Measurement of chemical oxygen demand (COD) in natural water samples by flow injection ozonation chemiluminescence (FI-CL) technique

COD determination based on ozone oxidation of alpha-naphthol combined with UV radiation (UV-O3) has been studied in the present work. Utilizing the phenomenon that luminol can be oxidized by the dissolved ozone to produce luminescence, we have established a new method of utilizing aqueous chemiluminescence to determine COD. The kinetics and mechanism of the ozonation reaction of alpha-naphthol have been investigated in order to gain a better understanding of the general applicability and limitation of the technique. Real world samples were analyzed and the results show that the relative error of COD(FI-CL) measurement for water samples was < 10%. Compared with the results of the conventional potassium permanganate method, the COD values of the FI-CL method are consistently higher (0-20% relative). The higher COD values suggest that the ozone-UV system is a more effective oxidation technique.     

Mesoscale ecohydrological modelling to analyse regional effects of climate change

Hydrological processes and crop growth were simulated for the state of Brandenburg (Germany) using the hydrological/vegetation/water quality model SWIM, which can be applied for mesoscale river basins or regions. Hydrological validation was carried out for three mesoscale river basins in the area. The crop growth module was validated regionally for winter wheat, winter barley and maize. After that the analysis of climate change impacts on hydrology and crop growth was performed, using a transient 1.5 K scenario of climate change for Brandenburg and restricting the crop spectrum to the three above mentioned crops. According to the scenario, precipitation is expected to increase. The impact study was done comparing simulation results for two scenario periods 2022–2030 and 2042–2050 with those for a reference period 1981–1992. The atmospheric CO₂ concentrations for the reference period and two scenario periods were set to 346, 406 and 436 ppm, respectively. Two different methods – an empirical one and a semi-mechanistic one – were used for adjustment of net photosynthesis to altered CO₂. With warming, the model simulates an increase of evapotranspiration (+9.5%, +15.4%) and runoff (+7.0%, +17.2%). The crop yield was only slightly altered under the climate change only scenario (no CO₂ fertilization effect) for barley and maize, and it was reduced for wheat (–6.2%, –10.3%). The impact of higher atmospheric CO₂ compensated for climate-related wheat yield losses, and resulted in an increased yield both for barley and maize compared to the reference scenario. The simulated combined effect of climate change and elevated CO₂ on crop yield was about 7% higher for the C₃ crops when the CO₂ and temperature interaction was ignored. The assumption that stomatal control of transpiration is taking place at the regional scale led to further increase in crop yield, which was larger for maize than for wheat and barley. The regional water balance was practically not affected by the partial stimulation of net photosynthesis due to higher CO₂, while the introduction of stomatal control of regional transpiration reduced evapotranspiration and enlarged notably runoff and ground water recharge.     

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.     

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.