Assessment of toxicity of heavy metals accumulated in lake sediments

Vladimir Dauvalter

Institute of the North Industrial Ecology Problems (INEP), Kola Science Centre, Russian Academy of Sciences, 14 Fersman St., 184200 Apatity, Murmansk region, Russia

Phone: +7 81555 79786, Fax: +7 81555 79772, E-mail: vladimir@inep.ksc.ru

 

     Sediments are habitat and energy supply for many freshwater organisms, which are used by man in food. The polluting substances are accumulated by sediments and then enter in water organisms as a result of live activity. Bioaccumulation and transition of polluting substances by food chain are the complex processes, on which geochemical, environment, physiological and biochemical features of organism influence. It is very difficult to give the exact prognosis of influence of the polluting substances accumulated in sediments on live organisms. It is difficult also to determine a degree of biological influence of polluting substances, particularly heavy metals, first, because different organisms in a various degree are subject to their influence, and, secondly, owing to complex behaviour of metals in reservoirs. The metals can be considered as biologically available chemical substances, when they are consumed by organisms and participate in their metabolism.

     The aim of the investigation is the assessment of toxicity of heavy metals (Ni, Cu, Zn, Mn, Fe) accumulated in lake sediments by ammonium acetate extraction technique. This extraction is offered as one of techniques to define an influence of the toxic forms of metals accumulated in sediment for the period of activity of the industrial enterprises on aquatic plants and animals and water ecosystems.

     Sediment samples were collected at 18 stations of various zones of Imandra Lake (the largest reservoir of Murmansk Region) polluted by air emissions and wastewaters of mining and metallurgical enterprises.

Metal concentrations were determined by flame atomic absorption spectrophotometry (Model Perkin-Elmer 460 and 560) using the standard addition technique. For total metal analyses ~ 0.4 g (dry wt.) was taken and digested in a Teflon “bomb” for 4 h at 140°C with 4 ml concentrated nitric acid.

To determine the metal contents in the mobile form the sediment samples of superficial (0-1 cm) and background (between 20 and 30 cm) layers were digested by 1M solution of NH4OAc (pH=4.65) in weight ratio 1:10 during ~15 h with subsequent agitation during 2 h. After centrifugation (at 6000 rev/min.) the metal concentrations by flame atomic absorption spectrophotometry were determined in the solution.

     From a wide spectrum of investigated elements the heavy metals essential to live of water organisms of Imandra Lake have been chosen. They are priority pollutants Ni, Cu, Zn; Mn and Fe, i.e. metals, oxides and hydrooxides of which are perfect adsorbents of heavy metals and behaviour of which depends on physical and chemical environment conditions (pH, Eh).

     Concentrations of the mobile forms of Ni (Nimob.) in sediment of Imandra Lake in superficial and background layers were 1-69 % (in average 23%) of total concentrations (Nitot.). The maximal value of Nimob. (10940 mg/g dry wt.) was found in most polluted water area of Imandra Lake – Monche Bay, where the wastewaters of Ni-Cu metallurgical Company “Severonickel” enter. The Nimob. value was 69% of Nitot. (15940 mg/g dry wt.). The part of the mobile forms of Ni in superficial layer was in 2.5 times more that in background. Therefore, increasing total concentrations in the superficial polluted sediment amplify the part of the mobile forms of Ni, i.e. alongside with increasing Nitot. in sediments of the polluted zones of Imandra Lake the percentage of the contents of the mobile forms was also raising. Therefore, the ecological risk for aquatic plants and animals and for whole lake ecosystem is increasing.

     The same appropriateness, as for distribution of Ni, is characteristic for distribution of the mobile forms of Cu in sediments of Imandra Lake. However, the part of the mobile forms of Cu in total concentrations is lower. Concentrations of Cumob. in sediments of Imandra Lake were 4-39% (in average 13%) of Cutot.. The part of Cumob. in superficial sediment layers, as well as Nimob., in average in 2.5 times is more, than in background layers. Therefore, as well as for Ni, with increasing Cutot. in sediments in the polluted zones of Imandra Lake the part of Cumob. was also raising, i.e. the ecological risk of Cu pollution for aquatic biota increased.

     Significant difference in distribution of Znmob. in superficial and background sediments of Imandra Lake was not noticed.

     The research of the mobile forms of Mn and Fe in sediments is very important, because Mn and Fe play one of the central roles in migration of elements, including heavy metals. Mn is able to be accumulated in water environment basically owing to reduction of Eh and pH; versus other heavy metals, for it the low involving in complex compounds are characteristic; Mn has the less ability to associate with organic compounds.

     The appropriateness of distribution of Mnmob. in sediments of Imandra Lake is different from that for Ni and Cu. Concentrations of Mnmob. in superficial and background sediment layers of Imandra Lake were 4-95% (in average 48%) of Mntot.. Of all investigated metals Mn has the largest part of the mobile forms. Versus Ni and Cu, with increasing Mntot. in superficial sediments of Imandra Lake the part of the mobile forms reduced. In background sediment layers the part of Mnmob. increased. To illustrate, distribution of Mn in sediments of Kurenga Bay, where during a half of the century the wastewaters of Olenegorsk ore dressing plant, which extracts and enriches of iron ores (magnetite and haematite quartzites) with a high content of Mn, enter. In superficial 0-1 cm layer Mnmob.=24% Mntot. (5500 and 22900 mg/g dry wt., respectively). In 19-20-cm background layer Mnmob.=83% Mntot. (3300 and 4000 mg/g dry wt., respectively). It is possible to explain this phenomenon, that in anoxic conditions at the lower depth of sediments in reduced conditions the significant part of Mn is in the mobile form, and in superficial layer owing to contact of sediment with superstratum water saturated with oxygen, Mn oxidized and passed in the insoluble forms.

     The appropriateness of distribution of Femob. in sediments of Imandra Lake was similar to that revealed for Mn. However, the part of the mobile form of Fe was much lower - 0.3-9% (in average 3.6%). As well as for Mn, it was found, that with increasing total concentration of Fe in superficial sediments of Imandra Lake the percentage of the mobile forms reduced in comparison with background layers. For example, in superficial 0-1 cm layer of the Kurenga Bay Femob. was 2.6% of Fetot. (1078 and 41635 mg/g dry wt., respectively). In 19-20-cm background layer Femob. was 6.0% of Feвал. (2030 and 34100 mg/g dry wt., respectively). The similar appropriateness, as well as for Mn, was noticed at all stations of Imandra Lake.

     Therefore, for assessment of toxicity of metals accumulated in sediments the definition of the mobile forms by ammonium acetate extraction technique is offered. In sediments of Imandra Lake the increase of the part of the mobile form of Ni and Cu was noticed as increase of total concentration in the superficial polluted sediment, so the ecological risk for aquatic biota and for lake ecosystem raised. With increasing total concentrations of Fe and Mn in superficial sediments the part of the mobile forms reduced.