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Statistical analysis of heavy metals concentration in water and sediments in

the lower part of the Danube River-Romanian section

Article · January 2016

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 Statistical Analysis of Heavy Metals Concentration in Water and
Sediments in the Lower Part of the Danube River – Romanian Section

ANA MARIA ANGHEL1, ELENA DIACU2, MIHAELA ILIE1*, ALEXANDRU PETRESCU1, GINA GHITA1, FLORICA MARINESCU1,
GYORGY DEAK1
1
National Institute for Research and Development in Environmental Protection - INCDPM, 294 Splaiul Independenei, 060031,
Bucharest, Romania
2
University Politehnica of Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7 Polizu Str., 011061, Bucharest,
Romania

The Danube River is a transboundary water body traversing many populated areas along its course and
therefore is highly vulnerable to heavy metal pollution due to urbanization and industrialization. In this study,
sixteen sites were sampled along the Danube River between Km 347 and Km 182 during September 2012
– August 2014 for assessment of heavy metal pollution status. Water and bottom sediment samples were
collected monthly from left and right bank of the Danube and were determined the temperature, the pH and
four heavy metals: Cu, Cr, Ni and Zn, by AAS technique. Total metals concentrations of water ranged between
0.05-13.63 µg/L for Cr, 0.41-49.84 µg/L for Cu, 0.02-32.0 µg/L for Ni and 0.20-93.50 µg/L for Zn. Meanwhile, for
sediment, it ranged between 23.53-46.64 mg/kg for Cr, 21.02-42.35 mg/kg for Cu, 26.23-38.47 mg/kg for Ni
and 78.66-106.22 mg/kg for Zn. These data revealed that metal concentration levels in the sediments
surpassed corresponding levels in flowing water. To complete the monitoring process, statistical analyses
were performed using software package Minitab 16 and JMP 9 (SAS). Pearson correlation coefficient revealed
a strong relationship between Cr-Ni (0.881), Cu-Ni (0.879) and Cr-Cu (0.829) for water samples and Cu-Zn
(0.772) for sediments.
Keywords: Danube River, heavy metals, sediments, statistical analysis

The Danube River is the longest river in the European shown in table 1 and sections were grouped in three
Union and Europe’s second longest river after Volga [1] sectors: upstream (S1-S12), middle (S13-S14) and
and its lower part is on Romanian territory [2]. The Danube downstream (S15-S16). Water and sediment samples were
River that crosses Romania at its southern part flows into collected monthly from sections S1, S2, S3, S4, S15, S16
the Black sea. This important river, serves as a resource for and quarterly from S5 to S14. Samples were collected from
various water uses and therefore, environmental quality of both left and right bank of the Danube and were analysed
the Danube River basin is under great pressure due to a for four trace metals: Ni, Cu, Cr and Zn. The pH and
diverse range of human activities [3-6]. temperature were measured in the field. Water samples
Heavy metals are known to constitute highly persistent were collected at the depth of 50cm below the surface
environmental pollutants [7-11] and non-biodegradable and using 1L polyethylene bottles with screw caps. The
they can be bio-accumulated through the biologic chains: samples of the first 5-10cm of the river deposits were
soil–plant–food and seawater–marine organism–food [12]. collected in polythene bags using antirust scoop. All
All heavy metals present in surface waters occur in the samples were kept in cooling boxes, at 4 oC, during
form of colloids, particulates and dissolved phases, although transportation, and the analyses were performed
dissolved concentrations are generally low compared to immediately after receiving the samples in the laboratory.
their levels in the underlying associated sediments. Also, The collected sediment samples were air-dried, large
determining the total content of heavy metals in the particles were hand-picked and the rest were ground to
sediment may be useful for the characterization of pollution powdery form. The fraction <63 mm was used for the
intensity [13-15]. In this context, the contamination of analysis of the metals.
Danube River sediments with heavy metals is a very old
problem; earlier studies have revealed some hot-spots Laboratory analysis of heavy metals
along the Danube [3, 16]. Water samples
The aim of this work was to show that statistical The collected water samples were digested with 1:1
analysis can provide a scientific basis for monitoring the (v/v) HNO3:HClO4 (nitric acid 65% and hydrochloric acid
heavy metals evolution in time and space in water and 37%, both Merck) until was ascertained a complete
sediment and for controlling a non-point source of digestion through a gentle boiling on a thermostated hot
contamination produced by human activities. This was plate. The digested samples were cooled down,
done by monitoring the levels of total heavy metals (Cu, Cr, quantitatively transferred to a 100 mL volumetric flask and
Ni and Zn) in the water and sediment samples taken along made up to the mark with distilled water and mixed
the lower part of the Danube River. thoroughly. A blank determination was carried out also.
The levels of Cu, Cr, Ni and Zn in the processed samples
Experimental part were assessed by flame atomic absorption spectro-
Sampling and pretreatment photometry using Solaar M5 instrument from Thermo
Sixteen sites were sampled along the Danube River manufacturer.
between Km 347 and Km 182 during September 2012 – Sediment samples
August 2014 (fig. 1). The sampling sections location are The previously dried sediment was digested using aqua-
regia (1:3 v/v HNO3: HCl). The acidified mixture was heated
* email: [email protected], [email protected], Phone: 021 3052 600
REV.CHIM.(Bucharest) ♦ 67 ♦ No. 11 ♦ 2016 http://www.revistadechimie.ro 2151
 Fig. 1. Sampling sections located
along the lower part of Danube
River, Romania

Table 1
GEOGRAPHICAL
COORDINATES OF
SAMPLING SECTIONS
ESTABLISHED BY GPS

to boiling point and then cooled to room temperature. The samples ranged from 7.28 to 8.08 and for the sediments
acidified mixture was filtered and distilled water was added samples from 7.44 to 8.12.
to the filtrate in a volumetric flask up to 50 mL mark. Clear According to the analytical data obtained for heavy
digestion solutions were then analysed for heavy metals metals (results were expressed for each metal in mg/kg
content. of sediment and in µg/L of metal for water), a complete
descriptive statistic summary of studied heavy metals in
Quality control and assurance water and sediments is given in tables 2 and 3.
Quality assurance procedures include the instrument In the study area, the mean concentrations of studied
calibration using certified standards and reagent blank. For heavy metals in water ranged between 0.52-1.21 µg/L for
these procedures were prepared for every 20 samples, both Cr, 3.06-5.20 µg/L for Cu, 1.61-2.78 µg/L for Ni and 10.60-
water and sediment, reagent blank and all concentrations 16.45 µg/L for Zn (table 2). These mean concentrations of
obtained were below the detection limit. Analytical quality metals have classified the Danube water within the limits
control was verified by the routine analysis of Certified of first quality class of water, in accordance with the
Reference Materials - CRMs (CRM no. LGC6187 used for European Water Framework Directive 2000/60/EC (WFD).
sediments; no. S-WW1 Batch 110 and no. S-WW2 Batch However, in sections S1 – S4, the maximum concentrations
109 CRMs used for water analysis). All acids used in this of Cu and Ni exceeded the values of 30 and 25 µg/L
research had an analytical quality degree. respectively, water limits stipulated within the WFD.
Although the level of heavy metals in water is low, there is
Statistical analysis the risk that aquatic plants aquatic to uptake and
The statistical analysis was performed using Minitab 16 accumulate significant amounts of heavy metals and,
and JMP 9 (SAS) software package. This aims at finding consequently, to transferred them to herbivorous fish
some components that explain the major variation within species and aquatic invertebrates, thus entering in aquatic
experimental data. For cluster analysis were selected only food chains and posing an ecotoxicological risk to species
sections sampled monthly (S1 – S4, S15, S16). on higher trophic levels [17].
The mean concentrations of Cr and Zn in sediments
Results and discussions were lower than the limits prescribed by WFD. In the case
Descriptive statistics of Ni, the mean concentrations exceeded the 35.0 mg/kg
The physicochemical parameters of the water and WFD sediment limit at sampling sections S3, S4 and S7.
sediments recorded in monitoried period in the Danube The exceeding of maximum limit for Ni in the Danube
River showed that water temperature ranged from 1.10C sediments was reported also in earlier studies [18-20] and
to 25.60C. The pH was slightly basic, thus for the water seems to reflect its background concentrations in
2152 http://www.revistadechimie.ro REV.CHIM.(Bucharest)♦ 67♦ No. 11 ♦ 2016
 Table 2
DESCRIPTIVE STATISTIC OF METAL CONCENTRATIONS IN WATER SAMPLES IN THE SELECTED SECTIONS OF DANUBE RIVER

Table 3
DESCRIPTIVE STATISTIC OF METAL CONCENTRATIONS IN SEDIMENT SAMPLES IN THE SELECTED SECTIONS OF DANUBE RIVER

sediments. The mean concentrations of Cu exceeded the water and sediments, showed no longitudinal patterns
40 mg/kg WFD sediment limit only in sampling sections along the Danube River, between Km 347 - 182. However,
S4. Moreover, the maximum levels of Cu and Ni were based on the data of published studies [3, 22], in the Danube
exceeded the WFD sediments limits in all sampling sediments, it was observed a general increase in the levels
sections, except sections S9 and S10 for Cu, and S10 for of Pb along the course of the Danube River, especially from
Ni; the maximum levels of Zn were exceeded the WFD Km 1500 - 130.
sediments limit in sections S1, S3, S4 and S16 (table 3). In statistics, the Pearson correlation coefficient
The increased concentrations of heavy metals in sediments (Pearson’s r) is a measure of the linear correlation between
might be attributed mainly to the metal retentions capacity two variables, giving a value between +1 and -1 inclusive,
of sediments as well as urbanizations and industrialization where 1 is total positive correlation, 0 is no correlation, and
activities along Danube River and may pose a hazard to -1 is total negative correlation [23].
the aquatic biota [21]. The correlative relationships between heavy metals
The calculation of the coefficient of variation (CV) for were analysed and presented in tables 6 and 7. A high
water revealed that for Cr, Cu and Ni, the CV value were positive correlation between Cr-Ni, Cu-Ni and Cr-Cu in water
higher than 80% in the section S1 – S4 and S15. In case of samples was revealed (table 6). For sediments samples, it
Zn, the CV values are higher than 100% in all section. For was obtained a strong relationship between Cu-Zn and Ni-
sediment, the coefficient of variation (CV) ranged between Zn (table 7). In agreement with the literature [24-25], if the
15.52 and 68.56. correlation coefficient between the heavy metal factors is
Average concentrations of analysed heavy metals from positive, these factors might have similar sources of input,
each sampling section decreased in the order presented mutual dependence and identical behaviour during the
in tables 4 and 5. Spatial distribution of heavy metals, both transport. Furthermore, associations between heavy metals
REV.CHIM.(Bucharest) ♦ 67 ♦ No. 11 ♦ 2016 http://www.revistadechimie.ro 2153
 Table 4
SAMPLING SECTIONS ORDERED BY DECREASING MEAN CONCENTRATIONS – WATER

Table 5
SAMPLING SECTIONS ORDERED BY DECREASING MEAN CONCENTRATIONS – SEDIMENTS

Table 6 Table 7
PEARSON PEARSON
CORRELATION MATRIX CORRELATION MATRIX
FOR HEAVY METAL FOR HEAVY METAL IN
CONCENTRATION IN SURFACE SEDIMENTS
WATER

are important, as they determine the bioavailability and cluster A were grouped at high similarity percentage, about
potential toxicity to organisms in aquatic ecosystems [26]. 90% for all studied heavy metals, which may indicate that
the sections within the groups had similar natural
Cluster analysis of data backgrounds or/and were likely affected by common
Cluster analysis or clustering is the most basic pollution sources.
quantitative method for estimating similarities [27]. After In case of sediments, it was observed that the grouping
it was carried out the hierarchical cluster analysis, the of sampling sections in clusters do not have the same
process was represented on a diagram known as a pattern as in the case of water, respectively grouping the
dendrogram. The diagrams illustrate which clusters have upstream and downstream sampling sections in two
been joined at each stage of the analysis and the distance different clusters, except Cr (fig. 3). It is know that
between clusters at the time of joining [28]. Cluster sediments are able to adsorb and retain significant
analysis grouped the studied sampling sections into amounts of toxic contaminants as heavy metals [29] from
clusters on the basis of similarities within a group and water column differently along the aquatic ecosystem. The
dissimilarities between different groups (figs.2 and 3). adsorption capacity depends on many factors of the
Spatial cluster analysis of water sampling sections sediment-water system, including pH, temperature, cation
produced dendrograms with two groups (fig. 2). Cluster A exchange capacity, ionic strength, surface area, grain size,
comprised sections S1 – S4 (located upstream of study mineralogical properties, activity of the benthic organisms
area) and cluster B contained sections S15 – S16 (located etc [31]. These might explain the dissimilarities between
downstream of study area). Moreover, the sections from studied sections on the Danube River in the monitored
period.

Fig. 2. Dendrograms
of the water sampling
(a) - Cr (b) - Cu sections from the
Danube River

(c) - Ni (d) - Zn
2154 http://www.revistadechimie.ro REV.CHIM.(Bucharest)♦ 67♦ No. 11 ♦ 2016
 (a) - Cr (b) - Cu Fig. 3. Dendrograms of the
sediments sampling
sections from the Danube
River

(c) - Ni (d) - Zn

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Lower concentrations than first quality class limits of Central European Journal of Energetic Materials, 13, no. 1, 2016
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