Heavy Metals in the Sediment of Sava River, Slovenia
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GEOLOGIJA 46/2, 263–272, Ljubljana 2003 doi:10.5474/geologija.2003.023 Heavy metals in the sediment of Sava River, Slovenia Te‘ke kovine v sedimentih reke Save, Slovenija Jo‘e KOTNIK1, Milena HORVAT1, Radmila MILA^I^1, Janez [^AN^AR1, Vesna FAJON1 & Andrej KRI@ANOVSKI2 1 Jozef Stefan Institute, Department of Environmental Sciences, Jamova 39, 1000 Ljubljana, Slovenia 2 Sava Power Generation Company, Hajdrihova 2. 1000 Ljubljana, Slovenia E-mail: [email protected] Key words: heavy metals, acetic acid extraction, normalization, river sediments, Slo- venia Klju~ne besede: te‘ke kovine, ekstrakcija z ocetno kislino, normalizacija, re~ni sedi- menti, Slovenija Abstract The Sava River is the longest river in Slovenia and it has been a subject of heavy pollution in the past ([tern & Förstner 1976). In order to determine the anthropogenic contribution of selected metals (Cd, Co, Cr, Cu, Fe, Hg, Ni, Pb and Zn) to background levels, concentrations of these metals were measured in sediments at several downstream locations. An extracting procedure using 25% (v/v) acetic acid was applied for estimation of the extent of contamination with heavy metals originating from anthropogenic activities. In addition, a normalization technique was used to determine background, naturally enriched and contamination levels. Aluminum was found to be good normalizer for most of the measured elements. The results suggest that an anthropogenic contamination of certain metal is not necessarily connected to easily extractable fraction in 25% acetic acid. As a consequence of anthropogenic activities the elevated levels of all measured elements were found near Acroni Jesenice steelworks and at some locations downflow from biggest cities. Kratka vsebina Reka Sava je najdalj{a slovenska reka in kot taka je bila v preteklosti podvr‘ena onesna‘evanju s te‘kimi kovinami ([tern & Förstner 1976). Da bi dolo~ili ~lovekov doprinos dolo~enih kovin (Cd, Co, Cr, Cu, Fe, Hg, Ni, Pb in Zn) k naravnemu ozadju so bile izmerjene vsebnosti teh kovin v sedimentu na nekaterih lokacijah dolvodno po reki Savi. Za oceno ~lovekovega doprinosa teh kovin smo uporabili metodo ekstrakcije s 25% ocetno kislino. Za dolo~itev naravnega ozadja, naravnega in antropogenega doprinosa smo uporabili metodo normalizacije. Za ve~ino merjenih kovin smo izbrali kot normalizator aluminij. Rezultati so pokazali, da antropogen doprinos dolo~ene kovine ni nujno povezan z lahkotopno frakcijo v 25% ocetni kislini. Dolvodno od Acroni Jesenice in {e na nekaterih dolvodnih lokacijah ob ve~jih mestih so povi{ane vsebnosti skoraj vseh merjenih kovin. Introduction sediment can therefore also result from their geological background (White & Tittle- River sediments can be used as an indica- baum, 1985; Murray 1996). Several stu- tor of anthropogenic, as well as natural con- dies used the normalization approach to qu- taminants that enter river ecosystem at up- antify the degree of anthropogenic pollution stream locations. Metal concentration in in different water environments (White & 264 Jo‘e Kotnik, Milena Horvat, Radmila Mila~i~, Janez [~an~ar, Vesna Fajon & Andrej Kri`anovski Figure 1. Sampling locations in Sava River and its inflows. Tittlebaum, 1985; Schropp et al., 1990, & Y a o , 1998). However, the use of Al or Fe Seidemann, 1991; D i n , 1992; Parude as a normalizer would be a problem if the et al. 1992; Covelli & Fontolan, 1997; contaminant sources introduce a large qu- T a m & Y a o , 1998). This involves dividing antity of Al or Fe into examined environ- the heavy metal concentration by that of a ment (Morse et al. 1993). reference element, which is geochemically As total metal concentration in sediment inactive and abundant in the fine-grained does not give adequate data about metal ori- material (Balls et al. 1997). Usually the Al gin it also does not provide any data about as a major constituent of alumosilicates metal solubility, mobility and potential bio- (D i n , 1992; T a m & Y a o , 1998) and Fe as a aviability in sediment. To study the bioavi- clay mineral indicator element (Morse et ability of the metals in sediment several ex- al., 1993; Kennicutt et al., 1994; Tam and traction techniques with different chemical Yao, 1998) have been used. In addition to Al extractants in single step and/or in sequence and Fe, some other conservative elements have been developed (Houba et al., 1996; such as Li (Loring, 1990), Cs (Acker- Tack & Verloo, 1996; M c G r a t h , 1996; m a n , 1980) and Sc (A c k e r m a n , 1980; Quevauviller 1997; Mainz et al., 1997; Grousset et al., 1995) have been sugge- [~an~ar et al., 2000). Chemical partition of sted. As an alternative organic carbon has sediments is used also to deduce the source also been used (D a s k a l a k i s & and pathways by which natural and anthro- O’Connor, 1995; Shine et al. 1995; T a m pogenic heavy metals have entered the envi- Heavy metals in the sediment of Sava River, Slovenia 265 ronment. For marine sediments a method ba- Zidani Most, the Savinja River flows into sed on the comparison of data for total metal the Sava River with industrial and munici- concentration and the portion extractable in pal releases from Velenje (coal mining), [o- acetic acid was suggested to asses the extent {tanj (thermal power plant), Celje (very of heavy metal contamination originating strong chemical industry) and [tore (steel- from anthropogenic activities (Loring & works). Rantala, 1992; UNEP/IOC/IAEA, 1995). The present study therefore aims: first to normalize heavy metal concentrations in ri- Sampling and sample preparation ver sediments with Al and Fe for anthropo- genic impact evaluation, and secondly to Samples were taken at all locations whe- evaluate extent of anthropogenic pollution re the Sava River is influenced by strong of heavy metals by using acetic acid extrac- industry or larger municipal releases. The tion to assess the mobility of the metal. most upstream sampling locations were on the Sava Dolinka River, which is not influ- enced by municipal and industrial releases. Experimental Further the samples were taken just few hundred meters downstream from Acroni Je- Site description senice steelworks, few kilometers upstream of Kranj, between Kranj and Ljubljana, The largest and longest Slovenian river, downstream from Ljubljana, upstream of Zi- the Sava River collects water from an area, dani most, and finally in accumulation ba- which is larger than one half of Slovenia sin of Vrhovo hydroelectric power plant (10.838 km2). Water quality in the Sava Ri- (HPP Vrhovo). The sediment samples were ver is influenced by several industrial and also collected on main the Sava’s effluents municipal releases and also by inflows of such as the Kokra River, the Kamni{ka Bi- waters that contribute naturally enriched se- strica River, the Ljubljanica River, the So- diments. In its upper flow (Sava Dolinka pota River and the Savinja River. The sam- River; Figure 1) it passes through typical pling locations are shown in Figure 1. alpine valley with clastic (claystones, sand- Sediment samples were taken by polyeth- stones, conglomerates etc.) and carbonate ylene corer (diameter 5 cm) up to depth of 5 (i.e. limestone and dolomite) rocks. The ma- cm, either from boat or in shallower waters in source of pollution in this area are the by hand. At every location at least three Acroni Jesenice steelworks, which in the past separate samples were taken. Samples were smelted iron ore and deposited byproducts transported and stored frozen at –20 °C. on landfill near HPP (Hydroelectric Power Further samples were removed from corers Plant) Moste water reservoir. Few kilome- and cut into sections that corresponded to ters downstream from Moste HPP is town the top layer of 0 to 5 cm of sediment. Then Kranj (population: 73.000) with strong in- the samples were wet sieved with deionized dustry. Nearby Ljubljana (population: Milli-Q water on a polyethylene sieve with 330.000) the Sava River receives two tribu- 0.2 mm pore size, lyophilized for 72 h to taries, the Ljubljanica River and the Kamni- constant weight, and then ground and ho- {ka Bistrica River, which are both heavily mogenized in agate mortar. The results were polluted with industrial and municipal rele- calculated to dry weight basis, determined ases that originate from Ljubljana, Dom’ale by heating a separate aliquote of the sample and Kamnik industry. Most industrial and at 105 °C until it reaches constant weight. municipal waste water from Ljubljana is cle- aned in waste water treatment plant. The water from the plant is released to the Ljub- Determination of total element ljanica River few hundred meters upstream concentrations before it reaches the Sava River. Downstre- am the Sava River passes across the Zasavje For the determination of total element region with strong chemical industry (Hrast- concentration of Al, Cd, Co, Cr, Cu, Fe, Ni, nik), coal mining (Trbovlje, Hrastnik) and Pb and Zn wet digestion method was used thermal power plant Trbovlje. Further in ([~an~ar, 2000). About 0.3 g of lyophili- 266 Jo‘e Kotnik, Milena Horvat, Radmila Mila~i~, Janez [~an~ar, Vesna Fajon & Andrej Kri`anovski zed sample was weighted into a platinum Acetic acid extraction beaker. After 2 ml of nitric acid (1:1, v/v) was added and left for 8 h. Then 12 ml of a The acetic acid extractable metal concen- mixture of perichloric and nitric acid (1:3, v/ tration was determined according to the Uni- v) was added and evaporated on a sand bath. ted Nations Environment Program (UNEP) After that 10 ml of hydrofluoric acid was procedure (Loring & Rantala, 1992; UNEP/ added and evaporated to dryness. The pro- IOC/IAEA, 1995).