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     

Toxicity of leachate from bottom ash in a road construction

A test road constructed with municipal solid waste incineration (MSWI) bottom ash was monitored over a period of 36 months. Using chemical and toxicological characterisation, the environmental impact of leachates from bottom ash was evaluated and compared with leachates from gravel used as reference. Initial leaching of Cl, Cu, K, Na, NH4-N and TOC from bottom ash was of major concern. However, the quality of the bottom ash leachate approached that of the gravel leachate with time. Leachates from the two materials were compared regarding the concentration of pollutants using multivariate data analyses (MVDA). A standardized luminescent bacteria assay using Vibrio fischeri did not show any toxicity, most likely because saline contamination can mask the toxic response and stimulate luminescence in these marine bacteria. A mung bean assay using Phaseolus aureus revealed that the toxicity of bottom ash leachate collected at the very beginning of the experimental period (October 2001 and May 2002) might be attributed to the following components and their respective concentrations in mg l(-1): Al (34.2-39.2), Cl (2914-16,446), Cu (0.48-1.92), K (197-847), Na (766-4180), NH4-N (1.80-8.47), total-N (12.0-18.5), and TOC (34.0-99.0). The P. aureus assay was judged as a promising environmental tool in assessing the toxicity of bottom ash leachate.     

REP-LECOTOX: an example of FP 6 INCO project to strengthen ecotoxicological research in WBC (Western Balkan countries)

Background

In order to map exceedances of critical atmospheric deposition loads for nitrogen (N) surface data on the atmospheric deposition of N compounds to terrestrial ecosystems are needed. Across Europe such information is provided by the international European Monitoring and Evaluation Programme (EMEP) in a resolution of 50 km by 50 km, relying on both emission data and measurement data on atmospheric depositions. The objective of the article at hand is on the improvement of the spatial resolution of the EMEP maps by combining them with data on the N concentration in mosses provided by the International Cooperative Programme on Effects of Air Pollution on Natural Vegetation and Crops (ICP Vegetation) of the United Nations Economic Commission for Europe (UNECE) Long-range Transboundary Air Pollution (LTRAP) Convention.

Methods

The map on atmospheric depositions of total N as modelled by EMEP was intersected with geostatistical surface estimations on the N concentration in mosses at a resolution of 5 km by 5 km. The medians of the N estimations in mosses were then calculated for each 50 km by 50 km grid cell. Both medians of moss estimations and corresponding modelled deposition values were ln-transformed and their relationship investigated and modelled by linear regression analysis. The regression equations were applied on the moss kriging estimates of the N concentration in mosses. The respective residuals were projected onto the centres of the EMEP grid cells and were mapped using variogram analysis and kriging procedures. Finally, the residual and the regression map were summed up to the map of total N deposition in terrestrial ecosystems throughout Europe.

Results and discussion

The regression analysis of the estimated N concentrations in mosses and the modelled EMEP depositions resulted in clear linear regression patterns with coefficients of determination of r ² = 0.62 and Pearson correlations of r _p = 0.79 and Spearman correlations of r _s = 0.70, respectively. Regarding the German territory a nationwide mean of 18.1 kg/ha/a (standard deviation: 3.49 kg/ha/a) could be derived from the resulting map on total N deposition in a resolution of 5 km by 5 km. Recent updates of the modelled atmospheric deposition of N provided a similar estimate for Germany.

Conclusions

The linking of modelled EMEP data on the atmospheric depositions of total N and the accumulation of N in mosses allows to map the deposition of total N in a high resolution of 5 km by 5 km using empirical moss data. The mapping relies on the strong statistical relationship between both processes that are physically and chemically related to each other. The mapping approach thereby relies on available data that are both based on European wide harmonized methodologies. From an ecotoxicological point of view the linking of data on N depositions and those on N bioaccumulation can be considered a substantial progress.     

Assessment of radionuclide and metal contamination in a thorium rich area in Norway

The Fen Central Complex in southern Norway, a geologically well investigated area of magmatic carbonatite rocks, is assumed to be among the world largest natural reservoirs of thorium ((232)Th). These rocks, also rich in iron (Fe), niobium (Nb), uranium ((238)U) and rare earth elements (REE), were mined in several past centuries. Waste locations, giving rise to enhanced levels of both radionuclides and metals, are now situated in the area. Estimation of radionuclide and metal contamination of the environment and radiological risk assessment were done in this study. The average outdoor gamma dose rate measured in Fen, 2.71 μGy h(-1), was significantly higher than the world average dose rate of 0.059 μGy h(-1). The annual exposure dose from terrestrial gamma radiation, related to outdoor occupancy, was in the range 0.18-9.82 mSv. The total activity concentrations of (232)Th and (238)U in soil ranged from 69 to 6581 and from 49 to 130 Bq kg(-1), respectively. Enhanced concentrations were also identified for metals, arsenic (As), lead (Pb), chromium (Cr) and zinc (Zn), in the vicinity of former mining sites. Both radionuclide and heavy metal concentrations suggested leaching, mobilization and distribution from rocks into the soil. Correlation analysis indicated different origins for (232)Th and (238)U, but same or similar for (232)Th and metals As, Cr, Zn, nickel (Ni) and cadmium (Cd). The results from in situ size fractionation of water demonstrated radionuclides predominately present as colloids and low molecular mass (LMM) species, being potentially mobile and available for uptake in aquatic organisms of Norsj? Lake. Transfer factors, calculated for different plant species, showed the highest radionuclide accumulation in mosses and lichens. Uptake in trees was, as expected, lower. Relationship analysis of (232)Th and (238)U concentrations in moss and soil samples showed a significant positive linear correlation.     

Rapid one-step assays for on-site monitoring of mouse and rat urinary allergens

Allergy to rodent proteins is common among laboratory animal workers. Sensitive methods to measure exposure to these allergens have been developed. These assays are, however, expensive, time-consuming, and require a laboratory facility and methodological expertise. A simple method to screen for allergen spread, or to test whether hygiene standards are maintained, would be useful. Lateral flow immunoassays (LFIAs) are especially suited for field settings; the tests are simple and results are visible within minutes. LFIAs were developed for detection of the rodent urinary allergens Mus m 1 and Rat n 1. Pilot studies were performed in animal facilities in three countries using both extracts from airborne dust samples and samples collected by wiping surfaces. For comparison and determination of sensitivity, the concentrations of rodent urinary allergens in the samples were also measured using enzyme immunoassays (EIAs). The LFIAs for rat and mouse urinary allergens had a detection limit of 31 pg allergen per mL in a buffer system with purified allergen standards. Results of environmental dust extracts tested in LFIAs correlated well with levels obtained using EIAs. Spread of rodent allergens, or non-adherence to hygiene around laboratory animal facilities, may aggravate rodent allergy. Using a simple, sensitive one-step assay, allergens can be detected to prevent allergen exposure. The results reveal that the rapid assays are suited for on-site demonstration of exposure to rodent allergens, and thus, useful in occupational hygiene practice.     

Biodegradation of Thermoplastic Polyurethanes from Vegetable Oils

Thermoplastic urethanes based on polyricinoleic acid soft segments and MDI/BD hard segments with varied soft segment concentration were prepared. Soft segment concentration was varied from, 40 to 70 wt%. Biodegradation was studied by respirometry. Segmented polyurethanes with soft segments based on polyricinoleic acid degrade relatively slow losing about 11% carbon after 30 days, but faster than corresponding petrochemical polyesterurethanes. Since biodegradation proceeds mainly through the soft segments, higher soft segment content polymers displayed slightly higher biodegradation. Polyurethanes with dispersed hard domains in the soft phase displayed slightly faster biodegradation than those with co-continuous morphology. Polyester diol degrades slower than castor oil but significantly faster than the polyurethanes with built in soft segments from the same diol. Castor oil biodegrades slower than soybean oil.     

Detection of elements and radioactivity in pellets from long-eared owls (Asio otus) inhabiting the city of Belgrade (Serbia)

In this study, we analysed pellets from long-eared owls (Asio otus) collected from four localities in Belgrade (Serbia). The pellets contained the remains of prey, namely voles (Arvicola terrestris) and field mice (Apodemus agrarius). The concentrations of 14 elements (Ca, P, Mg, Na, K, Fe, Zn, Sr, Ba, Mn, Ti, Cu, Si, B) were evaluated in whole pellets and in samples containing only bone tissue, which were dissected from the whole pellet. The increased levels of certain elements, including Mn, Zn, Ba, Cu and radioactive ⁴⁰K, indicate contamination of the soil by various sources, such as industrial plants and agricultural practices. From the results presented in this article, we suggest that the analysis of owl pellets may indicate the quality of the local environment.     

Antifungal activity of the pygidial gland secretion of <Emphasis Type="Italic">Laemostenus punctatus</Emphasis> (Coleoptera: Carabidae) against cave-dwelling micromycetes

The antifungal potential of the pygidial gland secretion of the troglophilic ground beetle Laemostenus punctatus from a cave in Southeastern Serbia against cave-dwelling micromycetes, isolated from the same habitat, has been investigated. Eleven collected samples were analyzed and 32 isolates of cave-dwelling fungi were documented. A total of 14 fungal species were identified as members of the genera Aspergillus, Penicillium, Alternaria, Cladosporium, Rhizopus, Trichoderma, Arthrinium, Aureobasidium, Epicoccum, Talaromyces, and Fusarium. Five isolates were selected for testing the antifungal activity of the pygidial gland secretion: Talaromyces duclauxi, Aspergillus brunneouniseriatus, Penicillium sp., Rhizopus stolonifer, and Trichoderma viride. The microdilution method has been applied to detect minimal inhibitory concentrations (MICs) and minimal fungicidal concentrations (MFCs). The most sensitive isolate was Penicillium sp., while the other isolates demonstrated a high level of resistance to the tested agent. L. punctatus has developed a special mechanism of producing specific compounds that act synergistically within the secretion mixture, which are responsible for the antifungal action against pathogens from the cave. The results open opportunities for further research in the field of ground beetle defense against pathogens, which could have an important application in human medicine, in addition to the environmental impact, primarily.