Obtaining accurate data for the contents of biogenic and fossil carbon in thermally-treated waste is essential for determination of the environmental profile of waste technologies. Relations between the variability of waste chemistry and the biogenic and fossil carbon emissions are not well described in the literature. This study addressed the variability of biogenic and fossil carbon in combustible waste received at a municipal solid waste incinerator. Two approaches were compared: (1) radiocarbon dating ((14)C analysis) of carbon dioxide sampled from the flue gas, and (2) mass and energy balance calculations using the balance method. The ability of the two approaches to accurately describe short-term day-to-day variations in carbon emissions, and to which extent these short-term variations could be explained by controlled changes in waste input composition, was evaluated. Finally, the measurement uncertainties related to the two approaches were determined. Two flue gas sampling campaigns at a full-scale waste incinerator were included: one during normal operation and one with controlled waste input. Estimation of carbon contents in the main waste types received was included. Both the (14)C method and the balance method represented promising methods able to provide good quality data for the ratio between biogenic and fossil carbon in waste. The relative uncertainty in the individual experiments was 7-10% (95% confidence interval) for the (14)C method and slightly lower for the balance method.
A dedicated sampling and measurement method was developed for long-term measurements of biogenic and fossil-derived CO(2) from thermal waste-to-energy processes. Based on long-term sampling of CO(2) and (14)C determination, plant-specific emission factors can be determined more accurately, and the annual emission of fossil CO(2) from waste-to-energy plants can be monitored according to carbon trading schemes and renewable energy certificates. Weekly and monthly measurements were performed at five Danish waste incinerators. Significant variations between fractions of biogenic CO(2) emitted were observed, not only over time, but also between plants. From the results of monthly samples at one plant, the annual mean fraction of biogenic CO(2) was found to be 69% of the total annual CO(2) emissions. From weekly samples, taken every 3 months at the five plants, significant seasonal variations in biogenic CO(2) emissions were observed (between 56% and 71% biogenic CO(2)). These variations confirmed that biomass fractions in the waste can vary considerably, not only from day to day but also from month to month. An uncertainty budget for the measurement method itself showed that the expanded uncertainty of the method was ± 4.0 pmC (95 % confidence interval) at 62 pmC. The long-term sampling method was found to be useful for waste incinerators for determination of annual fossil and biogenic CO(2) emissions with relatively low uncertainty.
A method to recover the fibers and monomers from epoxy-based and unsaturated polyester-based composites and characterize the liquid products using solid-phase microextraction has been investigated in this study. Experiments were performed using near-critical water in a batch reactor (1 L) at temperatures and pressures up to 350 °C and 170 bar. In-situ sampling was performed. The samples collected at temperatures in the range of 300 to 350 °C were divided into an aqueous phase and an oil phase. It was possible to identify various phenolic and aromatic compounds in both phases. In the samples collected during degradation of the polyester composites, the monomer phthalic acid precipitated nearly purified at temperatures in the range of 250−325 °C. By the recovery of fibers, an oil product, and the possibility to recover phthalic acid, the polymer composite end-of-life cycle is a step closer to completion.
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