Solidification/stabilization of metal polluted sediment of Krivaja river [Serbia] | Solidifikacija/stabilizacija sedimenta vodotoka Krivaja [Srbija] zagađenog metalima

The Krivaja River is the longest natural water body (109 km) that flows completely within the borders of Serbian province of Vojvodina. In the absence of national legislation, the sediment quality was assessed in accordance with the Dutch classification methodology. It was found that the river sediment is highly contaminated with copper and zinc (192 and 1218 mg/kg, respectively), and as such is an extreme risk to the environment and human health. The solidification/ stabilization (S/S) treatment with local clay, that has high capacity of cation exchange 70.2 meq/100 g and specific surface area of 630 square meter/g, was employed for remediation of the contaminated sediment. The sequential extraction procedure showed that the copper and zinc have medium risk for the environment, with the percentage in the carbonate fraction of 18 and 22;, respectively. The results of sequential extraction are not in full agreement with the results of pseudo-total metal concentration in the sediment, which only confirms that the total metal concentration is not sufficient to define the real danger to the environment. Based on the pseudo-total metals concentration, the sediment is of Class 4 (Dutch standards). However, judging from the results of sequential extraction, the metals show medium risk. Obviously, these results have to be taken into account in the assessment of the sediment quality, remediation procedures and sediment disposal in general. After the treatment, the proportion of these two metals in the first fraction is significantly reduced (Cu less than 2;, Zn 10;) in most of samples. In order to determine the long-term behavior of S/S mixtures, leaching tests were conducted in accordance with semi-dynamic ANS diffusion test for 90 days. The results indicated that clay can effectively immobilize Cu and Zn: the cumulative leached fraction of copper in mixtures with clay was in the range from 0.001; (mixture with 80; clay) to 0.15; (mixture with 10; clay), and the cumulative leached fraction of zinc in the range of 0.06; (mixture with 80; clay) to 0.10; (mixture with 10; clay). The diffusion coefficients, ranging from 1.5×10–12 to 3.7×10–14 square cm/s, showed an effective immobilization of both metals which suggests that these metals are practically immobilized in S/S mixtures even if the level of clay is low. From the point of LX values, all S/S mixtures can be used for the controlled utilization, because the leaching indices ranged from 11.8 to 13.4 for both metals. In all clay and sediment mixtures the dominant leaching mechanism is diffusion (slope values of 0.35 to 0.60), which once again confirms the effectiveness of the applied treatment and can be expected that only a very small amount of contaminants would leach into the environment over time. Future research is heading in the direction of troubleshooting the accumulation of used natural adsorbent after treatment, the possibility of permanent disposal, its regeneration or the possibility of its application as construction material.