Laboratory studies on formation and minimisation of polychlorinated dibenzodioxins and -furans (PCDD/F) in secondary aluminium process

The objectives of this work were to study the formation mechanisms of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/F) in thermal aluminium recycling processes by use of laboratory experiments. The pattern of isomers of PCDD/F indicates that de novo synthesis is important in aluminium smeltery. The mechanisms of PCDD/F formation in aluminium smelting are similar to that of various incineration processes of waste material. The results of bioanalysis (EROD-test) confirms the existence of de novo synthesis of PCDD/F, but points out to the existence to some additional, toxic compounds of unknown structure. To reduce the amount of PCDD/F the input of carbon at the metal should be reduced; in addition the metal smeltery plants should be cleaned from fly ash particles. It is suggested to use good primary methods in the technical plants like constant feeding of the metal into the oven will minimise PCDD/F concentration. The biological EROD-bioassay is a good tool to estimate PCDD/F-TEQ values also for this technical process simulated in the laboratory.     

Comprehensive analysis of the carbon impacts of vehicle intelligent speed control

In recent years sophisticated technologies have been developed to control vehicle speed based on the type of road the vehicle is driven on using Global Positioning Systems and in-car technology that can alter the speed of the vehicle. While reducing the speed of road vehicles is primarily of interest from a safety perspective, vehicle speed is also an important determinant of vehicle emissions and thus these technologies can be expected to have impacts on a range of exhaust emissions. This work analyses the results from a very large, comprehensive field trial that used 20 instrumented vehicles with and without speed control driven almost 500,000 km measuring vehicle speed at 10 Hz. We develop individual vehicle modal emissions models for CO₂ for 30 Euro III and Euro IV cars at a 1-Hz time resolution. Generalized Additive Models were used to describe how emissions from individual vehicles vary depending on their driving conditions, taking account of variable interactions and time-lag effects. We quantify the impact that vehicle speed control has on-vehicle emissions of CO₂ by road type, fuel type and driver behaviour. Savings in CO₂ of ≈6% were found on average for motorway-type roads when mandatory speed control was used compared with base case conditions. For most other types of road, speed control has very little effect on emissions of CO₂ and in some cases can result in increased emissions for low-speed limit urban roads. We also find that there is on average a 20% difference in CO₂ emission between the lowest and highest emitting driver, which highlights the importance of driver behaviour in general as a means of reducing emissions of CO₂.     

Mercury pollution in a mining area of Guizhou,China: Fluxes over contaminated surfaces and concentrations in air,biological and geological samples

A dynamic flux chamber has been used to estimate fluxes of mercury over different types of surfaces in an abandoned open‐cut mine of Tongren prefecture, Guizhou province, China during spring and summer of 1996. The highest fluxes were obtained over cinnabar slag and contaminated soils, whereas the emissions above cinnabar ore were substantially lower. These fluxes was scaled up to estimate the contribution of mercury emissions to air from mercury wastes, compared to anthropogenic activities in the province of Guizhou, China. Atmospheric mercury concentrations measured were enhanced in the mining area (<1.3 μg m^‐3) compared to regional background sites (1.8–5.1 ng m^‐3). The spreading of mercury was estimated by using biological and geological samples. Moss bags have been employed to estimate long‐time dry‐ and wet‐deposition to this area.     

Advanced solid-state carbon-13 nuclear magnetic resonance spectroscopic studies of sewage sludge organic matter: detection of organic "domains"

Two novel solid-state 13C nuclear magnetic resonance (NMR) spectroscopic techniques, PSRE (proton spin relaxation editing) and RESTORE [Restoration of Spectra via T(CH) and T(1rho)H (T One Rho H) Editing], were used to provide detailed chemical characterization of the organic matter from six Australian sewage sludges. These methods were used to probe the submicrometer heterogeneity of sludge organic matter, and identify and quantify spatially distinct components. Analysis of the T1H relaxation behavior of the sludges indicated that each sludge contained two types of organic domains. Carbon-13 PSRE NMR subspectra were generated to determine the chemical nature of these domains. The rapidly relaxing component of each sludge was rich in protein and alkyl carbon, and was identified as dead bacterial material. The slowly relaxing component of each sludge was rich in carbohydrate and lignin structures, and was identified as partly degraded plant material. The bacterial domains were shown, using the RESTORE technique, to also have characteristically rapid T(1rho)H relaxation rates. This rapid T(1rho)H relaxation was identified as the main cause of underrepresentation of these domains in standard 13C cross polarization (CP) NMR spectra of sludges. The heterogeneous nature of sewage sludge organic matter has implications for land application of sewage sludge, since the two components are likely to have different capacities for sorbing organic and inorganic toxicants present in sewage sludge, and will decompose at different rates.     

Response of Ceriodaphnia dubia to ionic silver: discrepancies among model predictions, measured concentrations and mortality

Silver thiosulfate, often a waste product of photoprocessing, is less bioavailable or toxic to aquatic organisms than is ionic silver. We conducted duplicate 48-h Ceriodaphnia dubia tests in reconstituted laboratory water using treatments of 92.7 nM Ag+ with various concentrations of thiosulfate. Expected Ag+ concentrations were generated for thiosulfate treatment levels using MINEQL + chemical equilibrium modeling. Ag+ concentrations in treatments were determined using a novel silicon-based sensor. Based on predicted Ag+ and published 48-h LC50 values for C. dubia, we did not expect to observe adverse effects. Yet, 100% mortality was observed at low thiosulfate treatments, whereas > 85% and > 95% survival was observed at higher thiosulfate treatment levels, respectively. Our results indicate that biotic responses match the sensor-based Ag+ concentrations. However, there is a discrepancy between these empirical results and responses expected to occur with Ag+ concentrations as predicted by MINEQL + chemical modeling. By correlating silicon sensor data with toxicity results obtained from our laboratory, our work clearly relates a specific chemical form (Ag+) to toxicity results.     

Inside-sediment partitioning of PAH, PCB and organochlorine compounds and inferences on sampling and normalization methods

Comparability of sediment analyses for semivolatile organic substances is still low. Neither screening of the sediments nor organic-carbon based normalization is sufficient to obtain comparable results. We are showing the interdependency of grain-size effects with inside-sediment organic-matter distribution for PAH, PCB and organochlorine compounds. Surface sediment samples collected by Van-Veen grab were sieved and analyzed for 16 PAH, 6 PCB and 18 organochlorine pesticides (OCP) as well as organic-matter content. Since bulk concentrations are influenced by grain-size effects themselves, we used a novel normalization method based on the sum of concentrations in the separate grain-size fractions of the sediments. By calculating relative normalized concentrations, it was possible to clearly show underlying mechanisms throughout a heterogeneous set of samples. Furthermore, we were able to show that, for comparability, screening at <125 μm is best suited and can be further improved by additional organic-carbon normalization.