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.     

Handling data uncertainties in event tree analysis

Event tree analysis (ETA) is an established risk analysis technique to assess likelihood (in a probabilistic context) of an accident. The objective data available to estimate the likelihood is often missing (or sparse), and even if available, is subject to incompleteness (partial ignorance) and imprecision (vagueness). Without addressing incompleteness and imprecision in the available data, ETA and subsequent risk analysis give a false impression of precision and correctness that undermines the overall credibility of the process. This paper explores two approaches to address data uncertainties, namely, fuzzy sets and evidence theory, and compares the results with Monte Carlo simulations. A fuzzy-based approach is used for handling imprecision and subjectivity, whereas evidence theory is used for handling inconsistent, incomplete and conflicting data. Application of these approaches in ETA is demonstrated using the example of an LPG release near a processing facility.     

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.     

Impacts of groundwater metal loads from bedrock fractures on water quality of a mountain stream

Acid mine drainage and metal loads from hardrock mines to surface waters is a significant problem in the western USA and many parts of the world. Mines often occur in mountain environments with fractured bedrock aquifers that serve as pathways for metals transport to streams. This study evaluates impacts from current and potential future groundwater metal (Cd, Cu, and Zn) loads from fractures underlying the Gilt Edge Mine, South Dakota, on concentrations in Strawberry Creek using existing flow and water quality data and simple mixing/dilution mass balance models. Results showed that metal loads from bedrock fractures to the creek currently contribute <1% of total loads. Even if background water quality is achieved upstream in Strawberry Creek, fracture metal loads would be <5%. Fracture loads could increase substantially and cause stream water quality standards exceedances once groundwater with elevated metals concentrations in the aquifer matrix migrates to the fractures and discharges to the stream. Potential future metal loads from an upstream fracture would contribute a small proportion of the total load relative to current loads in the stream. Cd has the highest stream concentrations relative to standards. Even if all stream water was treated to remove 90% of the Cd, the standard would still not be achieved. At a fracture farther downstream, the Cd standard can only be met if the upstream water is treated achieving a 90% reduction in Cd concentrations and the median stream flow is maintained.     

Reevaluation of ENCORE: support for the eutrophication threshold model for coral reefs

The results from the multimillion dollar Enrichment of Nutrients on Coral Reefs Experiment (ENCORE) on One Tree Island Reef (OTIR) suggest that increased nutrient loads to coral reefs will have little or no effect on the algal growth rates and, hence, on the associated effects that increased algal growth might have on the functioning and stability of coral reefs. However, a comparison of the concentrations of nutrients within the OTIR lagoon with the proposed nutrient threshold concentrations (NTC) for coral reefs suggests that all sites, including the control sites, were saturated with nutrients during ENCORE, and, hence, one would not expect to get any differences between treatments in the algal-growth related measurements. Thus, ENCORE results provide strong support for the proposed NTCs and support the ecological principle that algal productivity and, consequently, the functioning of coral reefs are sensitive to small changes in the background concentrations of nutrients. The principal conclusion of ENCORE, namely that the addition of nutrients did not cause the "pristine" OTIR to convert from coral communities to algal dominated reefs, is contrary to the fact that there was prolific macroalgal growth on the walls and crests of the experimental microatolls by the end of ENCORE.     

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.     

Reductive hydrogenation of polycyclic aromatic hydrocarbons catalyzed by metalloporphyrins

The hydrogenation of polycyclic aromatic hydrocarbons (PAHs) (naphthalene, anthracene, and phenanthrene) catalyzed by metalloporphyrins based on cobalt, nickel or iron was studied in aqueous solutions at room temperature and ambient pressure. Nickel porphyrin (P1) activated by nanosized zero-valent iron (nano-ZVI) and cobalt porphyrins (P2) and (P4) activated by titanium(III) citrate as the electron donor were demonstrated to be promising catalysts for the reductive hydrogenation of PAHs. In particular, partially saturated di-, tetra-, and octahydrogenated products were obtained for anthracene or phenanthrene using a nickel porphyrin activated by nano-ZVI, while naphthalene was transformed to tetralin. Systems containing cobalt porphyrins activated by titanium(III) citrate exhibited a high selectivity and activity toward hydrogenation of anthracene, producing 9,10-dihydroanthracene. However, no formation of hydrogenated hydrocarbons was observed from naphthalene or phenanthrene using cobalt porphyrins.     

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.     

Behavior and stability of organic contaminant droplets in aqueous solutions

The behavior of several hydrophobic organic compounds (HOCs) in water at concentrations close to and above their maximum solubility values was studied. For this purpose, solutions of benzene, toluene, xylene, trichloroethylene (TCE) and a mixture of them were prepared in excess in freshwater and in saltwater, and solution stability was examined. High organic concentrations were found to remain stable in both freshwater and saltwater. In saltwater, for example, toluene and xylene concentrations remained as high as 14 and 26 times their solubilities, respectively, over a period of 6 days, while in freshwater, their concentrations remained 8 and 30 times their solubilities over the same period. This phenomenon is attributed to the presence of stable organic droplets, which were observed using optical microscopy. In addition, the transport of HOC droplets through sand is demonstrated, using an experimental system consisting of a saltwater source reservoir connected by a porous inactive sand layer to a freshwater collector reservoir.     

Making a life in the physical sciences

As a practicing physical chemist, I argue that the challenges faced by the physical sciences have more parallels with organization science than it might first appear. While the physical sciences do represent a strong paradigm endeavor, many of the same issues that were raised in the article “Making a life in the field of organizational science” arise in physical sciences. An essential difference between the physical sciences and organization science is the essentially capital intensive nature of our research. Ironically, the constant pursuit of the requisite research dollars leads to substantial similarity between the fields. The state of academic physical sciences is analyzed in this context informed by the current state of research funding in the United States. Copyright © 2008 John Wiley & Sons, Ltd.