
Figure 2. Co maximum surface levels (depth = 5..25 cm): Târn ăveni area.

Int. J. Mol. Sci. 2008, 9 440

Table 3. Heavy metals concentrations in soil samples: Târn ăveni area.
Location
Depth (cm) Element
Co (ppm) Cr (ppm) Cu (ppm) Hg (ppm)
1 5 31.30 363.00 16.40 n.p.
15 41.00 245.00 6.42 n.p.
25 29.00 168.00 45.70 1.20
2 5 n.p. 281.00 24.30 n.p.
15 11.40 122.00 17.00 n.p. 25 n.p. 71.00 51.60 n.p.
3 5 42.00 1046.00 24.96 n.p.
15 48.20 1080.00 72.80 5.52 25 10.30 1012.00 49.90 0.96
4 5 n.p. 90.00 10.30 n.p.
15 1.60 102.00 16.00 n.p. 25 n.p. 87.00 25.30 n.p.
5 5 n.p. 512.00 1.28 n.p.
15 n.p. 384.00 14.96 n.p. 25 18.20 85.80 22.00 n.p.
6 5 10.30 632.00 19.20 n.p.
15 10.40 580.00 41.40 n.p. 25 16.60 614.00 36.00 0.30
7 5 11.80 348.00 19.60 n.p.
15 9.60 274.00 39.10 n.p. 25 15.00 259.00 52.00 n.p.
8 5 14.80 98.90 16.70 n.p.
15 25.50 140.00 30.40 n.p. 25 n.p. 81.00 26.05 n.p.
9 5 11.00 270.00 14.72 n.p.
15 8.2. 311.00 18.00 n.p. 25 n.p. 251.00 20.90 n.p.
n.p. = not present

Most of the higher concentrations of id entified soil metals were found in the 3rd location. These
concentrations were over the intervention level. Note that the 3rd location is situated near de Chemical
Platform where chemical fertilisers, carbide, ba sic inorganic chemicals, anti-pests are produced.
The concentration of Co at a depth of 5 and 15 cm in the soil exceeds the ALS in 1st (Figure 5) and
3rd location. The maximum value of 48.2 ppm was found at 15 cm depth in the 3rd location that is
situated near the Chemical Platform. It may be noticed that the absolute error as regards the
determiners through ICP varies from 0.1 to 1.6 ppm while for NAA determiners the absolute error
varies from 1.2 to 2 ppm.

Int. J. Mol. Sci. 2008, 9 441

10

Colour Range (ppm)
0-131
131-262
262-393
393-524
524-655
655-786
786-917
917-1048
Reference (0,0):
46°17' N 24°15' E Distances: Km 0
0 10
Figure 3. Cr surface levels (depth = 5 cm): Târn ăveni area.

10

Colour Range (ppm)
0-4
4-8
8-12
12-16
16-20
20-24
24-28
28-32
Reference (0,0): 46°17' N 24°15' E Distances: km 0
0 10
Figure 4. Cu surface levels (depth = 5 cm): Târn ăveni.
At 6 km east from the Chemical Platform (the 5th location), just the concentration of Cu was found
to be within limits, and did not exceed the ALLS level.
The Cr concentration exceeds eleven times the AL S (Table 3, Figure 6) while the quick silver
exceeds 5 times the ALS. These exceeding were noticed in the proximity of the chemical platform and
of the warehouse where waste products coming from the chemical plateau are found.
The correlation matrix applied on the experimental data showed that is was no strong correlation
between any groups of elements. The highest con centration of 0.64 was obtained for the couple Cu-
Hg, followed by Cr-Hg (r = 0.52, where r = Pearson correlation coefficient). For these values,
according with Colton’s classification of correlation coefficient [33] it can be say that there is a
moderate correlation between concentrations of those metals in investigated soil.

Int. J. Mol. Sci. 2008, 9 442

5 15 25
depth (cm) 01224364860concentration (ppm) ICP
NAA

Figure 5. Co concentration in Târn ăveni area (1st location): NAA vs. ICP

Figure 6. Cr concentration in Târn ăveni area (1st location): ICP vs. NAA
It was identified a weak relationship between th e following heavy metals couples: Co-Cr (r = 0.45),
and Cr-Cu (r = 0.38). No correlation was identified on the following two couples of heavy metals: Co-
Cu (r = 0.29), and Co-Hg (r = -0.05). The results obtai ned were in accordance with previously reported
results [34,35]. The distance between the investigated location and the Chemical Platform revealed to
be important element that leads to these results in investigated metals.
3.2. Copș a Mică area
In the area of Cop șa Mică was not detected the presence of Co and Hg in the investigated soil
samples. The concentrations of the metals measured by using the ICP method are presented in Table 4.
The surface plots for the identified heavy metals are presented in Figure 7 – 9.
The analysis of the concentrations presented in Table 4 revealed that the concentration of Co
slightly exceeded the ALS.
The concentration of Cr was within the normal limits. The lead concentrations revealed to exceed by 14 times the ALS. A spatial distribution of Pb in
Copșa Mică area at 5 cm depth was obtained and it is presented in Figure 9.

Int. J. Mol. Sci. 2008, 9 443

The correlation matrix of investigate heavy meta ls shown that a moderate correlation existed
between soil Cr and Pb concentration (r = 0.54). A weak relationship was identified for the following
couple of soil heavy metals: Cu-Pd (r = 0.44) and Cr-Cu (r = 0.32).
Table 4. Heavy metal concentrations in soil samples: Cop șa Mică area.
Location
Depth (cm) Element
Cu (ppm) Cr (ppm) Pb (ppm)
1 5 52.30 103.98 761.20
15 140.48 77.86 631.40
25 149.76 79.40 598.10
2 5 63.10 81.00 480.30
15 132.00 83.40 524.00
25 140.60 74.00 353.11
3 5 72.16 96.40 304.60
15 48.40 83.10 250.00 25 56.80 60.00 89.40
4 5 93.70 100.72 132.72
15 126.31 66.90 253.20 25 48.70 79.94 213.60
5 5 31.20 55.20 36.20
15 40.03 50.10 31.40 25 29.60 39.40 28.60
6 5 73.40 104.00 460.02
15 71.00 100.00 268.30 25 71.70 87.30 143.61
7 5 56.44 66.56 687.40
15 54.94 67.54 288.40 25 32.24 60.76 104.40
8 5 52.03 42.00 46.36
15 44.00 41.40 107.22 25 38.10 45.00 83.72
9 5 86.00 123.00 623.14
15 57.00 98.70 248.32 25 78.10 101.20 123.04

Int. J. Mol. Sci. 2008, 9 444

10

Colour Range (ppm)
0-12
12-24
24-36
36-48
48-60
60-72
72-84
84-96
Reference (0,0):
46°06' N 24°15' E Distances: km
0
0 10
Figure 7. Cu surface levels (depth = 5cm): Cop șa Mică area.

10

Colour Range (ppm)
0-16
16-32
32-48
48-64
64-80
80-96
96-112
112-128
Reference (0,0): 46°06' N 24°15' E Distances: km 0
0 10
Figure 8. Cr surface levels (depth = 5 cm): Cop șa Mică area.

The non-ferrous metalworking and chemical proce ssing plants from this area proved to have a
devastative effect on the environment that is still pres ent even if the pollutant facilities were forced to
close in 1993.

Int. J. Mol. Sci. 2008, 9 445

10

Colour Range (ppm)
0-96
96-192
192-288
288-384
384-480
480-576
576-672
672-768
Reference (0,0):
46°06' N 24°15' E Distances: km 0
0 10
Figure 9. Pb surface levels (depth = 5 cm): Copș a Mică area.
3.3. Zlatna
Four (Co, Cr, Cu, and Pb) out of five heavy metals were identified and their concentrations in soil at
3 depths were measured. The concentrations obtained by using the ICP method are presented in
Table 5.
The graphical representations of identified heavy me tal concentrations on this area are presented in
Figure 10 – 13.

10

Colour Range (ppm)
0-8
8-16
16-24
24-32
32-40
40-48
48-56
56-64
Reference (0,0):
46°06' N 23°08' E Distances: km 0
0 10
Figure 10. Cr surface levels (depth = 5cm): Zlatna area.

Int. J. Mol. Sci. 2008, 9 446

Table 5. Heavy metal concentrations in soil samples: Zlatna area.
Location Depth (cm) Element
Co (ppm) Cr (ppm) Cu (ppm) Pb (ppm)
1 5 n.p. 4.74 3954.00 1537.00
15 n.p. 35.86 1197.60 854.00
25 n.p. 35.64 974.80 1521.80
2 5 n.p. 41.42 193.04 n.p.
15 79.30 49.06 131.38 8.14
25 n.p. 30.94 41.84 263.00
3 5 n.p. 36.21 74.30 n.p.
15 n.p. 39.80 56.20 n.p. 25 n.p. 21.16 60.14 241.00
4 5 n.p. 30.06 19.40 n.p.
15 n.p. 40.14 36.40 n.p. 25 n.p. 30.14 20.70 n.p.
5 5 n.p. 58.88 843.40 n.p.
15 49.30 60.22 914.10 348.00 25 n.p. 67.30 722.00 293.00
6 5 n.p. 49.30 93.02 n.p.
15 n.p. 51.40 41.30 n.p. 25 n.p. 58.12 44.60 193.00
7 5 n.p. 36.70 18.70 n.p.
15 n.p. 48.20 46.32 n.p. 25 n.p. 50.04 30.70 143.00
8 5 n.p. 61.30 439.20 n.p.
15 54.30 67.20 512.10 983.20 25 17.10 37.15 376.40 3.06
9 5 n.p. 57.60 86.01 n.p.
15 n.p. 36.90 78.36 n.p. 25 n.p. 18.60 71.44 167.80
n.p. = not present

The quick silver was not detected at Zlatna area (see Table 5). Important exceeding in the
concentration of Cu, Pb and Co was found in this ar ea. Co was identified just in three out of nine
locations with up to 2.6 times exceed ALS (Table 5).
The lead and copper concentrations exceed in all lo cations the ALS. The Pb concentrations in the
soil samples exceeds up to 30 times the ALS level, while the Cu exceeds up to 40 times the ALS level (Table 5).

Int. J. Mol. Sci. 2008, 9 447

10

Colour Range (ppm)
0-495
495-990
990-1485
1485-1980
1980-2475
2475-2970
2970-3465
3465-3960
Reference (0,0):
46°06' N 23°08' E Distances: km 0
0 10
Figure 11. Cu surface levels (depth = 5 cm): Zlatna area.

10

Colour Range (ppm)
0-220
220-440
440-660
660-880
880-1100
1100-1320
1320-1540
Reference (0,0): 46°06' N 23°08' E Distances: km
0
0 10
Figure 12. Pb maximum surface levels (depth = 5..25 cm): Zlatna area.
The correlation matrix was applied to identify and quantify the relationship between couple of
investigated heavy metals. The results revealed that there exist:
o A good positive relationship between soil concentrations of Cu and Pb (r = 0.76)
o An acceptable degree of association between so il concentrations of Co and Cr (positive
relationship, r = 0.35), between Cr and Cu (negative relationship, r = – 0.32), and between Cr and Pb (negative relationship, r = – 0.26)
o No relationships between the following couple of heavy metals: Co-Cu (r = 0.01), and Co-Pb (r = –
0.06).
The high concentrations of heavy metals in the supe rior strata suggest that the polluting activity was
recently stopped.

Int. J. Mol. Sci. 2008, 9 448

10

Colour Range (ppm)
0-40
40-80
Reference (0,0):
46°06' N 23°08' E Distances: km
0
0 10
Figure 13. Co maximum surface levels (depth = 5..25 cm): Zlatna area.
3.4. Câmpia Turzii area
Câmpia Turzii can be considered the least pollute d area from the investigated zones. Three heavy
metals were identified and their concentrations in soil were quantified.
The results expressed as concentrations determined by using ICP are presented in Table 6.
The graphical representations of identified heavy me tal concentrations on this area are presented in
Figure 14 – 16.
The lead concentration exceeded 16 times the ALS (see Table 6). Spatial distribution of maximum
Pb soil concentration in Câmpia Turzii area is presented in Figure 14.
10

Colour Range (ppm)
0-218
218-436
436-654
654-872
Reference (0,0):
46°31' N 23°50' E Distances: km
0
0 10
Figure 14. Pb maximum surface levels (depth = 5..25 cm): Câmpia Turzii area.

Int. J. Mol. Sci. 2008, 9 449

Table 6. Heavy metal concentrations in soil samples: Câmpia Turzii area.
Location Depth (cm) Element
Cu (ppm) Cr (ppm) Pb (ppm)
1 5 38.54 40.62 n.p.
15 52.84 39.18 n.p.
25 48.28 43.72 n.p.
2 5 39.14 49.60 n.p.
15 41.60 51.20 n.p.
25 53.90 30.00 868.60
3 5 49.72 61.70 n.p.
15 49.70 53.28 735.00 25 46.72 51.26 837.20
4 5 31.60 29.70 n.p.
15 28.20 36.20 n.p. 25 15.70 42.11 27.00
5 5 46.19 36.18 n.p.
15 48.70 29.70 n.p. 25 41.30 20.30 n.p.
6 5 63.20 48.12 247.00
15 59.14 40.77 374.60 25 38.60 36.50 n.p.
7 5 42.90 41.20 n.p.
15 49.00 35.60 n.p. 25 33.70 29.80 n.p.
8 5 36.10 59.30 n.p.
15 40.12 62.40 n.p. 25 29.70 37.67 n.p.
9 5 56.24 43.28 n.p.
15 59.80 47.88 n.p. 25 51.28 41.44 69.00
n.p. = not present

The analysis of the correlation matrix of investigated heavy metals revealed that there is a degree of
association between Cu and Pb concentrations in soil (r = 0.33). It was not identified any association
between concentration in soil of Cr and Pb (r = 0.08) or between Cr and Cu (0.14).
4. Concluding Remarks
The presence of Cu, Co, Pb and Hg were determin ed in most of the investigated areas. Some
exceeding at the alert level was identified in the sens itive areas (agricultural ar eas). The results of the
study can lead to an image of the historical po llution, determining the concentration of several
elements, according to the depths in the soil.
Different correlation rapports were identified in different areas. The maximum correlation
coefficient was found between Cu and Pb, in Zlat na area. A negative correlation coefficient was
obtained between Hg and Co, in Târn ăveni area, and between Pb and Co, Pb and Cr, and Cu and Cr, in

Int. J. Mol. Sci. 2008, 9 450

Zlatna area. These observations may suggest a differe nt geochemical behaviour of the studied elements
in sediments and exemplify the complexity of the effects in the industrial systems [36].

10

Colour Range (ppm)
0-8
8-16
16-24
24-32
32-40
40-48
48-56
56-64
Reference (0,0):
46°31' N 23°50' E Distances: km 0
0 10
Figure 15. Cu surface levels (depth = 5 cm): Câmpia Turzii area.

10

Colour Range (ppm)
0-8
8-16
16-24
24-32
32-40
40-48
48-56
56-64
Reference (0,0): 46°31' N 23°50' E Distances: km 0
0 10
Figure 16. Cr surface levels (depth = 5 cm): Câmpia Turzii area.

The greatest excess for chromium was registered in Târn ăveni, for lead in Cop șa Mică and for
copper in Zlatna. The concentrations of studied hea vy metals in the areas near the chemical yard of
BICAPA, SOMETRA, INDUSTRIA SARMEI and AMPELUM companies exceeds the intervention threshold, and sometime the area intervention threshold.
Mercury’s presence was identified in some areas having concentrations that exceed 5.5 times the
intervention level.

Int. J. Mol. Sci. 2008, 9 451

Excepting the Zlatna area, the copper concentration ranges within normal limits.
The differences registered between ICP and NAA method can be explained by the existence of
several detection limits and by the problems connected to the homogeneity of solid samples.
The choice of locations for measures is very im portant. The measurement of the concentration in
air, in running waters or of the accumulations of chemical elements in lichens, provides data on the time of measurements or in a brief period of time [37]. Unlike th e method of studying the
accumulations in lichens [38], the method of direct study of element concentration in soil eliminates
the necessity of a reference batch and the corrections are not necessary.
The presence of heavy metals not detected in the supe rior strata of soils allows us to conclude that
the pollution was produced a long time ago and the pollu tant activities in the investigated areas were
discard.
Acknowledgment
The research was partly supported by the UEFISCSU Romania through research grants.
Notes
1 Wikipedia. [viewed: January 27, 2008]. Availabl e from: http://en.wikipedia.org/wiki/Copsa_Mica
2 Google Earth. ©2007 Google [viewed: January 27, 2008]. Available from: http://earth.google.com
3 Genie – soft. © Genie-Soft Corporation 2001-2008. [viewed: January 23, 20008]. Available from:
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