Selective removal of heavy metals from metal-bearing wastewater in a cascade line reactor

Goal, Scope and Background This paper is a part of the research work on ‘Integrated treatment of industrial wastes towards prevention of regional water resources contamination — INTREAT’ the project. It addresses the environmental pollution problems associated with solid and liquid waste/effluents produced by sulfide ore mining and metallurgical activities in the Copper Mining and Smelting Complex Bor (RTB-BOR), Serbia. However, since the minimum solubility for the different metals usually found in the polluted water occurs at different pH values and the hydroxide precipitates are amphoteric in nature, selective removal of mixed metals could be achieved as the multiple stage precipitation. For this reason, acid mine water had to be treated in multiple stages in a continuous precipitation system-cascade line reactor. Materials and Methods All experiments were performed using synthetic metal-bearing effluent with chemical a composition similar to the effluent from open pit, Copper Mining and Smelting Complex Bor (RTB-BOR). That effluent is characterized by low pH (1.78) due to the content of sulfuric acid and heavy metals, such as Cu, Fe, Ni, Mn, Zn with concentrations of 76.680, 26.130, 0.113, 11.490, 1.020 mg/dm³, respectively. The cascade line reactor is equipped with the following components: for feeding of effluents, for injection of the precipitation agent, for pH measurements and control, and for removal of the process gases. The precipitation agent was 1M NaOH. In each of the three reactors, a changing of pH and temperature was observed. In order to verify efficiency of heavy metals removal, chemical analyses of samples taken at different pH was done using AES-ICP. Results Consumption of NaOH in reactors was 370 cm³, 40 cm³ and 80 cm³, respectively. Total time of the experiment was 4 h including feeding of the first reactor. The time necessary to achieve the defined pH value was 25 min for the first reactor and 13 min for both second and third reactors. Taking into account the complete process in the cascade line reactor, the difference between maximum and minimum temperature was as low as 6°C. The quantity of solid residue in reactors respectively was 0.62 g, 2.05 g and 3.91 g. In the case of copper, minimum achieved concentration was 0.62 mg/dm³ at pH = 10.4. At pH = 4.50 content of iron has rapidly decreased to < 0.1 mg/dm³ and maintained constant at all higher pH values. That means that precipitation has already ended at pH=4.5 and maximum efficiency of iron removal was 99.53%. The concentration of manganese was minimum at pH value of 11.0. Minimum obtained concentration of Zn was 2.18 mg/dm³ at a pH value of 11. If pH value is higher than 11, Zn can be re-dissolved. The maximum efficiency of Ni removal reached 76.30% at a pH value of 10.4. Discussion Obtained results show that efficiency of copper, iron and manganese removal is very satisfactory (higher than 90%). The obtained efficiency of Zn and Ni removal is lower (72.30% and 76.31%, respectively). The treated effluent met discharge water standard according to The Council Directive 76/464/EEC on pollution caused by certain dangerous substances into the aquatic environment of the Community. Maximum changing of temperature during the whole process was 6°C. Conclusion This technology, which was based on inducing chemical precipitation of heavy metals is viable for selective removal of heavy metals from metal-bearing effluents in three reactor systems in a cascade line. Recommendations and Perspectives The worldwide increasing concern for the environment and guidelines regarding effluent discharge make their treatment necessary for safe discharge in water receivers. In the case where the effluents contain valuable metals, there is also an additional economic interest to recover these metals and to recycle them as secondary raw materials in different production routes. ESS-Submission Editor: PhD Hailong Wang, hailong.wang@ensisjv.com     

Distribution and fractionation of heavy metals in the Tisa (Tisza) River sediments

Introduction In this work, sediments of the River Tisa (Tisza) are studied to assess their environmental pollution levels for some major heavy metals, as well as to predict the investigated elements’ mobility on the basis of their association type with the substrate. The Tisa River catchments area is a subbasin of the River Danube. Part of this river, 166 km long, belongs to the Serbian province of Vojvodina, before it flows into the Danube. It has been chosen for our investigation, because it has been exposed to intense pollution in the last decades. Materials and Methods The river sediment samples were collected at 32 locations. The proportions of sand, silt and clay fractions were determined. The sequential extraction procedure following a modified Tessier method was applied for speciation of the metal forms in the collected samples. The metal concentrations of Zn, Cd, Pb, Ni, Cu, Cr, Fe and Mn in extracts were determined by atomic absorption spectroscopy. Results and Discussion Granulometric analysis showed that some 50% of the Tisa River sediments were silt and clay, while the rest was sand with quartz, as the main constituent. The average metal content of the surface river sediment samples for every fraction of sequential extraction was presented and discussed in relation to pH, Eh and metal fractionation. The average metal content from the Tisa River sediments, obtained as an average of the metal’s concentration released in all five sequential extraction fractions was compared with: average metal contents of the Tisa River sediments in Hungary, metal content in soils formed on the Tisa River alluvium of Vojvodina, average metal content in soils of Vojvodina, and average metal content in soils of Hungary. An assessment of metal pollution levels in Tisa River sediments was made by comparing mean values for obtained results for the Tisa River sediments with the freshwater sediment’s Quality Guidelines as published by US EPA, Environment Canada and soil standards for Serbia. Conclusion According to US EPA and Canadian Quality Guidelines for freshwater sediments, the concentration of heavy metals in Tisa sediments were: (a) much higher than defined concentrations below which harmful effects on river biota are unlikely to be observed, (b) below defined concentrations above which harmful effects on river biota are likely to be observed. The concentration levels of Pb, Ni, Cu and Cr in Tisa River sediments are safe when compared with Serbian MAQ (Maximum Allowed Quantity) standards for soils, but they are unsafe in the case of Zn and Cd. Recommendations and Outlook The quality of sediments in the Tisa River was on the border line between potentially polluted and polluted. This line could very easily be exceeded since the quality of sediments in the Tisa River in Hungary was already worse than in Serbia. These results indicated the need for further monitoring of heavy metals in that locality.     

Levels of PAHs in the soils of Belgrade and its environs

Polycyclic aromatic hydrocarbons (PAHs) were analysed in 39 soil samples (0–10 cm upper layer) collected in Belgrade, the capital of Serbia. The sampling sites were randomly selected from urban, urban/recreational and rural areas; the samples were collected in April and December 2003 and July and October 2004. The sum of the 16 PAHs corresponding to the recreational zone (298 μg/kg) was close to the urban zone (375 μg/kg). Mean soil ΣPAH concentration from rural areas was 18 μg/kg dry weight. Comparing to values observed in the urbanized locations around the world, the overall levels of PAHs in this study are low. The PAH ratios obtained pointed to a domination of pyrogenically formed PAHs in the examined soils. The dominant PAHs in soil samples in urban zones were fluoranthene, benz[a]anthracene, phenanthrene and pyrene, mostly emitted from noncatalyst vehicles which are still in use in Serbia. The total carcinogenic potency for each sampling site was calculated. Regardless of the used carcinogenic activity factors, carcinogenic potency of 7 sites were 3–9 times higher than the reference ones indicating the increased carcinogenic burden of soils from these sites.     

Bioaccumulation of Metals in Fish of Salmonidae Family and the Impact on Fish Meat Quality

The study was aimed at determining the levels of metals in water samples and muscles of the fish caught in the Una River basin, located in the northwestern part of Bosnia and Herzegovina. For that purpose, three fish species: Brown Trout (Salmo trutta m. fario), Grayling (Thymallus thymallus) and Californian Trout (Salmo gairdneri), together with stem water samples, were analyzed for metal concentrations (Pb, Hg, Cd, As, Mn, Ni, Cu, Cr, Se, Co, Sn, Zn, Fe, Ca, P) during a 2-year period. The fish was captured using electric fishing, nets or fishing equipment. The capture was undertaken on three sites (the river source, the middle flow and the river mouth) of each of the five biggest rivers belonging to the Una River basin (Unac, Krušnica, Sana, Klokot, and Una). The concentrations of metals in each sample were determined via atomic absorption spectrophotometry. In the tested waters, the presence of Mn in concentrations higher than permitted (0.07 mg/l) had been detected. In the tested meat, the following average concentrations of metals (mg/kg) had been found: Pb (0.67), Cd (0.06), Mn (0.65), Ni (0.15), Cu (0.79), Cr (1.05), Se (0.03), Zn (8.92), Fe (5.40), Ca (14.68), and P (10.85). The correlation between Mn concentrations identified in the tested waters and those identified in the meat of Brown Trout was revealed to be statistically significant, which confirms that, over time, bioaccumulation of metals took place. Even though the results were not indicative of contamination, they strongly suggest that constant monitoring of the ecosystems in reference should be implemented.