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Assessment of heavy metal in

water and sediments of the
Danube River

Article in Journal of environmental protection and ecology November 2014

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Mihaela Ilie
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Journal of Environmental Protection and Ecology 15, No 3, 825833 (2014)

Water pollution

Assessment of Heavy Metal in Water and Sediments

of the Danube River

M. Ilie*, F. Marinescu, G. Ghita, Gy. Deak, G. S. Tanase,

M. Raischi
National Institute for Research and Development in Environmental Protection,
294 Spl. Independentei Street, 6th District, 060 031 Bucharest, Romania
E-mail: mihaela.ilie@incdpm.ro; elailie@yahoo.com

Abstract. The Danube river, the most important European river serves as a resource for various
water uses and, therefore, environmental quality of the Danube river basin is under great pressure
from a diverse range of human activities. Although water is usually employed as a pollution indicator
by trace metals, sediments are also considered to be important in the assessment of anthropogenic
impacts. In this study, water and sediment samples were analysed for assessment of heavy metal
pollution status in the Danube river, with a view to determine its ability to sustain aquatic life. Four
sites were sampled along the Danube river between 347 km and 333 km during 20112013. Water
and bottom sediment samples were collected monthly from both left and right banks of the Danube
and samples were analysed for 6 trace metals: Cd, Pb, Ni, Cu, Cr, and Zn, by AAS techniques. Lower
concentrations than first quality class limits of the European Water Framework Directive 2000/60/
EC and Romanian law (161/2006) for heavy metals were found for water samples and higher
concentrations were found in sediments for Ni, Cu and Zn. The metal concentrations in sediments
(in mg/kg) ranged as follows: Ni between 11.93 and 93.52; Cu between 7.24 and 86.52 and
Zn between 32.05 and 206.99. Based on Water Directive 2000/60/EC limits, the results indicate
a long-term pollution for Ni, Cu and Zn in the river sediments which could be of concern for the
health of the aquatic ecosystem.
Keywords: river sediments, the Danube river, heavy metal, pollution status, water quality.

AIMS AND BACKGROUND

The Danube river, the most important European river serves as a resource for
various water uses and, therefore, environmental quality of the Danube river
basin is under great pressure from a diverse range of human activities. Although
water is usually employed as a pollution indicator by trace metals, sediments are
also considered to be important in the assessment of anthropogenic impacts1. The
lower part of the Danube river represents a significant habitat to numerous plant
and animal species. The occurrence of heavy metals in aquatic ecosystems has
become a problem of increasing concern about their influence on plant and animal
life, due to of their tendency to remain as an environmental contaminant for a long

*
For correspondence.

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period and also to be magnified through food chains2. Furthermore, some elements
(Pb, Cd, etc.) exhibit extreme toxicity even at trace levels3.
The contamination of the Danube river sediments with heavy metals is a very
old problem; earlier studies have revealed some hot-spots along the Danube46.
However, there is a lack of information on the metal pollution status in river sedi-
ment and the relationship between the concentrations of the metal pollutants in
sediment and water.
The aim of this study was to investigate the spatial and temporal variation in
heavy metal concentration in surface water and sediment for assessment of heavy
metal pollution status in the Danube river between km 347 and km 333, with a
view to determining its ability to sustain aquatic life.

EXPERIMENTAL

SAMPLING AND PRE-TREATMENT

Four sites were sampled along the Danube river between km 347 and km 333
during September 2011 December 2013 (Fig. 1). The sites characteristics are
shown in Table 1. Water and bottom sediment samples were collected monthly from
both left and right banks of the Danube and samples were analysed for six trace
metals: Cd, Pb, Ni, Cu, Cr and Zn. The pH and temperature were measured in the
field. Water samples were collected at the depth of 50 cm below the surface using
1-l polyethylene bottles with screw caps. The samples of the first 510 cm of the
river deposits were collected in polythene bags using antirust scoop. All samples
were kept in cooling boxes, at 4oC, during transportation, and the analyses were
performed immediately after receiving the samples in the laboratory.
The collected sediment samples were air-dried, large particles were hand-
picked and the rest were ground to powdery form. The fraction <63 m was used
for the analysis of the metals.

Table 1. Sampling sites characteristics

Site River Geographical coordinates pH Use land
(km) left bank right bank
S1 347 X: 704192.42 X: 704626.36 7.87 mixture residential,
Y: 301573.53 Y: 301023.59 agricultural and rural
S2 345 X: 706207 X: 706541 7.95 mixture residential,
Y: 302653 Y: 302123 agricultural and rural
S3 341 X: 712137 X: 712095 7.97 mixture residential,
Y: 304180 Y: 303961 agricultural and rural
S4 333 X: 716183 X: 716203 7.94 mixture residential,
Y: 303399 Y: 302992 agricultural and rural

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Fig. 1. Locations of the sites the Danube river

LABORATORY ANALYSIS OF HEAVY METALS

Water samples. Water sample was digested with hydrochloric acid 37% (Merck)
and nitric acid 65% (Merck) on a thermostatic hot plate. The remaining solution
was transferred to a 100-ml volumetric flask, diluted to the mark and mixed thor-
oughly. The quantitative determination of metals was performed using an atomic
absorption spectrophotometer (Solaar M5) with a mixture of air and acetylene for
flame combustion.
Sediment samples. Dry sediment was digested using aqua-regia (1:3 HNO3: HCl).
The acidified mixture was heated to boiling point and then cooled to room tempera-
ture. The acidified mixture was filtered and distilled water was added to the filtrate
in a volumetric flask up to 50-ml mark. Digestion solutions were then analyzed for
heavy metals content using atomic absorption spectrophotometry (Solaar M5).
Quality control and assurance. Quality control was assured by the use of procedural
blanks and standards. In all the cases of water and sediments and water a prepara-
tion/reagent blank was prepared for every 20 samples and all the concentrations
were below the detection limits. All acids used in this study were of analytical
grade quality control.

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RESULTS AND DISCUSSION
The values of heavy metal concentrations in water and sediment samples are
presented in Table 2. The minimum and maximum concentrations in water and
sediments are summarised in Table 3. The evaluation of the results was made
based on the European Water Framework Directive 2000/60/EC (Ref. 7) and the
Romanian law (Order 161/2006 transposed from Directive 2000/60/EC) (Ref.8)
limits and, also, on longitudinal trend of heavy metal concentrations along the
Danube river.

Table 2. Mean values of heavy metals in water and sediment obtained from the four sampling sites
along the Danube river
Site Cd Pb Ni Cu Cr Zn
W S W S W S W S W S W S
S1 0.067 0.434 0.784 14.45 1.82 36.52 3.10 34.24 0.718 29.44 23.0 104.3
S2 0.067 0.368 0.781 14.47 1.94 35.93 3.31 32.17 0.890 30.64 22.1 98.3
S3 0.065 0.396 0.884 16.94 1.74 42.18 3.20 33.23 0.867 33.55 23.7 112.0
S4 0.063 0.401 0.917 17.37 1.70 34.41 3.26 31.93 0.848 29.80 23.3 101.0
Soil 0.017 3.19 3.89 9.04 3.07 47.1
WDF 0.15 0.800 510 85.00 1025 35.00 2030 40.00 2550 100 100 150.0
limits 200
W metal concentration in water (g/l); S metal concentration in sediment (mg/kg); soil soil
background concentration (mg/kg).

Table 3. Range of heavy metal concentrations in water and sediment samples obtained from the four
sampling sites along the Danube river
Site Cd Pb Ni Cu Cr Zn
W S W S W S W S W S W S
S1 min. 0.02 0.130 0.06 1.01 0.38 11.93 0.44 10.92 0.25 4.09 1.40 33.89
max. 0.12 0.750 2.84 45.16 4.38 93.52 6.06 76.83 3.40 68.15 79.00 203.52
S2 min. 0.066 0.120 0.781 2.33 1.94 15.48 0.47 7.24 0.21 7.51 0.40 56.56
max. 0.19 0.757 2.79 38.15 4.92 69.75 6.57 80.17 3.97 53.75 75.00 146.75
S3 min. 0.02 0.143 0.07 1.21 0.33 16.82 0.43 11.82 0.24 10.56 0.90 32.05
max. 0.15 0.780 2.55 52.13 4.72 65.97 9.12 82.66 3.91 59.94 78.00 206.99
S4 min. 0.02 0.100 0.05 0.42 0.58 19.01 0.43 10.04 0.24 4.36 1.20 53.42
max. 0.12 1.330 3.81 77.67 3.54 63.81 7.81 86.52 3.47 48.57 77.00 179.30
W metal concentration in water (g/l); S metal concentration in sediment (mg/kg).

All sampling sites had pH>7 (Table 1) and some heavy metals like Cd and
Pb precipitated in alkaline water, forming complex products, which led to chemi-
cal speciation of metals and, therefore, influenced metal toxicity in both water
and sediment phase. Precipitation and sedimentation of Cu and Zn can also be
higher in alkaline waters and in the dry season, with the sediment phase serving

828
as an important sink for metals in water9,10. Water with a pH outside the normal
range (6.58.5) may contain excess toxic ions posing serious threat on the aquatic
organisms11.
In the study area, the heavy metal concentrations in surface water of the
Danube river were found within the quality class I limits of the European Water
Framework Directive 2000/60/EC (WFD). The general profile of mean metal
concentration in water for the study area was Zn>Cu>Ni>Pb>Cr>Cd, except for
site S2 (km 345) where Cr>Pb. The heavy metal concentrations in water obtained
in all the sampling sites were lower than what was previously reported in JDS2
Report6 for Cd and Ni (Cd = <0.2-<0.2 g/l, Ni = <0.212.2 g/l). However, the
Zn, Cu, Cr and Pb level obtained in this study was higher than the level obtained
in JDS2 survey (Zn = <0.516.1 g/l, Cu = <0.24.59 g/l, Cr = <0.51.26 g/l,
Pb = <0.22.0 g/l).

Fig. 2. Cadmium distribution

Fig. 3. Lead distribution

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Fig. 4. Nickel distribution

Fig. 5. Copper distribution

Fig. 6. Chromium distribution

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Fig. 7. Zinc distribution

The mean concentrations of all metals in sediments, except for Ni, were lower
than the limits of the Water Framework Directive 2000/60/EC, but higher than
background level in natural soil (Table 2). In the case of Ni, the concentration in
the bottom sediment exceeded the 35.0 mg/kg WFD sediment limit at sampling
sites located to km 347, 345 and km 341. This limit exceeding for Ni in the Danube
sediments was reported also in earlier studies6,12,13 and interpreted as a reflection of
geochemical background. Furthermore, significantly exceeding of the WDF sedi-
ment limits can be observed in the case of maximum values obtained for Cu, Zn
and Ni in all sampling sites (Table 3). According to U.S. EPA criteria, Cr, Pb and
Zn in the sediment are categorised as non-pollutant, Ni is moderate pollutant
and Cu is categorised as heavy pollutant3.
The mean concentrations of heavy metals in sediment varied slightly between
sites sampling, without showing any trends along the Danube river, except for Pb,
for which it was observed a general increase in the levels of Pb downstream from
km 347 to km 333. Similar longitudinal distribution of Pb in the Danube sediments
was reported in the results obtained in the second Joint Danube Survey Expedi-
tion (JDS2), the variation in the concentration of elements along the course of the
Danube river revealed a contamination of sediments especially from km 1500130
in case of Pb (Ref. 1). The order of heavy metal concentration in sediments in the
Danube river was: Zn > Ni > Cu > Cr > Pb > Cd.
Ratio of metals in the sediment phase to that in the water phase (bioconcentra-
tion) was estimated according to the following formula14:
BC = C1 / C2
where C1 is the concentration of metal in sediments; C2 concentration of metal
in water.
Bioconcentration factors calculated for the Danube river showed that metal
concentration in sediments were higher than the corresponding level in water.

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Chromium concentrations, followed by Ni concentrations were significantly
higher in sediments compared to those in water, as presented in Table 4. Metallic
bioconcentration order in the Danube river was: Cr > Ni > Pb > Cu > Cd > Zn.
Generally, the element mobilisation in the sediment environment is dependent on
physicochemical changes in water at the sedimentwater interface. The precipita-
tion of heavy metals in the form of oxides, insoluble hydroxides and carbonates
might be the result of alkaline pH. Moreover, the heavy metals can interact with
suspended particles in the aqueous phase and settle resulting in a high concentra-
tion of these elements in the sediment15,16.

Table 4. Ratio of metals in the sediments: water in the Danube river

Site Cd Pb Ni Cu Cr Zn
S1 6477.61 18456.63 20065.93 11045.16 41002.78 4534.78
S2 5492.53 18501.92 18520.62 9719.03 34426.97 4447.96
S3 6092.30 19162.89 24241.38 10384.37 38696.65 4725.74
S4 6365.07 18942.20 20241.18 9794.48 35141.51 4334.76

CONCLUSIONS
The obtained results showed that the heavy metal concentrations in surface water
of the Danube river were within the quality class I limits of the European Water
Framework Directive 2000/60/EC (WFD). Based on Water Directive 2000/60/EC
limits, the results indicate a long-term pollution for Ni, Cu and Zn in the river sedi-
ments which could be of concern for the health of the aquatic ecosystem. Special
attention should be given to the issue of elements re-mobilisation from sediments
because their effects may become significant during the seasons and the years of
low water flow in the river.

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6. ***Joint Danube Surevy 2 Report. 2007.
7. Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000.

832
 8. Order of the Ministry of Environmental and Water No 161/2006 for the Approval of the Norm
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Received 12 May 2014
Revised 6 June 2014

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