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Spatial Distribution of Trace Metals in the Krka River, Croatia

Spatial Distribution of Trace Metals in the Krka River, Croatia

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Chemosphere 72 (2008) 1559–1566

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Spatial distribution of trace metals in the Krka River, Croatia: An example of the self-purification
´ Neven Cukrov, Petra Cmuk, Marina Mlakar, Dario Omanovic *
´ Centre for Marine and Environmental Research, Laboratory for Physical Chemistry of Traces, Ruder Boškovic Institute, POB 180, 10002 Zagreb, Croatia

a r t i c l e

i n f o

a b s t r a c t
The spatial distribution of dissolved and total trace metals (Zn, Cd, Pb and Cu) in the Krka River (partly located in the Krka National Park) has been studied using a ‘‘clean” sampling, handling and analysis technique. Differential pulse anodic stripping voltammetry (DPASV) with a hanging mercury drop electrode (HMDE) has been used for trace metal analysis. The Krka River has been divided into the upper and lower flow region with respect to the metals concentration and main physico-chemical parameters. A significant increase in trace metal concentration as the result of the untreated waste water discharge downstream of Knin Town has been registered in the upper flow region. Due to a specific characteristic of the Krka, the so-called self-purification process, a decrease in the elevated trace metals concentration from the water column takes place at numerous small lakes formed by tufa barriers (at the end of the upper flow region). The clean groundwater input at the beginning of the lower flow region additionally contributes to the observed decrease in trace metals concentration in the Krka, maintaining them at a very low level in the remaining region of fresh-water flow. The determined median total concentrations were zinc 120–7400 ng lÀ1, cadmium 3–8 ng lÀ1, lead 11–250 ng lÀ1 and copper 110–440 ng lÀ1. Karst rivers, such as the Krka River, with extremely low natural concentrations of trace metals are highly sensitive to the anthropogenic influence. Therefore, such aquatic systems require implementation of strict protection regimes in the entire catchments area. Ó 2008 Elsevier Ltd. All rights reserved.

Article history: Received 22 November 2007 Received in revised form 14 April 2008 Accepted 14 April 2008 Available online 4 June 2008 Keywords: Karst Krka River River water Self-purification Stripping voltammetry Trace metals

1. Introduction Recent review of the ‘‘toolbox” for biological and chemical monitoring requirements for the European Union’s Water Framework Directive (2000/60/EC) (WFD) pointed out that environmental monitoring programmes should be cost effective and should be based on the use of emerging and low-cost tools (Allan et al., 2006). For this purpose passive samplers and/or (bio)sensors were recommended. Concerning trace metals, results obtained by such techniques correspond to the bioavailable concentration rather than to the total/dissolved concentration. Although the bioavailable concentration is of primary importance, the total/dissolved concentration gives a general overview of the particular water body and the watershed. In addition, since there are still no recommendations regarding criteria for use and correlation of data obtained using passive samplers and chemical sensors, classical ‘‘spot” sampling and analysis in laboratories by well established methods, although more expensive and time consuming, are still inevitable and widely exploited (Horowitz, 1997). According to the water quality guidelines, one of the parameters in evaluation criteria of the natural waters ecological status
* Corresponding author. Tel./fax: +385 14680231. ´ E-mail address: omanovic@irb.hr (D. Omanovic). 0045-6535/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.chemosphere.2008.04.038

is trace metals concentrations (WFD, 2000). The fundamental ecological characteristic of trace metals is their persistence (unbiodegradability). Once introduced in an aquatic system, trace metals are redistributed into the water column (in a particulate or dissolved form), deposited/accumulated in sediment and partly consumed by living organisms (Fichet et al., 1998). Aquatic sediments are reservoirs of trace metals, however, remobilization into the water column through biogeochemical processes can occur (Ouyang et al., 2006) and significantly increase their concentration to levels toxic for aquatic organisms (Long et al., 1996; Fichet et al., 1998). Determination of spatial and temporal distribution of trace metal concentrations is very important to distinguish natural from anthropogenically introduced concentrations (Long et al., 1996; Bourg et al., 2000; Gundersen et al., 2001; Hatje et al., 2001; Korfali and Davies, 2003, 2005; Jones et al., 2004; Nimick et al., 2005; Leung and Jiao, 2006; Ouyang et al., 2006). Natural aquatic systems characterized by very low concentrations of contaminants (trace metals) are very sensitive to the anthropogenic influence. However, for many aquatic systems naturally present concentrations of trace metals are unknown. This is of a particular problem in Karst regions of Croatia where naturally present concentrations of trace metals are usually extremely low. Because of specific characteristics of Karst areas (geomorphology

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and hydrology), sources of pollution could have an influence many kilometers away, through a well developed net of subterranean streams. Therefore, it is very important to monitor concentrations of contaminants (trace metals) over a wider area of such a complex and sensitive ecosystem. For estimation of trace metal concentrations in rivers it is necessary to monitor waters starting from a spring then further downstream, taking into account river bed characteristics, and a groundwater and tributaries inflow (Kim et al., 1996; Reid et al., 1999; Gundersen et al., 2001; Hatje et al., 2001; Korfali and Davies, 2005). In this way it is possible to identify sources of pollution, as well as the fate of trace metals along the river flow. Beside specific aquatic contaminants such as trace metals, it is of great importance to measure the major physico-chemical parameters in natural waters (temperature, pH, dissolved oxygen, total alkalinity, organic matter content), since they are benchmarks of a general status of a particular aquatic system (Hunter et al., 1999; Reid et al., 1999; Jones et al., 2004). Furthermore, pH, oxygen and alkalinity affect the trace metal speciation, which was found to be very important considering toxicity for aquatic organisms (Hunter et al., 1999). The Krka River estuary has been investigated extensively in the ´ past 20 years (Prohic and Kniewald, 1987; Elbazpoulichet et al., 1991; Petricioli et al., 1996; Mikac and Kwokal, 1997; Bilinski ´ ´ et al., 2000; Cuculic et al., 2006; Cukrov and Barišic, 2006; Kwokal ´ ´ and Lovric, 2006; Omanovic et al., 2006). However, only few papers presenting only the fresh part of the Krka River have been pub´ lished (Petricioli et al., 1996; Popovic et al., 1999; Briški et al., ´ 2000; Lojen et al., 2004; Spoljar et al., 2005; Vojvodic et al., 2005; Kralj et al., 2006), but none on trace metals as a subject. The aim of this study is the evaluation of the spatial and temporal distribution of trace metals concentrations (Zn, Cd, Pb and Cu) and main key physico-chemical parameters along the Krka, taking into account all tributaries, including subterranean streams. The significance of this study is strengthen by the fact that the Krka is a part of the Krka National park (of an area of 109 km2 along the Krka River). In addition, there is no available data on trace metal concentrations and there is a lack of information on the physico-chemical water quality of the Krka. The identification of heterogeneity of the measured parameters and identification of factors that influence the distribution of measured parameters, as well as the fate of trace metals along the Krka River comprising self-purification process, are of the particular interest. 2. Experimental section 2.1. Studied area The Krka is a medium sized river in the Dalmatian Karst area of the Republic of Croatia, and drains mostly carbonate terrains. The hydrogeological drainage area of the Krka is around 2427 km2 (Bonacci et al., 2006). An average flow of the Krka at Skradinski Buk Waterfalls in last 50 years has varied between 40 and 60 m3 sÀ1, with a minimum flow of 5 m3 sÀ1 and maximum of 565 m3 sÀ1 (Bonacci et al., 2006). Significant tributaries of the Krka ˇ ˇ ´ ˇ include Krcic, Kosovcica, Orašnica, Butišnica and Cikola. The length of the fresh-water section is 49 km, while the estuary is extended for additional 23.5 km. The canyon of the Krka is located at the Dinaric carbonate platform (Herak, 1986), and is composed of carbonate rocks, mostly limestones and dolomites. Carbonate deposits are made of dissolved calcium bicarbonate that build tufa barriers or thresholds, creating waterfalls. Tufa depositing is a constant, dynamic process, involving physico-chemical factors and organisms living in the water (Lojen et al., 2004). The uniqueness of these tufa barriers and waterfalls is basic natural phenomenon of the Krka National Park.

In Fig. 1 the studied area and locations of sampling sites are presented (see Table 1 for description and codes). In total, 13 sampling sites were selected from the spring to the end of the fresh-water part of the Krka. These sites represent the most critical points with regards to expected anthropogenic influence as well as to natural processes (like self-purification). Sampling of surface water on these 13 sites were performed during dry and rainy seasons during a period of 3 years: November 2004; January, May, July 2005; May and July 2006; and February 2007. Sampling locations were spotted by the GPS device (Garmin GPS Map 76CSx with the accuracy of ±5 m). 2.2. Materials and methods Measurements of physico-chemical parameters (water temperature, pH, dissolved oxygen) were performed in situ. pH was measured by a portable instrument Mettler MP 12, dissolved oxygen by Oxymeter Mettler MO 128, and water temperature by a mercury thermometer submerged under water for 5 min, with additional measurements by a thermometer built in a Mettler Oxymeter probe (a difference between these two measurements was always <1 °C). pH and Oxymeter were calibrated prior to each sampling event and checked every day. For alkalinity measurements, water samples were taken into glass Pyrex bottles (250 ml) and determined by the standard titration method. Samples for trace metal analyses (zinc, cadmium, lead and copper) were taken respecting a principle of a ‘‘clean sampling technique” (Horowitz, 1997), into high density polyethylene (HDPE) bottles (1 l), previously cleaned with nitric acid and rinsed with Milli-Q water. Surface water samples were taken 0.5–1 m away from the river coast at 20 cm depth. Analysis of both total (unfiltered) and dissolved (filtered with 0.45 lm cellulose–nitrate filters) trace metals was carried out. Prior to the measurements, water samples were digested by acidification with conc. HNO3 (suprapur, Merck, Darmstadt, Germany), pH < 2 (2 ml of acid to 1 l of sample) and additionally irradiated by UV-light (mercury lamp 150 W, Hanau, Germany) for at least 24 h. Typical blank values for all measured metals were below a detec-

Fig. 1. Overview of the studied Krka River area and locations of sampling sites.

N. Cukrov et al. / Chemosphere 72 (2008) 1559–1566 Table 1 Codes, description and geographical coordinates of sampling sites for Krka River and tributaries Code Krka River NPK 1 NPK 2 NPK 3 NPK 4 NPK 5 NPK 6 NPK 7 NPK 8 NPK 9 NPK 10 Tributaries BR MC CK ZR Site description ˇ ´ Krka spring (before mouth of river Krcic) Knin (bridge) ´ Waterfall Bilušica buk (below waterfalls) Brljan lake (above water-gate) Power plant Miljacka (before effluent) Krka monastery (port) Waterfall Roški (upper part) Visovac lake (west coast) Visovac lake (east coast – port) Waterfall Skradinsk buk (above waterfalls) Butišnica (before tributary into the Krka River) Miljacka cave IV (near power plant Miljacka) ˇ Cikola River (bridge) Zrmanja River (sink) Coordinates N N N N N N N N N N N N N N 44°02.5510 , 44°01.9650 , 44°00.7880 , 44°00.5750 , 44°00.1330 , 43°57.7000 , 43°54.4430 , 43°51.8650 , 43°51.7470 , 43°48.2070 , 44°02.7780 , 44°00.2100 , 43°50.2520 , 44°05.7190 , E E E E E E E E E E E E E E 16°14.1090 16°11.4340 16°04.0750 16°02.1570 16°01.1000 15°59.5310 15°58.5790 15° 7.6750 15°58.7350 15°58.3080 16°10.2300 16°01.1450 16°02.9350 16°01.2450

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Distance from spring (km) 4.6 7.1 17.7 20.7 24.2 31.2 37.8 42.5 43.2 50

Table 2 Main measurement parameters used for the determination of trace metals in water samples by DPASV Parameter pH Accumulation potential, Eacc Accumulation time, tacc Initial potential, Eini Final potential, Eend Interval time, tind Pulse time, tpuls Amplitude, A Step increment, Est inc Cd, Pb, Cu <2 À0.8 V 600 s À0.75 V 0.24 V 0.1 s 0.04 s 20 mV 2 mV Zn $3.5 À1.3 V 180 s À1.15 V À0.75 V 0.1 s 0.04 s 20 mV 2 mV

Water Reference Material for Trace Metals (SLRS-4), purchased from the National Research Council Canada. A very good agreement with the certified data was obtained (Table 3). 3. Results and discussion 3.1. Temperature, pH, total alkalinity and dissolved oxygen A spatial and temporal distribution of the surface water temperatures of the Krka is presented in Fig. 2A. The river water temperature at all sites, except NPK 1 and MC, showed typical seasonal variability, reflecting changes of air temperature and dynamics of the river flow. Sites with the lowest temporal/seasonal changes were the Krka spring (NPK 1), and two sites next to the Miljacka hydroelectric power plant (MC and NPK 5) where new fresh-water originating from Zrmanja River enters into the Krka by subterranean streams. Spatial and temporal distributions of pH values are presented in Fig. 2B. Although seasonal variations of pH were not registered, there was a strong spatial variability along the Krka. Starting from the Krka spring (NPK 1), pH increased from about 7.5 to 8.3 (NPK 3, NPK 4) due to CO2 degassing. Around site NPK 5 there are several groundwater inputs to the Krka with lower pH (due to the carbonate terrain, such is cave water MC), causing pH to decrease to about 7.4. The ratio of the water mass of Krka and groundwater at this site (NPK 5) is unknown, but according to the difference in temperature and pH, it seems that more water is entering from subterranean streams than it is brought by the Krka. Downstream of the site NPK 5, pH rises to about 8.1 and remains constant to the end of fresh-water part (NPK 10). The highest pH values (about 8.6) were detected in waters of the tributary ˇ Cikola, due to clastic rocks and the Drniš city anthropogenic influence. Fig. 2C shows the spatial distribution of total alkalinity (TA). For each sampling period average values are plotted to show clear distinction between the upper and lower flow of the Krka. As the Krka flows through the carbonate terrain, the measured TA can be considered predominantly to be carbonate. A higher TA was measured during a cold period because solubility of carbon dioxide was enhanced, and therefore, the concentration of dissolved carbonate from carbonate rocks was also higher. The highest average TA value was measured in cave water (MC) characterized by the lowest pH. In contrary, the lowest TA was measured in waters of the ˇ tributary Cikola, with the highest pH values. In overall, the systematic trend of spatial TA distribution was opposite to that of pH, which agrees well with results obtained by Lojen et al. (2004). However, our TA values were twice of that obtained by Lojen

Table 3 Measured and certified concentrations of trace metals (in ng lÀ1) in River Water Reference Material for Trace Metals (SLRS-4) Zn Measured Certified LOQa 931 ± 40 930 ± 100 10 Cd 10.8 ± 0.4 12.0 ± 2.0 1 Pb 83.3 ± 1.5 86.0 ± 7.0 2 Cu 1721 ± 86 1810 ± 80 5

a LOQ (limit of quantification) – obtained in acidic MQ water, based on standard addition method and 10r rule (for 10 min accumulation time).

tion limit, or were insignificant in comparison to concentrations measured in natural waters. Trace metal concentrations were measured by differential pulse anodic stripping voltammetry (DPASV) using AUTOLAB PGSTAT12 instrument (Eco-Chemie, Utrecht, Netherlands). A three electrode system was used with hanging mercury drop as a working electrode (VA stand 663, Metrohm, Herissau, Suisse), with a drop surface of 0.25 mm2. A platinum wire was used as a counter electrode and Ag|AgCl with saturated NaCl as a reference electrode. The standard addition method was used for determination of trace metal concentrations. All measurements were carried out automatically, by means of the PROJECT mode integrated in the GPES 4.9 software and by using Cavro XL 3000 burette system (Tecan, USA). Trace metals concentrations were measured in the same sample solution. In the first step concentrations of Cd, Pb and Cu were determined, and after adjusting pH to about 3–4 by the addition of 100–200 ll of sodium acetate, a zinc concentration was determined. The applied parameters for DPASV technique are presented in Table 2. Quality control of the applied voltammetric method was verified by determining the concentration of these four metals in River

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Fig. 2. Distribution of the temperature, pH and total alkalinity in the Krka River.

et al. (2004). According to a theoretical ratio of Ca2+ and TA, which is 2 for CaCO3 dissolution, our measured TA values (about 4.7 ± 0.7 mmol lÀ1) were in accordance with values of Ca2+ concentrations presented by Lojen et al. (2004). However, according to the author’s personal information, a calculation error in the order of a factor of 2 was introduced in the paper of Lojen et al. (2004). Besides the importance of TA in characterization of chemical composition of a particular water body, TA it is also important in determining the stream’s ability to neutralize acidic pollution from rainfalls or waste waters (it serves as a buffer, mainly bicarbonate ðHCOÀ Þ and carbonate ðCO2À Þ). 3 3 In addition to temperature, pH and TA, the concentration of dissolved oxygen was also measured. A systematic trend in the oxygen content along the Krka, such as in the case of temperature and pH, was not observed. In general, lowest variations of the oxygen content were observed in regions of slow and calm flow, while in parts with a relatively fast river stream and small waterfalls, variations were higher. 3.2. Distribution of trace metals Examination of results of total and dissolved trace metal concentrations (zinc, cadmium, lead and copper) for all sampling periods (seven events) did not show evident seasonal variations. For presentation of specific conditions of the Krka River with regards

to trace metals concentration median values were chosen for graphical presentation, while the Electronic Supplementary Material (ESM) of this paper summarizes all measured values. A spatial distribution of total and dissolved zinc, cadmium, lead and copper median concentrations along the Krka, is presented in Fig. 3. As pointed out, the Krka can be divided into two regions with respect to hydrology conditions and measured physico-chemical parameters. These two regions could also be clearly distinguished on the basis of their trace metal concentrations. In general, extremely low concentrations were found in the spring water. Only a few kilometers downstream the Knin Town is located. The position of a sampling site in the town (NPK 2) is selected in order to obtain a clear evidence of the expected anthropogenic influence (in the vicinity of a waste water discharge). In that sampling site (Fig. 3) trace metal concentrations were considerably enhanced. A significant increase in zinc concentration was detected (about 60 times for total, and about 25 times for dissolved concentration) compared to spring waters. Although the total Cd concentration was by about 70% higher, dissolved fraction was about 25% of that in the spring water. Total and dissolved concentrations of lead were 25 and 3 times higher, respectively. The total concentration of copper was about 4 times higher and that of dissolved copper by about 50% higher. The highest values registered at this site were 64 000 ng lÀ1 Zn, 60 ng lÀ1 Cd, 7800 ng lÀ1 Pb and 6000 ng lÀ1 Cu. However, these high concentra-

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Fig. 3. Spatial distribution of median dissolved and total trace metal concentrations in the Krka River.

tions were measured in the sample taken during the unusual very intensive untreated waste water discharge in the vicinity of the sampling site. As the concentration of suspended particulate matter was not measured in this study, it was not possible to calculate partition coefficients. However, it is evident that the ratio of dissolved and total metal concentrations is the lowest at NPK 2 (the town of Knin) indicating high portion of trace metals associated to particulate matter of an anthropogenic source (see Fig. 3). Downstream, at sites NPK 3 and NPK 4, trace metal concentrations in river water decreased, but were still appreciably influenced (especially zinc and lead) by untreated waste waters from the town of Knin. Namely, gradual dilution by the waters of Krka River itself and by the water of surface tributary Butišnica (which merges with the Krka River about 1 km downstream of the last

waste water discharge) caused lowering of trace metal concentrations at sites NPK 3 and NPK 4. Moreover, the deposition of particulate fraction of trace metals into the sediment additionally contributed to the observed concentration decrease. It is important to emphasize that the physico-chemical forms of cadmium in water at these three sampling sites (NPK 2, 3, and 4) revealed the same behaviour, in comparison to all other sites, as well as other metals. Namely, the lowest dissolved cadmium concentrations and consequently the highest ratio of its total and dissolved forms were registered. It is known that cadmium has a relatively weak adsorption affinity onto natural particulate matter (Bilinski et al., 1991). However, one can presume that the specific type of particulate matter from waste water contributes to cadmium adsorption.

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Furthermore, at NPK 3 and NPK 4 only total concentrations of zinc and copper were decreased, while their dissolved concentrations remained practically unchanged. This means that the majority of particular zinc and copper was removed from the water column between NPK 2 and NPK 3. Thus, the expected decrease of total zinc and copper concentrations in the water sampled at NPK 4 (located at the end of Lake Brljan), was not registered. Lead concentrations underwent different profile. A gradual decrease in total lead concentrations starting from NPK 2 to NPK 4, was registered (as the consequence of the particulate form sinking – self-purification process). Dissolved concentrations remained at a relatively low level, due to lead affinity to adsorption onto particulate matter (Bilinski et al., 1991). The most important section of the Krka River regarding trace metal concentrations is between sites NPK 4 (Lake Brljan) and MC/NPK 5. In this part, numerous small cascade lakes with related waterfalls are formed (the Manojlovac waterfalls) by tufa barriers. These lakes/barriers operate as traps for particulate forms of trace metals, resulting in self-purification of the water. The self-purification takes place due to the intensive sedimentation process, which starts in the Lake Brljan and the subsequent tufa barriers. It was recently observed that rivers whose drainage basin is underlain by limestone and characterized by high aqueous pH and alkalinity, posses a self-purification capacity for trace metals, primarily through association with carbonate species (Korfali and Davies, 2003, 2005). The same mechanism could be attributed to the water system of the Krka. This natural process of water purification, together with the groundwater input downstream of these barriers, lowers total concentrations of trace metals to the level registered in Krka River spring (evident mostly for zinc and lead). Considering main physico-chemical parameters, downstream of sites MC/NPK 5 starts the lower region of the Krka flow. In water samples taken at the first downstream site (NPK 6), slightly increased trace metal concentrations (except cadmium) were determined. This is probably caused by the water returned back into the river flow previously collected for the hydroelectric power plant purpose. Additionally, enhanced median trace metal concentrations were partly a consequence of tourist boat traffic in this region, which was registered in samples collected during the summer (tourist) season. Weathering processes also contributed to the trace metal input in the river water. In general, the lower flow region of the Krka was characterized by the relatively uniform distribution of the trace metal content. In July 2005, very high total concentrations of copper (5900 and 3200 ng lÀ1) at two sites (NPK 7 and NPK 9), were registered. At the same time, at site NPK 8, which is located in Lake Visovac as site NPK 9, a total concentration of copper was 112 ng lÀ1. However, this site is a little outside of the main water flow in the lake. Since only copper concentrations were enhanced, sample contamination is less probable. The reason of the enhanced copper concentrations at these two sites for this particular sampling event is unknown. ˇ The periodic tributary Cikola (CK) is merged with the Krka downstream of Lake Visovac and upstream of Skradinski Buk ˇ Waterfall (NPK 10). Total metal concentrations in water of Cikola were slightly increased, but without a significant influence on trace metal concentrations in the water at NPK 10. Downstream of NPK 10 starts Skradinski Buk Waterfall, which consists of seventeen tufa cascades, islands and lakes, and extends 800 m in length. At the end of Skradinski Buk Waterfall starts Krka River Estuary. According to the results presented above, three main features regarding the distribution of trace metal concentrations could be extracted. First is the appreciable anthropogenic influence in the upper flow region of the Krka River, caused by untreated waste waters from the town of Knin. Secondly, this pollution maintains elevated trace metal concentrations several kilometers downstream to the section characterized by several cascade lakes where

self-purification takes place. Subsequently, the third essential segment includes the subterranean inflow of the fresh, very clean groundwater, which diminishes trace metal content by dilution. As pointed out in Introduction, there is no published scientific data on trace metals in the Krka. However, in the document available at ‘‘http://www.voda.hr/docs/Krka_EN.pdf”, concentrations of these trace metals at two sampling sites were denoted. According to these data, trace metal concentrations at NPK 10 (‘‘clean” site) were higher than at NPK 2 (the town of Knin, ‘‘polluted” site). Furthermore, concentrations of zinc, cadmium, lead and copper present at NPK 10 were about 50, 150, 70 and 30 times higher than our values, respectively. For very sensitive aquatic systems as the Krka River, such data are adverse, because they do not reflect authentic conditions. It is important to point out the importance of accurate determination of natural, very low trace metal concentrations, prevalent in rivers of Karst regions in Croatia. According to the national water quality guidelines (OG 77/98), the Krka River is classified mostly within Class I, concerning the trace metal concentrations. Exceptions are only two sites downstream of the town of Knin, where concentrations of some metals pass into Class II. Such generally

Table 4 The input parameters used for the speciation modelling (a) and the predicted distribution of dissolved Zn, Cd, Pb and Cu in water of the Krka River (b) Concentration (a) pH DOC Zn Cd Pb Cu Ca Mg Na Carbonate Chloride Nitrate Sulphate Metal (b) Zn(II) 8 0.5 5 0.05 0.05 2 2.1 0.45 0.565 4.5 0.31 4.00E-03 0.6 Metal specie Free Zn+2 ZnOH+ Zn(OH)2 (aq) ZnSO4 (aq) ZnCO3 (aq) ZnHCOþ 3 FA-Zn HA-Zn free Cd+2 CdCl+ CdSO4 (aq) þ CdHCO3 CdCO3 (aq) FA-Cd HA-Cd free Pb+2 PbOH+ PbðCO3 ÞÀ2 2 PbCO3 (aq) þ PbHCO3 FA-Pb HA-Pb CuCO3 (aq) FA-Cu FA-CuOH HA-Cu HA-CuOH unit

mg lÀ1 nmol lÀ1 nmol lÀ1 nmol lÀ1 nmol lÀ1 mmol lÀ1 mmol lÀ1 mmol lÀ1 mmol lÀ1 mmol lÀ1 mmol lÀ1 mmol lÀ1 % of total 41.7 3.2 3.6 2.1 29.7 3.8 10.4 4.9 45.8 0.9 2.5 4.2 13.3 21.9 10.5 0.8 1.4 2.2 31.6 1.8 42.1 19.9 0.4 25.6 41.0 12.7 20.3

Cd(II)

Pb(II)

Cu(II)

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low concentrations of measured trace metals in the Krka do not mean that the capacity of trace metals reception is high (e.g. to fit into Class I). Contrariwise, they show that clean Karst aquatic systems are very sensitive on anthropogenic influence, which is clearly evident for the upper flow of the Krka River. 3.3. Speciation modelling of dissolved trace metals

This study identified the magnitude of the anthropogenic influence on spatial distribution of trace metal in the Krka River. As the majority of the trace metals introduced by sewage effluents are deposited in small lakes in the upper flow of the river, further investigations are required to assess the risk of the remobilization of metals from the sediment. Acknowledgements

The major ion composition of the Krka water was not measured in this work. However, some information could be found in the lit´ erature (Lojen et al., 2004; Vojvodic et al., 2005; Kralj et al., 2006) and are given in Table 4a. VisualMinteq is used for the prediction of trace metal distribution (speciation) according to the major and trace metal composition representing the mean composition of the Krka River. A Stockholm humic model (SHM) is used for the trace metal–organic matter interactions. Typical fulvic acid (FA) and humic acid (HA) parameters offered by the program were used in the calculation. It is assumed that 70% of active dissolved matter (DOM) is FA (Table 4b). Speciation modelling shows a different pattern of the trace metal distribution regarding the inorganic and organic distribution. The content of organically bound metals reflects their common affinity for association to natural and synthetic organic ligands (Cu > Pb > Zn $ Cd). Although the assumed DOC concentration is relatively low (0.5 mg/L), the model shows that copper is bound more than 99% to organic matter. Carbonate is the main inorganic species for lead, while free (hydrated) ion and carbonate are predominant inorganic species for cadmium and zinc. Precipitation of trace metal carbonates is not likely to occur because the calculated saturation index (SI) for all trace metals is negative. The model predicted a relatively high free ion portion (the most toxic form) of zinc and cadmium. As the total dissolved concentration of cadmium in the Krka is extremely low, this level of free ion concentration could be considered as non-toxic. Model calculations showed that the river water is oversaturated with respect to calcite and aragonite, having SI of 0.7 and 0.85. These values are similar to those calculated and reported in the paper of Lojen et al. (2004) and indicate that precipitation of carbonates is likely to occur under specific conditions in the river water (see Lojen et al. (2004) for details). Under such conditions a part of dissolved trace metals could co-precipitate from the water column contributing to the self-purification process taking place in the lakes formed by the tufa barriers (Korfali and Davies, 2003, 2005). 4. Conclusions This study provides the first survey of trace metal content in the Krka River using ‘clean’ methods and techniques of sampling, handling and analysis. Consequently, concentrations of Zn, Cd, Pb and Cu measured in the water of the Krka River are amongst the lowest reported in the literature for freshwater systems. Concerning spatial distribution of main physico-chemical parameters and trace metals, the Krka was divided into the upper and lower flow region. In the upper flow region, near the spring, trace metal concentrations are significantly increased (by factors up to 60) due to the input of Knin Town untreated waste waters. Downstream, concentrations of trace metals decrease, but still remain at elevated values. At the end of the upper flow region, a significant self-purification process takes place trough several small lakes (Manojlovacki Waterfalls) formed by tufa barriers resulting in significant decrease of trace metal concentrations. Low trace metal concentrations at the lower flow region of the Krka are supported by the considerable subterranean inflow of the clean groundwaters originating from the Zrmanja River.

The financial support of the National Park ‘‘Krka”, under Project ‘‘Geochemistry of Ecotoxic Metals in the National Park of Krka” and Ministry of Science, Education and Sports of the Republic of Croatia, under Project 098-0982934-2720, ‘‘Interactions of trace metals in aquatic environment”, is gratefully acknowledged. Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.chemosphere.2008.04.038. References
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