Environ Monit Assess (2011) 173:883–897 DOI 10.1007/s10661-010-1431-6

Concentrations, distributions, and sources of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in bed sediments of the water reservoirs in Slovakia Edgar Hiller · Lenka Zemanová · Maroš Sirotiak · L’ubomír Jurkoviˇc

Received: 27 February 2009 / Accepted: 25 February 2010 / Published online: 20 March 2010 © Springer Science+Business Media B.V. 2010

Abstract Dredging water reservoirs is necessary to maintain accumulation capacity and to prevent floodings. As a first step, the quality of the bed sediments in water reservoirs must be determined before dredging operations. In this study, sediment samples from 34 stations of three selected water reservoirs (Zemplinska Sirava, Velke Kozmalovce, and Ruzin) were collected to investigate concentrations, distributions, and hazards of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) and to predict their possible sources. Total PCB concentrations were in the range of 20.4 to 2,325 ng/g. The maximum concentrations of PCBs were found in sediments from Zemplinska Sirava, which is in the vicinity of a former manufacturer of PCBs. The composition of PCBs was characterized by tri-

E. Hiller (B) · L. Zemanová · L. Jurkoviˇc Faculty of Natural Sciences, Department of Geochemistry, Comenius University in Bratislava, Mlynska dolina, 842 15, Bratislava 4, Slovak Republic e-mail: [email protected] M. Sirotiak Faculty of Materials Science and Technology in Trnava, Department of Environmental Engineering, Institute of Safety and Environmental Engineering, Slovak University of Technology in Bratislava, Botanicka 49, Trnava, 917 24, Slovak Republic

and hexa-CB congeners, indicating the influence of contamination from the use of specific Delor mixtures, formerly produced and massively used on the territory of Slovakia. The data showed that the highest total PAH concentrations were associated with the sediments from the Velke Kozmalovce, ranging from 7,910 to 29,538 ng/g. On the other hand, the lowest total PAH concentrations (84–631 ng/g of dry weight) were found in the sediments of Zemplinska Sirava, an important recreational area in eastern Slovakia. The distribution of individual PAHs was similar among the three water reservoirs, and this, together with principal component analysis and diagnostic PAH ratios, suggests mainly pyrolytic contamination of the sediments. However, petrogenic inputs appear to be important in the Zemplinska Sirava sediments. Keywords Polycyclic aromatic hydrocarbons · Polychlorinated biphenyls · Bed sediments · Distribution · Sources

Introduction Among various organic pollutants, the aquatic sediment contamination caused by polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) has received a great attention worldwide (Kelderman et al. 2000; El

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Nemr et al. 2007; Vane et al. 2007; Wang et al. 2007; Klánová et al. 2008; Ma et al. 2008). The main reason is that PCBs and PAHs are persistent in the environment, resistant to any degradation processes, and bio-accumulative through the food chain, with several of them exhibiting a wide range of hazardous effects to living organisms, including mutagenicity and carcinogenicity (Delistraty 1997). PCBs had numerous industrial applications, including mainly coolant and electronic industries (capacitors, transformers), but they were also used in paints, sealants for wood, cutting and lubricating fluids, plasticizers, and as dielectric fluids. Industrial production of PCBs in Slovakia proceeded from 1959 to 1984 as Delors 106, 105, 104 and 103. The production of PCBs has been estimated to be 21,500 metric tons. As a consequence, high concentrations of PCBs have been found in soils, sediments, humans, and wildlife in the area of former PCB manufacture in Slovakia (Kocan et al. 2001; Petrik et al. 2001). Although the production of PCBs has been stopped since 1984, they can still be produced as by-products in a wide variety of chemical processes containing chlorine and hydrocarbon sources. PAHs are a class of diverse organic compounds containing two or more fused aromatic rings of carbon and hydrogen atoms. They are ubiquitous organic pollutants that can result from natural processes such as forest fires, petroleum products, short-term degradation of biogenic precursors and anthropogenic sources such as combustion of fossil fuels. PAHs generated by natural oil seepage, oil spills, and discharge of petroleum products are considered to be of petrogenic origin, whereas those generated by incomplete combustion of recent and fossil organic matter are of pyrolytic origin (Budzinski et al. 1997; Yunker et al. 2002). Atmospheric transport is the primary pathway of global distribution of PCBs and PAHs in the environment (Jones and de Voogt 1999). PCBs and PAHs enter the surface soils and waters mainly by dry and wet deposition and road runoff, but also from industrial wastes and waters containing PCBs and PAHs. Due to their low aqueous solubilities, PCBs and PAHs are adsorbed strongly to the organic fraction of soils (Means et al. 1980; Girvin and Scott 1997), and hence, soils are considered as the primary sinks for these

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organic pollutants. Soils contaminated with PCBs and PAHs may be eroded and transported either directly or indirectly by rivers to the water reservoir environment where they are converted into bed sediments. Therefore, bed sediments play an important role as sinks for PCBs and PAHs in the aquatic environment. It is well-known that water reservoirs in Slovakia are exposed to a constant silting up as a result of soil erosion and suspended solid loads from rivers (Abaffy and Lukáˇc 1991). To prevent the reduction of accumulation capacity of the water reservoirs and the risk of flooding, bed sediments will have to be dredged in a near future. A common practice is that the dredged sediments are then disposed of to land, applied to agricultural soils, and deposited as a dangerous waste in waste dumps, depending on the type of present pollutants and their concentrations. To predict better environmental risks relating to the dredged contaminated sediments and to decide on their further treatment and management, the concentrations and sources of persistent organic pollutants such as PCBs and PAHs in bed sediments have to be determined in the first step. The present study gives an overview of the concentrations of PCBs and PAHs in bed sediments from the three water reservoirs located in highly industrialized regions of Slovakia, namely, Ruzin, Velke Kozmalovce, and Zemplinska Sirava. Relative distributions and diagnostic ratios were also analyzed for the identification of possible sources of the PCB and PAH contaminations.

Materials and methods Study areas and sample collection Figure 1 shows the study areas and the sampling locations. The Ruzin reservoir, with an area of 3.9 km2 and a water volume of 59 × 106 m3 , lies at the northwest of Kosice, eastern Slovakia. Two rivers enter the reservoir: Hornad and Hnilec. The two rivers drain the Spiš-Gemer Rudohorie Mountains, the area with long-time mining activities, ore treatment, and procesing industrial activities. Moreover, numerous urban waste discharges drain directly into the rivers. The reservoir of Velke Kozmalovce, with an area of 0.62 km2 and

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Fig. 1 Map of the studied water reservoirs and the sampling locations for sediments

a total water volume of 2.7 × 106 m3 , lies on the Hron River near the village of Stary Tekov, western Slovakia (Fig. 1). The Hron River receives organic pollutants from direct discharges of industrial waste waters and atmospheric deposition. The largest reservoir is Zemplinska Sirava, with an area of 15.1 km2 and a water volume of 185 × 106 m3 . It lies at the northeast of Michalovce in eastern Slovakia and serves as flood control, irrigation, and recreational purposes. Kocan et al. (2001) have shown that Zemplinska Sirava is highly contaminated with PCBs produced by the Chemko chemical factory (Strazske) during the period of 1959–1984. Sediment samples (0–20 cm)

were collected using a stainless steel corer in June 2005 from the 19, six, and nine locations in the Ruzin, the Velke Kozmalovce, and the Zemplinska Sirava water reservoirs, respectively (Fig. 1). Sediment samples in the Ruzin reservoir were taken from its two sedimentation basins as shown in Fig. 1. These sedimentation basins are located at the sites of the inflows of Hornad and Hnilec Rivers into the Ruzin reservoir. After collection, all samples were transferred to glass jars and stored at −20◦ C until extraction. Frozen aliquots of sediment samples were air-dried and then ground and sieved through a 2-mm sieve before analysis.

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Sample analysis Total organic carbon (TOC) contents were determined using a CS analyser (Metalyt CS 100/100, Eltra, FRG). The analyses of PCBs and PAHs were performed at the accredited laboratory of the Czech Geological Survey, branch Brno, Czech Republic. Briefly, a 10-g sediment was extracted by ultrasonication for 60 min with a 30-ml mixture of n-hexane and acetone (1:1 v/v) in two cycles. The extracts were centrifuged at 4,000 rpm for 15 min and combined. The extract was passed through a column filled with anhydrous Na2 SO4 to remove residues of water and then eluted with n-hexane and acetone mixture (1:1 v/v). The combined extracts were concentrated using Turbovap evaporator (Zymark, USA) to approximately 2 ml and purified in a silica gel column with activated copper fillings. The column was eluted with a 20-ml mixture of dichloromethane and n-hexane (1:10 v/v). The extracts were evaporated to dryness, and the residues were dissolved in acetonitrile and isooctane before PAH and PCB analysis, respectively. PCBs in the extracts were analyzed on a HP 5890 series II gas chromatograph equipped with a 63 Ni electron capture detector and HP Chemstation software package. Basic parameters of the high-resolution gas chromatography experimental arrangement for analysis of PCBs were: hydrogen as carrier gas, capillary column HP 5 (60 m × 0.25 mm i.d., 0.25 μm), and the volume of sample injected in splitless mode was 1 μl. The temperature program was as follows: initial temperature of 60◦ C held for 2 min, increased to 180◦ C at a rate of 5◦ C/min, isothermal at 180◦ C for 10 min, followed by 220◦ C at 1◦ C/min, 220–280◦ C at 2◦ C/min, and a final 280◦ C held for 20 min. The injector temperature was 280◦ C. By this method, 12 PCB congeners were determined with the limit of detection of about 0.1 ng/g and the relative standard deviation (SD) of <15%. PCB conceners analyzed were 18, 28, 31, 44, 52, 101, 118, 138, 149, 153, 180, and 194. To assure representativeness and reliability of the data obtained and to determine recoveries of the method, analytical procedure included sediment samples spiked with PCB Congener Mix-1 (Supelco) and the analysis of certified reference material CRM BCR-

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536. Recoveries of the method ranged from 84% to 102%. A high-performance liquid chromatographic system (HP-Agilent 1100 Series) with a fluorescence detector (HP 1046A) was used for PAH analysis. The separation of PAHs was carried out on a LiChrospher PAH (250 mm × 4 mm i.d.) column with the LiChrospher PAH precolumn (Merck, Germany) under the following conditions: gradient elution with acetonitrile/water at the beginning and then with 100% acetonitrile, a mobile phase flow rate of 1 ml/min, an injection volume of 20 μl, and a column temperature of 35◦ C. By this method, 15 PAH compounds were determined with the limit of detection of about 1.0 ng/g and relative SD of 10%. The PAHs detected were naphthalene (Na), acenaphthene (Ac), fluorene (Flu), phenanthrene (Phe), anthracene (Ant), fluoranthene (Flt), pyrene (Pyr), benzo(a)anthracene (BaA), chrysene (Chr), benzo(b )fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), dibenzo(a,h) anthracene (DA), benzo(g,h,i)perylene (BP), and indeno(1,2,3,c,d)pyrene (InP). To demonstrate the accuracy of the data obtained by analysis of sediments, analyses were conducted on spiked sediment samples with known quantities of PAH mixture and reference material CRM BCR-535 (PAHs in freshwater harbor sediment). The recovery of the method used for PAH analysis was in a range of 76–97%, depending on the individual PAH compounds.

Results and discussion PCB concentrations and distributions in sediment samples from three water reservoirs Mean concentrations, minimum and maximum for the individual PCB congeners and the sum of 12 PCBs (denoted as 12 PCBs) determined are shown in Table 1. Notable differences could be observed between the mean total PCB concentrations in bed sediments from the Zemplinska Sirava reservoir and those found in sediments from the other two water reservoirs (Table 1). The total PCBs in sediments from Zemplinska Sirava ranged from 23.5 to 2,325 ng/g dry weight, with

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Table 1 Concentrations, range (minimum-maximum) and SD of individual PCB congeners and total PCBs (in nanograms per gram of dry weight) and TOC contents (in percent) in the sediment samples

CB18 CB28 CB31 CB44 CB52 CG101 CB118 CB138 CB149 CB153 CB180 CB194 12 PCBs TOC

Ruzin (N = 19) Mean Range

SD

Velke kozmalovce (N = 6) Mean Range SD

Zemplinska sirava (N = 9) Mean Range SD

3.19 6.04 4.24 2.62 3.19 3.01 1.17 4.59 3.84 4.96 3.53 0.71 41.09 4.95

3.02 5.46 3.69 2.07 2.18 0.77 0.42 1.21 0.91 1.27 0.99 0.16 16.45 1.55

2.03 3.68 3.15 1.97 2.63 4.18 1.70 5.95 4.97 6.30 4.15 0.82 41.53 7.28

54.2 137.8 95.6 39.6 68.7 58.9 31.9 69.3 63.9 72.4 48.2 19.7 760.1 2.13

0.5–11.5 1.3–21.8 0.9–14.4 0.5–7.0 0.9–7.6 1.6–4.4 0.6–1.9 2.3–7.0 2.0–5.4 2.5–7.3 1.7–5.3 0.5–1.0 20.4–84 2.26–7.40

0.8–2.9 1.6–4.7 1.3–4.0 1.0–2.7 1.5–3.5 2.8–5.7 1.2–2.2 4.3–6.8 3.4–6.0 4.5–7.2 3.2–5.0 0.7–1.0 26.3–49.9 6.12–8.72

0.69 1.08 0.96 0.56 0.66 0.95 0.33 0.94 0.91 1.00 0.64 0.12 8.44 0.89

1.3–209 3.4–501 2.2–378 1.2–113 2.1–205 2.3–149 1.0–85.1 2.6–176 2.5–165 2.8–197 1.7–121 0.4–86 23.5–2,325 0.74–3.93

64.1 149.3 113.9 33.5 58.1 42.1 23.9 48.4 45.3 54.7 32.6 25.8 665.3 0.89

N number of samples, CB18 2,2 ,5-trichlorobiphenyl, CB28 2,4,4 -trichlorobiphenyl, CB31 2,4 ,5-trichlorobiphenyl, CB44 2,2 ,3,5 -tetrachlorobiphenyl, CB52 2,2 ,5,5 -tetrachlorobiphenyl, CB101 2,2 ,4,5,5 -pentachlorobiphenyl, CB118 2,3 ,4,4 ,5pentachlorobiphenyl, CB138 2,2 ,3,4,4 ,5 -hexachlorobiphenyl, CB149 2,2 ,3,4 ,5 ,6 -hexachlorobiphenyl, CB153 2,2 ,4,4 ,5,5 hexachlorobiphenyl, CB180 2,2 ,3,4,4 ,5,5 -heptachlorobiphenyl, CB194 2,2 ,3,3 ,4,4 ,5,5 -octachlorobiphenyl,  12 PCBs sum of 12 PCBs, TOC total organic carbon

a mean value of 760 ng/g, whereas 12 PCBs in sediments from the Ruzin and the Velke Kozmalovce were, on the average, 18-fold lower than the former. The high concentrations of 12 PCBs determined in the Zemplinska Sirava reservoir are in a close agreement with the results by Kocan et al. (2001), who reported total PCBs (9 PCBs) ranging from 3,900 to 6,000 ng/g in sediments from the Laborec River flowing into the reservoir and from 1,700 to 3,100 ng/g in sediments collected from three stations in Zemplinska Sirava. The contamination of the Zemplinska Sirava reservoir and surrounding watercourses with PCBs is a notorious environmental “hot spot,” and it is caused by the effluent canal of the former PCB manufacturer since PCB concentrations found in the canal sediments have reached still 3,000 μg/g (Kocan et al. 2001). The concentrations of PCBs in sediments from the Zemplinska Sirava reservoir (Table 1) are comparable with values found in other countries, resulting from local sources of contamination. For example, Vanier et al. (1996) reported concentrations (31 PCBs) ranging from 260 up to 11,020 ng/g in sediments from the Saint Lawrence River (Canada), and in Italy, Frignani et al. (2001) found a maximum concentration of

2,049 ng/g (12 PCBs) in a sediment contaminated by the discharge of industrial wastes. Fernández et al. (1999a) reported 1,772 ng/g (13 PCBs) in sediment from the Ebro River (Spain). To provide the environmental significance of the results obtained in this study, they were compared with sediment quality guidelines (SQGs) established by Canada (CCME 2001), which are frequently used to assess the potential risk of organochlorine compounds in sediments for the water quality and aquatic life. The threshold effect level (TEL), interim sediment quality guidelines (ISQG), and probable effect level (PEL) are used as SQGs. The TEL or the ISQG represents the concentration below which adverse biological effects are not expected, whereas the PEL defines the concentration above which adverse effects are expected to occur frequently (MacDonald et al. 2000). The ISQG and PEL values of PCBs are 34.1 and 277 ng/g, respectively. When considering the sums of PCBs (Table 1; see also Fig. 5) there are seven sediment samples from the Zemplinska Sirava reservoir exceeding the PEL value and one sample above the ISQG value. This comparison indicates that PCBs in the Zemplinska Sirava sediments represent relevant ecological

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Environ Monit Assess (2011) 173:883–897 CB CB CB CB CB CB

Factor 2 : 6.01%

0.0

better understanding of the relations in the data set. The results point to the low dimensionality of the data. More than 92% of the variability can be explained by the first factor. Figure 2 shows the plot of factor coordinates of the individual PCB congeners for the first two factors. Factor 1 correlates well with all the PCB compounds, except congener CB 194, which is the only congener showing reasonably high loading for factor 2. This indicates factor 1 as a component corresponding to the total PCB concentration. Most sediment samples are aligned along the factor 1 axis, following the total PCB concentration criterion (Fig. 3). Samples taken from the Zemplinska Sirava reservoir are arranged at the negative part of factor 1 axis, having the highest total PCB concentrations of the three reservoirs studied. The only sediment with a high score on factor 2 is the ZS4 sample. This is probably related to its remarkably high CB 194 content compared to the other samples. Despite the anomalous position of this sample, PCA indicates the tendency of the sediments to cluster only according to their total PCB concentrations. There is no sign of the differences resulting from different proportions of individual congeners. However, when performing the analysis for each reservoir separately (figures not shown), the more detailed view of the Ruzin samples shows their tendency to cluster according to

18, CB 28, 31, CB 44, 52, CB 101, 118, CB 138, 149, CB 153, 180

-0.5

CB 194 -1.0

-1.0

-0.5

0.0

Factor 1 : 92.32%

Fig. 2 The PCA loading plot of factor 1 vs. factor 2, illustrating the distribution of individual PCB congeners

risk. Five samples from the Velke Kozmalovce and 11 samples from the Ruzin have PCB levels that are higher than the ISQG value. Thus, the PCB concentrations in these two studied reservoirs may be also of an environmental significance for the ecology of the reservoirs. Principal component analysis (PCA) was performed to examine the data structure and gain Fig. 3 Plot of factor coordinates of the sediments used in the study according to their PCB contents

3 Zemplinska Sirava

2

Ruzin + Velke Kozmalovce

ZS5

1

ZS7 ZS3 ZS2 ZS6 ZS1 ZS9

Factor 2: 6.01%

0 -1 -2 -3 -4 -5

ZS4

-6 -7 -25

-20

-15

-10

-5

Factor 1: 92.32%

0

5

10

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the exact sampling site. Sediments sampled at the inflow of the Hnilec River correlate well with the axis represented by the CBs 18–118, while samples from the Hornad River inflow correlate with the axis characterized by the heavier congeners (CBs 138–194). Indeed, further investigation of the data confirmed considerable differences between HO and HN samples. Figure 4 shows the mean PCB profiles (mean percentage of each group within the sum of 12 PCBs) in sediments from each reservoir. In general, tri-CBs (CBs 18, 28, and 31) and hexa-CBs (CBs 138, 149, and 153) are the most abundant PCB congeners in the sediments regardless of the reservoir locations. In sediment samples from Zemplinska Sirava, tri-CBs and hexaCBs are equally the most dominant congeners, together accounting for more than 60% of the total PCB concentrations. The obtained profile may be explained by the contamination of the Zemplinska Sirava reservoir with all types of Delors, a commercial PCB mixture produced formerly by Chemko Strážske in eastern Slovakia. It has been found that in Delors 103 and 104, tri-CB congeners were the most abundant ones, whereas in Delors 105 and 106, hexa-CBs were the dominant congeners (Taniyasu et al. 2003). Indeed, the profile obtained here for sediments from Zemplinska Sirava resembles these types of Delor. Sediment samples from the Velke Kozmalovce reservoir are characterized

60

Abundance (%)

Ruzin-Hnilec Ruzin-Hornad Velke Kozmalovce Zemplinska Sirava

40

20

0 Tri-CB

Tetra-CB Penta-CB Hexa-CB Hepta-CB Octa-CB

Fig. 4 PCB profiles (mean percentage of each group within the sum of 12 PCBs) in bed sediments. Error bars represent the SD

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by the dominance of hexa-CBs congeners followed by tri-CBs congeners (Fig. 4), indicating a contamination with both groups of Delor. Notable differences in PCB congener distribution were observed between the sediments collected at the inflow of the Hnilec River into the Ruzin reservoir (denoted as HN sediments) and those taken at the inflow of Hornad River (HO sediments) (Figs. 1 and 4). As can be seen from Fig. 4, hexa- and hepta-CBs were the dominant congeners in HO sediments, whereas tri-, tetra-, and hexa-CBs were the most abundant in HN sediments. This finding suggests that different input sources are responsible for the contamination with PCBs in HO and HN sediments. The profile for HO sediments may indicate the influence of contamination from the use of specific Delor mixtures, mainly Delors 105 and 106 with the typical dominance of hexa- and hepta-CBs congeners. It seems that the major source of PCBs in HN sediments is associated with the upper stream contamination of the Hnilec River from ore treatment and processing industrial activities, which have a long history in this area. In general, natural organic matter in sediments and soils is the main property controlling the retention and distribution of hydrophobic organic pollutants such as PCBs and PAHs under wellcontrolled laboratory conditions (Karickhoff et al. 1979; Weber et al. 1983; Girvin and Scott 1997). However, when considering the distribution of PCBs in sediments under natural conditions, a positive relationship between the sum of PCBs and TOC is rarely observed (Camacho-Ibar and McEvoy 1996; Lee et al. 2001). In this study, only the total PCB concentrations in sediments from the Ruzin reservoir were significantly correlated with TOC (r2 = 0.617, p < 0.001, n = 19). There were no significant correlations between 12 PCBs in sediments from each of the other two reservoirs and TOC, although some positive relationships could be observed (Fig. 5). This suggests that factors other than retention of PCBs by organic matter may be important for the PCB distribution in sediments. Obviously, distribution of PCBs in sediments controlled by organic matter may be masked by different factors such as soil erosion, dynamics of river flows, pathway and history of

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Environ Monit Assess (2011) 173:883–897 2500 Zemplinska Sirava

Σ 12PCBs (ng/g)

2000

Ruzin

1500

Velke Kozmalovce

1000 500 the PEL value (277 ng/g)

100 80 60 40

the ISQG value (34.1 ng/g)

20 0

2

4

6

8

10

TOC (%)

Fig. 5 Relationship between the sum of 12 PCBs and TOC contents in bed sediments of the three water reservoirs. The ISQG and PEL values of PCBs are denoted by horizontal dashed lines

contamination, and local PCB inputs. The results are in agreement with those reported for PCBs in other countries (Carpentier et al. 2002; Vane et al. 2007; Wang et al. 2007). PAH concentrations and distributions in sediment samples from three water reservoirs The mean concentrations and the range (minimum and maximum concentrations) of each PAH

and total PAHs (expressed as the sum of the concentrations of 15 parent PAH compounds and denoted as 15 PAH) are given in Table 2. The total PAH concentrations in sediments varied widely among the three water reservoirs. The maximum concentrations of total PAH were recorded in the sediments from the Velke Kozmalovce (7,910– 29,538 ng/g), with a mean value of 19,034 ng/g, followed by sediments from the Ruzin (2,697– 7,561 ng/g). The lowest total PAH concentrations, ranging from 84 to 631 ng/g were observed in sediments from Zemplinska Sirava. The high contamination level of the Velke Kozmalovce sediments with PAHs and also relatively high TOC contents in these sediments could be ascribed to the direct discharges of organic-rich waste waters from wood-processing industry into the Hron River, which supplies the reservoir with water. For example, Metelková et al. (2003) reported relatively high concentrations of PAHs in industrial waste waters (from 0.023 up to 455 μg/l depending on the individual PAHs) from a wood-processing factory in Bucina Zvolen discharging into the Hron River. Moreover, atmospheric deposition might also be a significant source of PAHs as the whole catchment area of the Hron River is highly

Table 2 Concentrations, range (minimum to maximum) and SD of individual and total PAHs (in nanograms per gram of dry weight) in the sediment samples

Na Ac Phe Ant Flu Flt Pyr BaA Chr BbF BkF BaP InP DA BaP 15 PAHs

Ruzin (N = 19) Mean Range

SD

Velke kozmalovce (N = 6) Mean Range

SD

Zemplinska sirava (N = 9) Mean Range SD

55.4 26.6 373 90.6 37.2 887 725 372 398 385 236 450 389 49.7 242 4,719

15.7 17.3 119 44.6 17.2 258 203 94.2 101 88.6 71 110 90.2 10.8 60.5 1,232

123 308 1,464 361 466 6,982 4,861 1,671 1,132 512 282 473 223 33.2 145 19,034

90.2 194 713 163 254 3,250 2,387 675 409 124 73.1 129 31.2 6.37 26.6 8,227

11 ND 58 5.89 11 69.1 54.9 13.8 31.3 43.4 18.4 34.6 44.3 5.78 31.1 434

26–85 11–83 212–654 48–229 19–91 492–1,569 417–1,227 211–580 229–585 227–544 122–374 272–680 227–583 32–72 152–354 2,697–7,561

59–296 122–665 662–2,604 150–597 198–910 2,580–11,720 1,808–8,270 654–2,440 521–1,630 336–678 173–382 294–636 194–282 26-44 119–193 7,910–29,538

5–15

3.94

19–100 1–9 6–18 9–103 4–87 1–27 3–51 8–70 2–27 5–55 6–71 3–9 12–48 84–631

28.7 3.26 4.21 35.6 31.6 8.2 17.4 22.8 9.45 18.7 19.9 2.17 13.9 205

N number of samples, ND below detection limit, Na naphthalene, Ac acenaphthene, Phe phenanthrene, Ant anthracene, Flu fluorene, Flt fluoranthene, Pyr pyrene, BaA benzo(a)anthracene, Chr chrysene, BbF benzo(b )fluoranthene, BkF benzo(k)fluoranthene, BaP benzo(a)pyrene, InP indeno(1,2,3-cd)pyrene, DA dibenzo(a,h)anthracene, BP benzo(g,h,i)perylene,  15 PAHs sum of 15 PAHs

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industrialized, with activities associated with the consumption of coals. The total PAH concentrations covering a wide range of contamination levels observed in this study are comparable with those from other studies. For example, data published by Boháˇcek et al. (2003) in the Horní Becva reservoir (Czech Republic) showed a total PAH concentrations ranging from 3,550 up to 80,400 ng/g in sediments collected from up to a depth of 30 cm. Even the sediments from high-altitude lakes of the High Tatra Mountains (Slovakia) appear to be contaminated with PAHs (18,000 ng/g; Fernández et al. 1999b) compared with the sediments from Velke Kozmalovce. The mean PAH concentration in the dredged sediments from the Seine River (France) was 10,900 ng/g (Carpentier et al. 2002) and in the Netherlands, Kelderman et al. (2000) reported that total PAH concentrations in canal sediments of the inner city of Delft had a median value of 11,000 ng/g. However, even the sediments from the Velke Kozmalovce reservoir appear to be only moderately contaminated with PAHs when compared with the river sediments in the northern France containing far higher total PAH concentrations that can reach 770,000 ng/g (Ruban et al. 1998). On the other hand, Baran et al. (2002) reported a lower contamination with PAHs in the sediments from the Narew River (Poland) ranging from 21 to 600 ng/g, with an overall level lower than 160 ng/g for most of the sediments.

Table 3 ISQGs and PELs for PAHs (in nanograms per gram) in freshwater sediments (CCME 1999) LMW PAHs Naphthalene Acenaphthene Fluorene Phenanthrene Anthracene HMW PAHs Fluoranthene Pyrene Benzo(a)anthracene Chrysene Benzo(a)pyrene Dibenzo(a,h)anthracene

ISQG

PEL

34.6 6.71 21.2 41.9 46.9

391 88.9 144 515 245

111 53.0 31.7 57.1 31.9 6.22

2,355 875 385 862 782 135

To give a general overview of the PAH contamination of sediments in the three water reservoir and to assess the ecological toxicity of individual PAHs in sediments, total PAH concentrations were compared with the ISQG and PEL values included in SQGs (CCME 1999) and summarized in Table 3. Considering the results given in Table 2, it could be stated that concentrations of individual PAHs in the sediments from the Ruzin reservoir exceeded their respective ISQG values in almost all stations. There were only two samples having naphthalene and fluorene below the ISQG value but two samples from stations HN2 and HO6 exceeding the PEL value for phenanthrene and one sample from station HO6 above the PEL value for fluoranthene. Moreover, the concentrations of pyrene and benzo(a)anthracene in sediments at five and eight stations of the Ruzin reservoir, respectively, were higher than the PEL values for these PAHs. In Zemplinska Sirava, most of the sediment samples had concentrations below the ISQG values for individual PAHs, with the exception of phenanthrene, pyrene, benzo(a)pyrene, and dibenzo(a,h)anthracene at six, six, five, and four stations, respectively, whose concentrations were above the ISQG values. The worst case represented sediments from the Velke Kozmalovce, with naphthalene, benzo(a)pyrene, and dibenzo(a,h)anthracene concentrations at all stations above their ISQG values and the rest of PAHs at almost all stations above the PEL values. The simple ISQG/PEL analysis suggests that the Velke Kozmalovce sediments are the most contaminated with acutely toxic PAHs when compared with the sediments from the other two reservoirs. These results should increase a concern about the possible risk posed for the water quality and the ecology of the Velke Kozmalovce reservoir. The sediment TOC has been found to be a key property influencing PAH concentrations in sediments (Wang et al. 2001; Chen et al. 2006; El Nemr et al. 2007; Feng et al. 2007). However, the correlation analysis indicated that neither individual PAHs nor 15 PAHs in sediments samples were correlated with TOC in the study, which might be a result of non-equilibrium distribution between TOC and PAHs. The absence of correlation might be due to the continuous input of fresh PAH contamination into the reservoirs in which there

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were selected for the interpretation of the results. They together account for >94% of the data variability. Figure 6 shows the plot of factor coordinates of the PAHs for the first two factors. Factor 1 correlates well with Ant, Phe, Pyr, Chr, Flt, BaA, and BbF. All these compounds gave strong correlations with the total PAH concentrations in the samples (r ≥ 0.89), except BbF. These facts indicate factor 1 to be a quantitative correlation component and to correspond to the total PAH concentrations. PAHs tend to cluster according to their chemical properties, with factor 1 being more correlated to the 3 + 4-ring PAHs, while factor 2 is characterized by the 5 + 6-ring compounds (best correlations found with InP, DA, and BP). Figure 7 shows the plot of factor coordinates of all sediment samples for the first two factors. The samples cluster according to their sampling sites— three clusters represent the sediments taken from the Ruzin, the Velke Kozmalovce, and the Zemplinska Sirava reservoirs. Samples from the Velke Kozmalovce score high on factor 1. This might be caused by the highest total PAH concentrations found in these sediments when compared to those taken from the other two water reservoirs. The cluster representing samples from Zemplinska Sirava possessing the lowest total PAH concentrations within the tested sites is situated at the

5 + 6 rings DA 5 rings

InP BP

Factor 2 : 26.02%

BaP 0.5

BkF BbF

Na

0.0

Chr

-0.5

Ant BaA Pyr Flt Ac Phe Flu

-1.0

2 + 3 + 4 rings

-0.5

0.0

Factor 1 : 68.38% Fig. 6 The PCA loading plot of factor 1 vs. factor 2, illustrating the distribution of individual PAHs

is no sufficient time to achieve equilibrium state between sediment TOC and PAHs. No correlations between PAHs and TOC were also reported in other studies (Storelli and Marcotrigiano 2000; El Deeb et al. 2007; Arias et al. 2009). Again, PCA was used to examine the relationships between the variables. First two components

Fig. 7 Plot of factor coordinates of the sediments used in the study according to their PAH contents

4 3 HN1 - HN12 HO1 - HO7 Ruz in

Factor 2: 26.02%

2 1 0 -1

V K1 - V K6 V elke Koz malov ce

-2 -3 ZS 1 - ZS 9 Zemplinska S irav a

-4 -5 -6 -14

-12

-10

-8

-6

-4

-2

Factor 1: 68.38%

0

2

4

6

8

Environ Monit Assess (2011) 173:883–897

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opposite part of factor 1 axis. Besides, its position is opposite to the position of high-molecularweight (HMW) PAHs (especially InP, DA, and BP). Indeed, the Zemplinska Sirava samples have the highest low-molecular-weight (LMW)/HMW PAH ratios of the sediments studied. On the contrary, the sediments from the Ruzin cluster at the positive side of factor 2 axis, being the only group of samples having high scores on this component, correlate well with the 5 + 6-ring PAHs. The distribution of the clusters found in the PCA analysis indicates different quality of sediment contamination by PAHs in the three sampling sites. Therefore, the assumption of different contamination sources was considered in further interpretation of the results. According to the number of aromatic rings, the 15 PAHs were divided into three groups representing 2 + 3-ring, 4-ring, and 5 + 6-ring PAHs. The mean composition and relative abundance of each group in the sediment samples from each reservoir is shown in Fig. 8. First, it could be seen from Fig. 8 that 4-ring PAHs (36.7–76.1%) together with 5 + 6-ring PAHs (9.7–41.6%) were present in higher proportions than 2 + 3-ring PAHs (11.8–21.8%). Second, the compositions and relative abundance of individual PAHs were quite similar, except for the sediment samples collected from the Velke Kozmalovce, in which the 4-ring PAHs strongly prevailed over the other PAH groups. In general, the composition profile of PAHs in sediment samples from the reservoirs

100 Ruzin-Hnilec Ruzin-Hornad

Abundance (%)

80

Velke Kozmalovce Zemplinska Sirava

60

40

20

0 2+3 ring PAHs

4 ring PAHs

5+6 ring PAHs

Fig. 8 Composition profiles of PAHs (mean percentage of each group within the sum of 15 PAHs) in bed sediments. Error bars represent the SD

investigated was characterized by the dominance of HMW PAHs (HMW = 4-ring + 5 + 6-ring), accounting for 78–88%. Fluoranthene and pyrene were by far the most dominant PAHs, accounting for 11–40% and 5–28% of the 15 PAHs, respectively, followed by phenanthrene, chrysene, benzo(b )fluoranthene, benzo(a)pyrene, and benzo(a)anthracene comprising 6–22%, 4–10%, 2–13%, 2–10%, and 1.2–10% of the 15 PAHs, respectively. The results strongly indicate that pyrolitic (combustion) inputs are the major source of PAHs in the reservoir sediments. It is well reported that the anthropogenic inputs of PAHs are of pyrolytic and petrogenic origins. The PAHs of petrogenic origins are typical by the abundance of 2 + 3-ring PAHs, and the PAHs of pyrolytic origins contain a high proportion of 4-ring and more-ring PAHs (Soclo et al. 2000; Zakaria et al. 2002). To further characterize sources of PAHs in the reservoir sediments, the selected diagnostic ratios were calculated (Fig. 9) since they are often used to distinguish between petrogenic and pyrolytic sources (Budzinski et al. 1997; Yunker et al. 2002; Agarwal et al. 2006). These ratios are based on the differences in thermodynamic stability of various structural isomers (Yunker et al. 2002). For example, anthracene and phenanthrene are isomers, but phenanthrene has the higher thermodynamic stability; therefore, the ratio of Ant/(Ant + Phe) is typically high in samples contaminated with PAHs of pyrolytic origin but low when contamination is due to petrogenic inputs. In general, the ratio of Ant/(Ant + Phe) <0.1 indicates petrogenic inputs, while a ratio >0.1 is an indication of pyrolytic sources. The ratio of Flt/(Flt + Pyr) is another commonly used indicator for source apportionment. The values <0.4 are characteristic of the petrogenic source, the values between 0.4 and 0.5 indicate liquid fossil fuel combustion, while the values above 0.5 are taken as an indication of biomass and coal combustion. Moreover, the ratio of BaA/(BaA + Chr) <0.2 is associated with petrogenic sources, the ratio between 0.2 and 0.35 suggests either petrogenic or pyrolytic inputs, and >0.35 implies combustion processes. Similarly, the ratio of InP/(InP + BP) <0.2 indicates petrogenic source, the ratio from 0.2 to 0.5 indicates liquid fossil fuel combustion, while the ratio >0.5 results

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Fig. 9 Plots of selected diagnostic ratios for the identification of PAH sources in bed sediments of the water reservoirs

petroleum combustion

biomass & coal combustion

Ant / Ant + Phe

0.3

Ruzin(Hnilec) Ruzin(Hornad) Velke Kozmalovce Zemplinska Sirava

biomass, coal & petroleum combustion

0.2

0.1

petroleum

0.0 0.4

0.5

0.6

0.7

Flt / Flt + Pyr

0.6

biomass & coal combustion

BaA / BaA + Chr

0.5

0.4

mixed sources

0.3

0.2

petroleum 0.1 0.4

0.5

0.6

0.7

Flt / Flt + Pyr

from biomass and coal combustion (Yunker et al. 2002). In this study, the ratio of Ant/(Ant + Phe) in most of the sediment samples ranged from 0.14 to 0.26, except the sediments at seven stations in the Zemplinska Sirava reservoir, while the values of Flt/(Flt + Pyr) were higher than 0.5 in all of them (Fig. 9). The ratio of BaA/(BaA + Chr) was >0.35 for the most sediment samples, but again with an exception of the sediment samples from Zemplinska Sirava, and the InP/ (InP + BP) ratio varied from 0.53 to 0.67 for most of the sediments samples; only one of the sediment samples exhibited the value of 0.33. These

results suggested that the combustion of biomass and coal was the predominant source of PAHs in sediment samples regardless of the reservoir location. However, it seems that petrogenic inputs might contribute to the sediment contamination with PAHs in the Zemplinska Sirava reservoir as indicated by the Ant/(Ant + Phe) and BaA/(BaA + Chr) ratios being lower than 0.1 and 0.35, respectively. The Zemplinska Sirava reservoir is a well-known recreational area with many auto-camps, yacht clubs, and shipping activities. Therefore, accidental and intended seepages of liquid fuels during the loading and repair might

Environ Monit Assess (2011) 173:883–897

contribute to the petrogenic origin of PAHs in these sediments.

Conclusions To prevent the reduction of accumulation capacity of the water reservoirs in Slovakia and the risk of flooding, bed sediments will have to be dredged in a near future. However, before dredging, the quality of the sediments to be dredged must be monitored to determine the further treatment and management of dredged materials. Data from the current study showed that the concentrations of 12 PCBs in bed sediments from the Zemplinska Sirava, the Velke Kozmalovce, and the Ruzin reservoirs (Slovakia) varied widely and were in the range of 23.5 to 2,325, 26.3 to 49.9, and 20.4 to 84 ng/g, respectively. The distribution of PCBs in sediment samples from the reservoirs seemed to be controlled by sediment TOC, although factors other than the retention of PCBs by organic matter might be important for the PCB distribution in sediments. The composition of PCBs was characterized by tri- and hexa-CBs congeners, indicating the influence of contamination from the use of specific Delor mixtures, which were formerly produced and massively used in the territory of Slovakia. In this study, PAHs in sediment samples were also analyzed. The concentrations of 15 PAHs in bed sediments from the Zemplinska Sirava, the Velke Kozmalovce, and the Ruzin reservoirs were in the ranges of 84–631, 7,910–29,538, and 2,697–7,561 ng/g, respectively. The extent of contamination with PAHs seemed to be related directly to the industrial history in the surroundings of the water reservoirs. In general, the composition profile of PAHs in sediment samples from the reservoirs was characterized by HMW PAHs, namely, fluoranthene, pyrene, chrysene, benzo(b )fluoranthene, benzo(a)pyrene, and benzo(a)anthracene, as well as phenanthrene, which indicated mainly pyrolytic inputs augmented with petrogenic sources in sediments from the Zemplinska Sirava reservoir. The main pyrolytic origin of PAHs with a petrogenic contribution in the Zemplinska Sirava sediments was indicated also using PCA and selected diagnostic ratios. Comparison of the total PCB and PAH

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concentrations with the limits given by the Slovak norm no. 188/2003 on the quality of bed sediments intended for the soil application (Ministry of Environment of the Slovak Republic) showed that the bed sediments from Zemplinska Sirava and Velke Kozmalovce were not suitable for the soil application due to the high concentrations of PCBs (limit value of 800 ng/g) and PAHs (limit value of 6,000 ng/g), respectively. Acknowledgement This research was financially supported by grants VEGA no. 1/4036/07 and 1/0312/08. We thank the Czech Geological Survey, Branch Brno (Czech Republic) and the Water Research Institute Bratislava (Slovak Republic) for helping us collect sediment samples and perform the analyses.

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