Bromine in waste incineration partitioning and influence on metal volatilisation

INTENTION, GOAL, SCOPE, BACKGROUND: The halogen bromine is far less abundant than chlorine, but it can be found at high concentrations in special materials like flame retarded plastics. The fate and effects of Br in waste incineration are not well understood. It may have similar implications like Cl for the volatilisation of heavy metals and the formation of low volatile organic compounds. Due to its lower oxidation potential, there is a risk of formation of elementary Br2 in the offgas. OBJECTIVE: Co-combustion tests of different types of Br containing plastic waste materials (up to 22%) and MSW in the TAMARA pilot plant for waste incineration were conducted to investigate the Br partitioning and the influence of Br on metal volatilisation. METHODS: The Br inventory of the fuel mix was elevated to approx. 1 wt-%. All input and output mass flows of the furnace have been sampled and the partitioning of Cl, Br, S, and a number of heavy metals, has been calculated on the basis of closed mass balances. RESULTS AND DISCUSSION: Organically-bound Br was typically released to more than 90% into the raw gas. Elementary Br2 was detected at high Br levels. Its presence was always analysed when all SO2 in the raw gas was oxidised to SO3. Br enhances the volatilisation of metals like K, Zn, Cd, Sn, Sb, and Pb out of the fuel bed principally in the same way as Cl. The tests gave strong indication that the promoting influence of the halogens on metal volatilisation is more pronounced than that of the fuel bed temperature. The volatilised metals are condensated on the fly ashes and are discharged along with the filter ashes. CONCLUSIONS: As long as a surplus of SO2 is present in the raw gas no Br2 is formed. Although the halogen induced transfer out of the fuel bed causes high concentrations of volatile metals in the filter ashes, a recovery is not economically feasible for the time being. The volatilisation gives no rise to metal emission problems as long as efficient dedusting is achieved. RECOMMENDATION AND OUTLOOK: If there is a risk of Br2 formation, in wet scrubbing a reducing agent has to be added to the neutral scrubber for efficient abatement. Filter ashes should be disposed of in a way that enables access for recovery in the future. The exact volatilisation characteristics of the various metals have to be studied in future using specifically tailored experiments.     

Marine macroalgae in polar regions as natural sources for volatile organohalogens

Marine macroalgae species from the polar regions were investigated for their importance as natural sources of volatile halogenated compounds released into the biosphere. Several different halogenated C1 to C4 hydrocarbons were identified and their release rates determined. The compounds contained mainly bromine and iodine, and form was the dominant compound released. Although an annual atmospheric input of approximately 10(8)-10(10) g bromine and 10(7)-10(8) g iodine was calculated from the release rates, marine macroalgae are apparently not the major source on a global scale, as the release is up to four orders of magnitude lower than a presumed annual flow from the oceans. Despite this, macroalgae may be more important on a local scale due to their occurrence at a high biomass in the coastal regions. The present paper gives an overview about studies done on the release of volatile halocarbons by macroalgae from polar regions. Furthermore, the function of these compounds in the macroalgal metabolism is discussed.     

A Simple Field Method to Determine Mercury Volatilization from Soils (3 pp)

Background Estimations of gaseous mercury volatilization from soils are often complex, stationary and expensive. Our objective was to develop a mobile and more simple, easy to handle and more cost-effective field method allowing rapid estimates of potential Hg emissions from soils. Methods. The study site is located in Germany, about 100 kilometers south-westerly of Berlin and influenced by the river Elbe and its tributary Saale river. The site is representative for a lot of other floodplain locations at the river Elbe and highly polluted with Hg and other heavy metals. For our study we developed a system consisting of a glass chamber gas, two gold traps, a battery operated pump and a gas meter. Adsorbed total gaseous mercury (TGM) in the gold traps was determined by use of atomic absorption spectrometry (AAS). Results and Discussion. In contrast to the common used flux chambers we designed a chamber without inlet and named it gas suck up chamber (GSC). TGM fluxes determined with the GSC showed a very close linear correlation (r = 0.993) between the TGM content in the gold traps and the corresponding pumped gas volume. The TGM adsorbed, increased proportional with increasing gas volume indicating homogenous concentrations of gaseous mercury in the soil air sucked. In contrast to the commonly used dynamic flux chamber with the aim of precisely measuring actual fluxes of Hg from a defined soil area, we focused on developing of a measurement system which will allow rapid estimates of potential Hg emissions of a site. Earlier research at the study site indicated a high potential for releasing volatile Hg from the soil to the atmosphere. Indeed, due to the high Hg content of the soil significant amounts of TGM could be detected and no shortage was reached. Conclusion. Our initial measurements are still too few in number neither to generalize the achieved results nor discuss controlling factors and processes. However, we are pleased to communicate that the developed GSC is well suited to become an effective sampling set up to rapidly estimate the magnitude of Hg volatilization from soils. Outlook. Further measurements at other polluted locations are necessary to verify the GSC method. In addition the use of a mercury analyzer instead of gold traps is planned for faster risk assessments.     

MODELKEY. Models for assessing and forecasting the impact of environmental key pollutants on freshwater and marine ecosystems and biodiversity (5 pp)

BACKGROUND: Triggered by the requirement of Water Framework Directive for a good ecological status for European river systems till 2015 and by still existing lacks in tools for cause identification of insufficient ecological status MODELKEY (http:// www.modelkey.org), an Integrated Project with 26 partners from 14 European countries, was started in 2005. MODELKEY is the acronym for 'Models for assessing and forecasting the impact of environmental key pollutants on freshwater and marine ecosystems and biodiversity'. The project is funded by the European Commission within the Sixth Framework Programme. OBJECTIVES: MODELKEY comprises a multidisciplinary approach aiming at developing interlinked tools for an enhanced understanding of cause-effect-relationships between insufficient ecological status and environmental pollution as causative factor and for the assessment and forecasting of the risks of key pollutants on fresh water and marine ecosystems at a river basin and adjacent marine environment scale. New modelling tools for risk assessment including generic exposure assessment models, mechanistic models of toxic effects in simplified food chains, integrated diagnostic effect models based on community patterns, predictive component effect models applying artificial neural networks and GIS-based analysis of integrated risk indexes will be developed and linked to a user-friendly decision support system for the prioritisation of risks, contamination sources and contaminated sites. APPROACH: Modelling will be closely interlinked with extensive laboratory and field investigations. Early warning strategies on the basis of sub-lethal effects in vitro and in vivo are provided and combined with fractionation and analytical tools for effect-directed analysis of key toxicants. Integrated assessment of exposure and effects on biofilms, invertebrate and fish communities linking chemical analysis in water, sediment and biota with in vitro, in vivo and community level effect analysis is designed to provide data and conceptual understanding for risk arising from key toxicants in aquatic ecosystems and will be used for verification of various modelling approaches. CONCLUSION AND PERSPECTIVE: The developed tools will be verified in case studies representing European key areas including Mediterranean, Western and Central European river basins. An end-user-directed decision support system will be provided for cost-effective tool selection and appropriate risk and site prioritisation.     

Characterization and phosphate stabilization of dusts from the vitrification of MSW combustion residues

The use of soluble PO₄³⁻ as a heavy metal chemical stabilization agent was evaluated for a dust generated from melting or vitrification of municipal solid waste combustion residues. Vitrification dusts contain high concentrations of volatile elements such as Cl, Na, K, S, Pb, and Zn. These elements are present in the dusts largely as simple salts (e.g. PbCl₂, ZnSO₄) which are highly leachable. At an experimental dose of 0.4 moles of soluble PO₄³⁻ per kg of residue, the pH-dependent leaching (pH 5,7,9) showed that the treatment was able to reduce equilibrium concentrations by factors of 3 to 100 for many metals; particularly Cd, Cu, Pb and Zn. Bulk and surface spectroscopies showed that the insoluble reaction products are tertiary metal phosphate [e.g. Zn₃(PO₄)₂] and apatite [e.g. Pb₅(PO₄)₃Cl] family minerals. Geochemical thermodynamic equilibrium modeling showed that apatite family and tertiary metal phosphate phases act as controlling solids for the equilibrium concentrations of Ca²⁺, Zn²⁺, Pb²⁺, Cu²⁺, and Cd²⁺ in the leachates during pH-dependent leaching. Both end members and ideal solid solutions were seen to be controlling solids. Soluble phosphate effectively converted soluble metal salts into insoluble metal phosphate phases despite the relatively low doses and dry mixing conditions that were used. Soluble phosphate is an effective stabilization agent for divalent heavy metals in melting dusts where leachable metals are present in high concentrations.     

Photocontrol of Weeds Without Herbicides

First presented at the European Symposium Photomorphogenesis in Plants, Freiburg/Br., September 24–29, 1989, West Germany.