Quecksilbergasfeinreinigung mittels metall- und salzpartikelbelegter Trägermaterialien (G/S-Reaktor) Ökotoxizität von Quecksilber und seiner Verbindungen

Waste and process gases from thermal power and metallurgical plants or such products from alkali-chloride industries contain metallic, inorganic and organic mercury. Widespread processes applied to remove the greatest amount of mercury are absorption and adsorption. Caused by the lowering of the emission limit from 200 to 50 µg/m³ [STP] by national and European legislators, considerable efforts have been made to enhance the efficiency of the main separation units of flue gas cleaning plants by applying the appropriate technological measures. This article is focused on the removal of mercury from waste gases. The state of engineering is described, especially with regard to enhancing the efficiency of separation in the raw gas, in wet, dry and quasi-dry processes as well as in tail-end process units. Specially impregnated ceramic carriers can be used for the selective separation of metallic, inorganic and organic mercury. Amalgamation has been investigated as a possible separation mechanism both experimentally and in theory. Using the ceramic reactor, removal rates for gaseous mercury and its compounds can be achieved which are even lower than 50 µg/m³ [STP]. The technology, the separation mechanisms and the ecological advantages through the use of ceramic reactors are presented in the article as well.     

Determination of trace perchlorate in water: a simplified method for the identification of potential interferences

Background

Perchlorate contamination of water and food poses potential health risks to humans due to the possible interference of perchlorate with the iodide uptake into the thyroid gland. Perchlorate has been found in food and drinking, surface, or swimming pool waters in many countries, including the United States, Canada, France, Germany, and Switzerland, with ion chromatography (IC) being the preferred analytical method. The standardization of a robust ion chromatographic method is therefore of the high interest for public health and safety. This article summarizes the experiments and results obtained from analyzing untreated samples, considering the sample’s electrical conductance as guidance for direct sample injection as described in EPA 314.0.

Results

The suitability of ion chromatography with suppressed conductivity detection was tested for water samples in order to check the influence of matrix effects on the perchlorate signal of untreated samples. A sample injection volume of 750 μL was applied to the selected 2 mm?IC?column. The IC?determination of perchlorate at low µg/L levels is challenged by the presence of high loads of matrix ions (e.g., chloride, nitrate, carbonate, and sulfate at 100 mg/L and above). Perchlorate recovery is impaired with the increasing matrix ion concentrations, and its chromatographic peak is asymmetric particularly at low perchlorate concentrations. The identification of the individual maximum concentration of interfering anions like chloride, nitrate, and sulfate that influence perchlorate recovery helps to reduce the number of sample preparation steps or an obligatory measurement of the electrical conductivity of the sample. Within the scope of this study, samples containing less than 125 mg/L of either anion did not need sample preparation.

Conclusion

The identification of the maximum concentration of interfering anions like chloride, nitrate, and sulfate influencing perchlorate recovery provides a simplified alternative to the EPA 314.0 method. This approach reduces unnecessary sample preparation steps while allowing a reliable prognosis of possible interferences and maintaining result quality. This study was performed to support the development of a respective international standard, which is being established by the International Organization for Standardization (ISO). The results of the study are also intended to be used as guidance for interested laboratories to optimize the analytical workflow for trace perchlorate determination.

     

Heavy-metal ion complexation by particulate matter in the leachate of solid waste: a multi-method approach

The metal ion binding characteristics of particulate matter obtained from column experiments on the anaerobic digestion of solid waste were studied using a titrimetric approach. The experimental set-up allowed us to study the dynamics of particle bound ligand concentrations during digestion processes typically found in landfills.We developed a continuous titration method by simultaneously using a Cd-sensitive and pH electrode and combining metal and acid/base titrations. This technique allows for a more precise determination of pK_a-log K_M pairs for each ligand than metal titrations alone. The results were compared with titration methods using differential pulse anodic stripping voltammetry (DPASV) and atomic absorption spectroscopy (AAS) with longer equilibration times in order to further characterize ligand properties such as reaction kinetics, the electrochemical lability of the respective complex during DPASV, the distinction between metal adsorption to particulate matter and metal complexation by soluble ligands adhered to particles, reversibility of the binding process by competition studies, and resistance against purging with nitrogen gas.The properties of seven major metal binding ligands were identified and assignments to the most likely functional groups were made. The most important ligand properties are for ligand A: pK_a ≈ 9.2, log K_cd ≈ 7.0 fast reaction kinetics (mercapto groups); ligand B: pK_a = 4.8, log K_Cd ≈ 6.0, slow reaction kinetics (chelates with 3 or 4 carboxylic groups); ligand C: pK_a ≈ 6.0, log K_Cd ≈ 13.0, irreversible metal binding at basic pH-values (uptake inside bacterial cells); ligand D: pK_a = 7.7, log K_Cd = 4.0, runs parallel to N content of particulate matter with digestion time (primary amines neighboring oxo groups); ligand E: pK_a ≈ 12.0, log K_Cd = 9.0, runs parallel to P content of particulate matter (phosphate); ligand F:pK_a > 9.0, log K_{Cdf = pKa + 0.4}, runs parallel to N content of particulate matter (primary amines neighboring SH groups); and ligand G: pK_a ≤ 4.8, log K_Pb ≈ 4.3, strong Pb²⁺ ligand, even at low pH-values.Metal ions were found to be irreversibly bound by ligand C at low heavy-metal concentratins, whereas at higher concentrations the binding is reversible and can be predicted using the mass of the digestion process (methanogenic phase). All other ligands have their concentration maximum in the transition phase between acetogenic and methanogenic phase.     

Evaluation and further development of the activated sludge respiration inhibition test

The activated sludge respiration inhibition test is an important bacterial test system for the determination of bacterial toxicity of chemical compounds. The exposure period recommended by OECD 209 and ISO 8192 protocols is 30 and 180 min. A modified version of the test was developed which allowed a prolonged incubation period of 27 h to enhance the possibilities of the test system. The test system with the prolonged incubation time was evaluated by the recommended reference compound 3.5-dichlorophenol and showed an EC50 of 6.3 mgl(-1) with a coefficient of variation of 12.7%. Furthermore, the use of an open test system was evaluated showing a comparable toxicity but a higher coefficient of variation than the closed test system. A storage of activated sludge for several days accompanied by a daily feed with OECD nutrient solution should be avoided, for it can cause a decreased sensitivity of the inoculum. Different statistical fit procedures were tested indicating that Weibull fit procedures were superior for extended data sets covering a wide range of concentrations whereas Gamma and Probit fits were appropriate for smaller data sets mainly restricted to the linear part of the dose response curve.     

Using SFA indicators to support environmental policy

In order to improve the link from Substance Flow Analysis (SFA) studies to environmental policy, a translation is made from the SFA overview of flows and stocks into a limited set of indicators. This set is designed to evaluate a region’s substance regime with regard to environmental quality and sustainable development, including problem shifting in time and space.