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The Fluvisol and Sediment Trace Element Contamination Level As Related to Their Geogenic and Anthropogenic Source

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The Fluvisol and Sediment Trace Element Contamination Level As Related to Their Geogenic and Anthropogenic Source Vol. 59, 2013, No. 3: 136–142 Plant Soil Environ. The Fluvisol and sediment trace element contamination level as related to their geogenic and anthropogenic source R. Vácha1, M. Sáňka2, O. Sáňka2, J. Skála1, J. Čechmánková1 1Research Institute for Soil and Water Conservation, Prague, Czech Republic 2Masaryk University Brno, Brno, Czech Republic ABSTRACT The upper values of the extractability of trace elements (As, Be, Cd, Co, Cr, Cu, Ni, Pb and Zn) in 2 mol/L HNO3 and 0.025 mol/L ethylenediaminetetraacetic acid (EDTA) (compared with their pseudototal content in aqua regia) for determination of prevailing anthropogenic and geogenic soil load were proposed and compared with the results of the other 30 Fluvisol samples collected from the Labe fluvial zone. The increased geogenic load of Fluvisols was confirmed in the case of Be and As in some localities where low extractability with increased pseudototal contents were detected as opposed to the other elements when their increased pseudototal contents were followed by their increased extractability. The maps of probability of increased geogenic soil load in the area of the Czech Republic based on the comparison of geological substrates and trace element load were constructed. The combination of proposed elements extractability values for geogenic load together with developed maps is a suitable tool for the definition of prevailing Fluvisol or sediment load on some localities in the whole area of the Czech Republic. The results can be also a useful tool in the decision making processes regarding dredged sediment application on agri- cultural soil (support tool for legislative norms, Direction No. 257/2009 Sb.). Keywords: soil; dredged sediments; soil contamination; geological substrates The soil load with trace elements is caused by methods for prevailing contamination source; like natural (geogenic) and anthropogenic sources geoaccumulation index, enrichment factor or pol- of contamination. The frequent aim of chemical lution index, were described (Rafiei et al. 2010). methods is the evaluation of critical trace element Generally, the load of sediments and Fluvisols is contents in soils reducing their transfer into food predominantly connected with anthropogenic fac- chains, and respectively the other matrices of the tors in the Czech Republic (Podlešáková et al. 1994, environment (Hellmann 2002). Anthropogenically Vaněk et al. 2005). Similar results were presented induced contents of trace elements in soil support by Netzband et al. (2002) and Zerling et al. (2006) an increase of their mobility and bioavailability, in Germany. Some authors, however, pay attention generally (Němeček et al. 1996, Száková et al. 2005). to more detailed principles of Fluvisols and sedi- Although the geogenic load is connected with low ments contamination by respecting the geogenic element mobility, in some cases of extreme geo- sources of trace elements load (Schwartz et al. 2006, genic loads an increased trace element mobility was Anawar et al. 2010, Deng et al. 2010). The Fluvisol observed (Filipinsky and Kuntze 1990, Němeček et contamination can markedly limit the agricultural al. 2002). These findings show the importance of use of these soils with high fertility potential. contamination source determination for the pre- Similarly, the increased trace element load of river diction of trace element mobility and their subse- sediments was described (Heise et al. 2005). These quent transfer into plant production when different results restrict the use of dredged sediments in ag- Supported by the Ministry of the Interior of the Czech Republic, Project No. VG 20102014026, and by the Ministry of Agriculture of the Czech Republic, Project No. MZE 0002704902. 136 Plant Soil Environ. Vol. 59, 2013, No. 3: 136–142 riculture when trace element contents in dredged pointed to the local authorities responsible for the sediments exceed valid limits (Directive No. 257/2009 decision making process for example. Sb.) in many cases in the Czech Republic (Vácha et al. 2011). This legislative norm allows the use of sediment with increased trace element contents of MATERIAL AND METHODS geogenic origin in agriculture (direct application on the soils) but unfortunately does not provide a suit- The set of 30 soil samples from fluvial zones of able tool for geogenic load determination (especially the Labe river was collected. The Fluvisol sam- mobile trace element contents criteria in sediments ples (soils developed on alluvial sediments) were and soils are missing). taken from Ap horizons of agriculturally used soils We utilized the results of studies focused on (meadows, arable soils) in widths of up to 50 m from sensitivity of the extract of 2 mol/L HNO3 and river channels. This area is periodically flooded (in 0.025 mol/L EDTA for the assessment of anthro- the spring usually). The length of the study area pogenic and geogenic load with trace elements in was up to 100 km (Figure 1). The coordinates of the soils (Borůvka et al. 1996, Vácha et al. 2002) sampled localities and soil characteristics (pHH2O, and we verified this data on a set of 30 Fluvisol Cox, depth of humic horizon) were specified. The samples. These extracts seem to be promising contents of trace elements (As, Be, Cd, Co, Cr, Cu, for Fluvisols and sediments contrary to weaker Hg, Mn, Mo, Ni, Pb, V and Zn) were analysed in extracts of 1 mol/L NH4NO3 or 0.01 mol/L CaCl2 soil samples in the following extracts. for mobile trace elements contents determination Aqua regia extraction (CSN EN 13346) – pseu- because of their low contents in Fluvisols and dototal content. The extract is quantified in Czech sediments thanks to continual leaching by water legislation giving limit values to trace elements in an aquatic environment (Vácha et al. 2011). in agricultural soils (Direction No. 13/1994 Sb.) The connection of proposed upper limit values of and limit values in sediments for agricultural use trace elements extractability for geogenic load in (Direction No. 257/2009 Sb.). combination with constructed maps to determine The procedure is provided in the laboratory the areas with increased geogenic load potential temperature 2 mol/L HNO3 extraction (20°C, and the areas of Fluvial zones (polygons of the reciprocating shaker, 200 cycles per minute, 6 h, river basin of 4th order) in the area of the Czech Zbíral et al. 2004). The extract is quantified in Republic was developed as a suitable support tool Czech as 0.025 mol/L EDTA extraction – poten- for current legislation to assess the prevailing soil tially mobile contents of trace elements in soils and sediment load (geogenic, anthropogenic) ap- and sediments (Zbíral et al. 2004). Figure 1. The Labe water basin and sample points 137 Vol. 59, 2013, No. 3: 136–142 Plant Soil Environ. The soil samples for analysis were prepared from The register of contaminated sites was processed soil particles < 2 mm following the methodology by the Central Institute for Supervising and Testing CSN ISO 11464. Contents of trace elements in the in Agriculture in the Czech Republic (Kubík 2009). extract were analysed by the Atomic Absorption The database is an output of the soil agronomical Spectrometry (AAS) method using the following testing process following the Czech legislation, equipment: VARIAN AA 240Z – ETA (Palo Alto, Act No. 156/1998 Sb. USA; electrother-mic atomization) for Cd and Based on the register of the contaminated sites Be analysis, VARIAN AA 240 – FAAS (Palo Alto, database, the localities exceeding the limit values USA; flame technique) for Co, Cr, Cu, Ni, Pb and for sediment use in agriculture (Direction No. Zn analysis and VARIAN AA 240 – VGA (Palo 257/2009 Sb.) were selected (at least one element Alto, USA; hydride technique) for As analysis. exceeded the limit value on such locality). The The analyses were done in the accredited labora- geological map of the Czech Republic including 20 tory of the Research Institute for Soil and Water substrate units was divided into three categories Conservation in Prague. The quality assurance of based on the probability of geogenic load. On the analytical data is guaranteed by the control process basis of localisation of the contaminated points using matrix certificated materials (soils and sedi- from the register of contaminated sites, water ments, CRM 7001–7004, Prague, Czech Republic) basins of the 4th order were delimited using an and certified methods of the analyses. The laboratory intersect function and were depicted on a layer of test protocol of every analysis is available. geological map selected on the basis of geogenic The approach using geographical information load potential. system (GIS) was applied for the demarked ar- The data was processed by the use of elementary eas (river basin) where geogenic load could be statistical methods (Microsoft Excel, Redmont, expected. USA) and geographic information systems (ESRI The maps of geogenic load with trace elements ArcGIS 9.2, Redlands, USA). potentially influencing fluvial zones were gener- ated using following sources: Vector layer of the river basin of 4th order in RESULTS AND DISCUSSION the scale of 1:1 000 000 loaded in ESRI shapefile format, source Digital Base of water economic The selection of extracts and trace elements data (DIBAVOD, Prague, Czech Republic). extractability assessment in Fluvisol samples were Geological map of the Czech Republic in the scale calculated and evaluated with the use of previous 1:500 000, coordinate system JTSK and S42, source works (Němeček et al. 1996, Vácha et al. 2002)
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