ACCUMULATION IN FOODS AND CROPS Determining Trace Elements in the Land and Water Material G. Dembska 1, G. Sapota, M. Bogdaniuk, Ł. Zegarowski, S. Wiśniewski, A. Flasińska, B. Aftanas

Maritime Institute in Gdańsk, Department of Environmental Protection, Długi Targ 41/42, 80-830 Gdańsk POLAND, [email protected]

Abstract The aim of the work was devising the method of the mineralization and determination trace metals in the land and water . As part of the work a method of the mineraliza- tion (reducing to ashes) of land and water plants samples was working out. The measuring parameters of determining chosen trace elements on the PERKIN-ELMER spectrometer ICP-OES Optima 2000DV with excitation in plasma were optimized. The method valida- tion was conducted, uncertainties of the method were estimated for individual elements, and a correctness of method was tested in the comparing investigations (intercalibration). The devised method was used for indicating the content of metals in growing grass around hearth waste sites and water plants from the Gulf of Gdansk. Key words: Heavy metals, land and water plant material, ICP-OES, Baltic Sea, Gulf of Gdansk, Puck Bay

Introduction alization with acids, in the closed arrange- The toxicological meaning of heavy ment, under the increased pressure with the metals results mainly from their perma- application of the microwave energy. This nence in the environment, of the accumula- method apart from many virtues (short time tion and selective working on some tissues of analysis, simplicity of the method, little of organisms. Plants are an essential link in reagent's consuming etc.) has two funda- the migration of metals from soil and air to mental faults: price of apparatus to the min- the animals and the man. Some species of eralization and need to apply small amount plants can be bioindicators of environmental of analysed samples. pollution. Abilities of plants can also be used The second method of the "on wet" for removing and the detoxification of heavy mineralization is warming plant samples metals for cleaning and monitoring the land with oxidizing acids under the manoeu- and water environmental - fitoremediation vrable radiator (Rashed, 1995; Lavid et al., techniques. 2001; Kara, 2009). This method is charac- Environmental samples are very diverse terized by a possibility of the use bigger research material, both on account of the amount of analysed samples. The fault of place of taking a sample, the type of the the method is long time of analysis (often matrix, as well as the possible spectrum of necessary to repeat with reason of not com- analytes. The preparation for analysis of plete mineralization). plant samples is a usually complicated task. The most popular of the "on drily" min- The operations and processes being included eralization is incineration. This method con- in this stage can be with both the cause of the sists of the slow decomposition of organic loss and the source of additional contamina- matter in the oven in the temperature 5500C tion (Namieśnik et al., 2000). The majority on ash mainly composing from carbonates of analytical methods require conducting and oxides, which next are dissolute in right samples to solution, as well as sometimes acid or mixture of acids (Ostrowska et al., allocating, dividing and concentrating of ana- 1991; Isildak et al., 2004; Aberoumand et al., lyte. Conducting analysed samples to solu- 2009). The time of analyse is long, however tion most often reaches through the mineral- the method is very good for appointing non- ization. We can distinguish two main ways of volatile elements (total spreading of organic the mineralization: "on wet" and "on drily". matter, eliminating it from the matrix, elimi- The most popular method of the "on nation of interference). wet" mineralization of the plant material is a microwave mineralization (Sardas and Materials Penuelas, 2006; Baldantoni and inn., 2009; The samples for examinations were Lafabrie et al., 2009). It is most often miner- terrestrial grass and aquatic plants.

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The terrestrial grass was taken in Division: Angiosporous (Magnoliophyta November 2009 near hearth landfill sites in Cronquist) Rewa (R4, R 5, R6, R7, and R16), Letnica Class: Monocotyledonus (Liliopsida Brongn.) (L1, L5) and Przegalina (P11, P22, P24, KP Order: and WG - soil-forming layer). Species com- Family: Dumort. position of samples weren't established. Genus: Potamogeton L. The aquatic plants were taken in Species: Potamogeton sp. (Pondweed) November and December 2007. The Sea-grass The pondweeds are high underwater plants (Zostera marina ) was collected in the Gulf of constituting the team usually farthest dis- Gdansk close to dripping breakers - Orłowo tant from the shoreline of the lake with the area (O/I/1, O/II, O/III, O/V, O/VI/1, O/VI/2). sludgy bottom. They are also found in brack- The Pondweed ( Potamogeton sp. ), ish waters e.g. in the Puck Bay. Horned pondweed ( palustris ) and Baltic stonewort ( Chara baltica ) were Division: Angiosporous (Magnoliophyta collected around exploitation hollows in the Cronquist) Puck Bay (I, II, III, IV, V, VI, IV-V/w, VI/w) - Class: Monocotyledonus (Liliopsida Brongn.) fig. 1. The air-dried samples were stored in Order: Alismatales polythene bags in the room temperature Family: Zannichelliaceae Dumort. until the time of analysis. Genus: Zannichellia L. Description of examined species Species: Zannichellia palustris (Horned Division: Green algae (Chlorophyta) pondweed) Class: Charophyceae The horned pondweeds most often grow in Order: Charales the dispersion in shallow waters (to 1 m Family: Characeae depth). It is a species threatened with Genus: Chara becoming extinct, also in Polish waters. Species: Chara baltica (Baltic stonewort) The Baltic stonewort can tolerate salinities Division: Angiosporous (Magnoliophyta up to 18 PSU but it more frequently occurs Cronquist) in lower salinities (to less than 1 PSU). How- Class: Monocotyledonus (Liliopsida Brongn.) ever, it does seem to require some salt, even Order: Alismatales if only carried to the site by the wind. Family: Zosteraceae Genus: Zostera L. Species: Zostera marina (Sea-grass)

Figure 1. Location of the sampling stations in the Puck Bay (the Baltic Sea) - (Kruk - Dowgiałło and Opioła, 2009).

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In Poland the sea-grass is provided with the The concentrations of heavy metals in rigorous species protection and put in the investigated plant samples were determined. group of extinct species (treat category: E) on It is stated that hearth waste gathered on the Red List of Plants and Mushrooms of investigated dumps didn't influence nega- Poland (Mirek et al., 2006). tively to the content of metals in grass grow- ing around them. The grass (according to Methods Institute of Soil Science and Plant (IUNG) The incineration method in the oven guidelines of Puławy - Kabata-Pendias, (5500C) was selected for plants samples 1993) is suitable for fodders in the state fresh (Polish Norm PN-R-04014:1991). In miner- and dried off. alizated samples the concentration of heavy The highest concentration of mercury metals (Pb, Cu, Zn, Ni, Cd, Cr) were deter- was stated in Sea-grass samples collected mined using atomic spectrometry emission between the southern and centre bar and with excitation in plasma inductive coupled between the centres and northern bar. The (ICP-OES) on the spectrometer Optima highest concentrations of Zn, Pb, Cu, Cd, Cr 2000 DV, PERKIN - Elmer. and Ni were determined in samples collect- The concentration of Hg (in non - min- ed behind northern bar. The low concentra- eralizated samples) was determined using tions of analysed elements were in samples the atomic absorption after the thermal taken in the centre bar area - fig.2. decomposition on the spectrometer MA- 2, The high concentrations of Pb, Cu, Zn, Nippon Corporation Instrument. The dry Ni, Cd and Cr in examined aquatic plants mass was determined according to the norm were stated in Zannichellia palustris and Hg PN-R-0401: 1998. in Potamogeton sp - fig. 3. The low concen- The method was validated and uncer- trations of examined metals were observed tainty of each analysed element was calculated. in Chara baltica . The conducted investigations of aquat- Results and Discussion ic plants had pilot character. In order to state The methodology of determining met- whether examined species are bioindicators als in terrestrial grass and aquatic plants was of pollutants in the given area, we should drawn up with method ICP-OES, after incin- compare concentrations of metals from eration the sample. The measuring parame- more samples with the results of sediments ters of determining selected elements on and water from the given area. spectrometer OPTIMA 2000DV, PERKIN - ELMER and MA-2 Nippon Corporation Reference Instrument were optimize. The method was Aberoumand A., Deokule S. S., 2009, validated and the limit of detection, limit of Determination of Elements Profile of Some determination, working scope, precision in Wild Edible Plants, Food Anal. Methods limit of the repetitiveness, accuracy, linearity (2009) 2,116-119. and selectivity were determined. The stan- Baldantoni D., Ligrone R., Alfani A., dard and extended uncertainty of the method 2009, Macro- and trace- element concentra- was estimated for the extending coefficient tions in leaves and roots of Phragmites 101, k= 2, by the probability level 95% - tab.1.

Table1. Results of validation and extended uncertainty determining trace elements in the land and water plant material ICP-OES methods, after reducing to ashes and AAS methods (Hg) after the thermal decomposition on the spectrometer MA- 2.

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Figure 2. Content of heavy metals [mg/kg d.m.] (Hg- µg/kg d.m.) in Zostera marina from the Gulf of Gdansk - Orłowo area

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