De-novo formation of dioxins and furans and the memory effect in waste incineration flue gases

The formation of dioxin (polychlorinated-rho-dibenzodioxins - PCDD) and furan (polychlorinated dibenzofurans - PCDF) in waste incineration flyash in relation to temperature has been investigated in a bench scale reactor. The PCDD/PCDF released into the exhaust gases of the reactor and trapped in a condensation and vapour phase adsorption system were also determined. The concentrations of PCDD/PCDF in the flyash were analysed in detail for all congeners and isomers including the mono-, di- and tri-PCDD/PCDF. De-novo synthesis of PCDD/PCDF was clearly seen in the flyash with large changes in concentrations of PCDD/PCDF with only small changes in temperature. Exhaust gas PCDD/PCDF were detected at all temperatures, with the maximum emission occurring at a flyash temperature of 350 degrees C, where the equivalent of over 42 times the total dioxin/furan concentration of the original flyash was lost to the vapour phase per unit mass of initial flyash. Although the desorbed species were mainly the lower mono- to tri-congener group of dioxins and furans, the desorbed dioxin/furans had a considerable toxic equivalent value.     

Characterisation of Particulate Matter Sampled during a Study of Children's Personal Exposure to Airborne Particulate Matter in a UK Urban Environment

The personal exposure of children aged 9 – 11 years to particulate matter (PM₁₀ and PM_2.5) was carried out between January and September 1997 in the London Borough of Barnet. Personal sampling along with home, garden and classroom microenvironmental monitoring was completed for all ten children. Each child was monitored for five days during winter, spring and summer. All children completed daily time activity diaries to provide information on any potential activities that could influence their exposure to particulate matter. Each evening a household activity questionnaire was also completed by the parents. Personal Environmental Monitors were used to sample personal exposure to PM₁₀ and PM_2.5. Harvard Impactors were used for the microenvironmental sampling of both size fractions. The children's mean personal exposure concentrations for PM₁₀ during winter, spring and summer were 72, 54 and 35 µg/m³ respectively and for PM_2.5 22, 17 and 18 µg/m³ respectively. In order to determine the potential sources of particulate matter, analysis of the Teflon filters has been undertaken. The physical characteristics of the particles have been identified using Scanning Electron Microscopy. The relationships between personal exposure concentrations and the different microenvironments will be discussed.     

PCDD/PCDF Isomer patterns in waste incinerator flyash and desorbed into the gas phase in relation to temperature

The influence of temperature on the PCDD and PCDF isomer profiles of a municipal waste incinerator flyash and the PCDD/PCDF desorbed from the ash under an inert atmosphere was investigated using a bench-scale reactor. Exposure to temperatures of 250 degrees C and above resulted in significant changes in the distribution of isomers within most dioxin and furan congener groups. The PCDD content tended to become more evenly distributed across the range of isomers than was the case for the raw flyash, while the PCDF content became concentrated across a relatively lower number of isomers. In most cases the desorbed PCDD/PCDF were mainly mono- to tri-chlorinated, and hence had a relatively low I-TEQ value. The isomer profiles of the desorbed species were also influenced by temperature. There were some significant differences between the PCDF isomer profiles of the desorbed species and those of the treated flyashes under the same conditions, but no clear differences between the PCDD isomer profiles.     

Desorption of PCDD/PCDF from municipal solid waste incinerator flyash under post-combustion plant conditions

The influence of temperature on the levels of PCDD and PCDF remaining in, and desorbed from, a municipal solid waste incinerator flyash was investigated by heating the ash to between 200 and 400 degrees C under a simulated flue gas for four days reaction time. Considerable desorption of PCDD/PCDF from the flyash was seen at 275 degrees C and above. Maximum desorption occurred at 350 degrees C, with the equivalent of nearly eight times the total PCDD/PCDF concentration of the original flyash being lost to the vapour phase per unit mass of initial flyash. The I-TEQ value of the desorbed PCDD/PCDF was considerable, being over fourteen times that of the original flyash at 325 degrees C. The results indicate that formation of PCDD/PCDF on flyash deposits in the post-combustion plant of incinerators can result in the release of significant amounts of PCDD/PCDF to the flue gas stream.     

Effect of decabromodiphenyl ether and antimony trioxide on controlled pyrolysis of high-impact polystyrene mixed with polyolefins

The controlled pyrolysis of polyethylene/polypropylene/polystyrene mixed with brominated high-impact polystyrene containing decabromodiphenyl ether as a brominated flame-retardant with antimony trioxide as a synergist was performed. The effect of decabromodiphenyl ether and antimony trioxide on the formation of its congeners and their effect on distribution of pyrolysis products were investigated. The controlled pyrolysis significantly affected the decomposition behavior and the formation of products. Analysis with gas chromatograph with electron capture detector confirmed that the bromine content was rich in step 1 (oil 1) liquid products leaving less bromine content in the step 2 (oil 2) liquid products. In the presence of antimony containing samples, the major portion of bromine was observed in the form of antimony bromide and no flame-retardant species were found in oil 1. In the presence of synergist, the step 1 and step 2 oils contain both light and heavy compounds. In the absence of synergist, the heavy compounds in step 1 oil and light compounds in step 2 oils were observed. The presence of antimony bromide was confirmed in the step 1 oils but not in step 2 oils.     

Automated riverine landscape characterization: GIS-based tools for watershed-scale research, assessment, and management

River systems consist of hydrogeomorphic patches (HPs) that emerge at multiple spatiotemporal scales. Functional process zones (FPZs) are HPs that exist at the river valley scale and are important strata for framing whole-watershed research questions and management plans. Hierarchical classification procedures aid in HP identification by grouping sections of river based on their hydrogeomorphic character; however, collecting data required for such procedures with field-based methods is often impractical. We developed a set of GIS-based tools that facilitate rapid, low cost riverine landscape characterization and FPZ classification. Our tools, termed RESonate, consist of a custom toolbox designed for ESRI ArcGIS®. RESonate automatically extracts 13 hydrogeomorphic variables from readily available geospatial datasets and datasets derived from modeling procedures. An advanced 2D flood model, FLDPLN, designed for MATLAB® is used to determine valley morphology by systematically flooding river networks. When used in conjunction with other modeling procedures, RESonate and FLDPLN can assess the character of large river networks quickly and at very low costs. Here we describe tool and model functions in addition to their benefits, limitations, and applications.     

The use of multiple tracers for tracking wastewater discharges in freshwater systems

The assessment of potential impacts of wastewater effluent discharges in freshwater systems requires an understanding of the likely degrees of dilution and potential zones of influence. In this study, four tracers commonly present in wastewater effluents were monitored to compare their relative effectiveness in determining areas in freshwater systems that are likely to be impacted by effluent discharges. The four tracers selected were the human pharmaceutical carbamazepine, anthropogenic gadolinium, fluorescent-dissolved organic matter (fDOM), and electrical conductivity (EC). The four tracers were monitored longitudinally in two distinct freshwater systems receiving wastewater effluents, where one site had a high level of effluent dilution (effluent <1 % of total flow) and the other site had a low level of effluent dilution (effluent ～50 % of total flow). At both sites, the selected tracers exhibited a similar pattern of response intensity downstream of discharge points relative to undiluted wastewater effluent, although a number of anomalies were noted between the tracers. Both EC and fDOM are non-specific to human influences, and both had a high background response, relative to the highly sensitive carbamazepine and anthropogenic gadolinium responses, although the ease of measuring EC and fDOM would make them more adaptable in highly variable systems. However, the greater sensitivity and selectivity of carbamazepine and gadolinium would make their combination with EC and fDOM as tracers of wastewater effluent discharges highly desirable to overcome potential limitations of individual tracers.