Structural characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2,5,6-tetrabromocyclooctane (TBCO)

1,2,5,6-Tetrabromocyclooctane (TBCO) is a commercial brominated flame retardant that is employed mainly as an additive in textiles, paints and plastics. Very little is known about its presence or behavior in the environment or its analysis. TBCO can exist as two diastereomers, the stereochemistries of which have not been previously reported. We have named the first eluting isomer, under HPLC conditions, as alpha-TBCO (α-TBCO) and the later eluting isomer as beta-TBCO (β-TBCO) when using an Acquity UPLC BEH C₁₈ column with methanol/acetonitrile/water as the mobile phase. The structural elucidation of these two isomers was accomplished by ¹H NMR spectroscopy, GC/MS, LC/MS and X-ray structure determinations. α-TBCO is (1R,2R,5S,6S)-1,2,5,6-tetrabromocyclooctane and β-TBCO is rac-(1R,2R,5R,6R)-1,2,5,6-tetrabromocyclooctane. As with some other brominated cycloaliphatic compounds, TBCO is thermally labile and the isomers easily interconvert. A thermal equilibrium mixture of α- and β-TBCO consists of approximately 15% and 85% of these isomers, respectively. Separation of the two diastereomers, with minimal thermal interconversion between them, is achievable by careful selection of GC-capillary column length and injector temperature. LC/MS analyses of TBCO also presents an analytical challenge due to poor resolution of the isomers on chromatographic stationary phases, and weak intensity of molecular ions (or major fragment ions) when using LC-ESI/MS. Only bromide ions were seen in the mass spectra. APCI and APPI also failed to produce the molecular ion with sufficient intensity for identification.     

Models,Assumptions, and Stakeholders: Planning for Water Supply Variability in the Colorado River Basin1

Abstract: Declining reservoir storage has raised the specter of the first water shortage on the Lower Colorado River since the completion of Glen Canyon and Hoover Dams. This focusing event spurred modeling efforts to frame alternatives for managing the reservoir system during prolonged droughts. This paper addresses the management challenges that arise when using modeling tools to manage water scarcity under variable hydroclimatology, shifting use patterns, and institutional complexity. Assumptions specified in modeling simulations are an integral feature of public processes. The policymaking and management implications of assumptions are examined by analyzing four interacting sources of physical and institutional uncertainty: inflow (runoff), depletion (water use), operating rules, and initial reservoir conditions. A review of planning documents and model reports generated during two recent processes to plan for surplus and shortage in the Colorado River demonstrates that modeling tools become useful to stakeholders by clarifying the impacts of modeling assumptions at several temporal and spatial scales. A high reservoir storage‐to‐runoff ratio elevates the importance of assumptions regarding initial reservoir conditions over the three‐year outlook used to assess the likelihood of reaching surplus and shortage triggers. An ensemble of initial condition predictions can provide more robust initial conditions estimates. This paper concludes that water managers require model outputs that encompass a full range of future potential outcomes, including best and worst cases. Further research into methods of representing and communicating about hydrologic and institutional uncertainty in model outputs will help water managers and other stakeholders to assess tradeoffs when planning for water supply variability.     

A comparison of five high-resolution spatially-explicit,fossil-fuel,carbon dioxide emission inventories for the United States

The quantification of fossil-fuel-related emissions of carbon dioxide to the atmosphere is necessary in order to accurately represent carbon cycle fluxes and to understand and project the details of the global carbon cycle. In addition, the monitoring, reporting, and verification (MRV) of carbon dioxide emissions is necessary for the success of international agreements to reduce emissions. However, existing fossil-fuel carbon dioxide (FFCO₂) emissions inventories vary in terms of the data and methods used to estimate and distribute FFCO₂. This paper compares how the approaches used to create spatially explicit FFCO₂ emissions inventories affect the spatial distribution of emissions estimates and the magnitude of emissions estimates in specific locales. Five spatially explicit FFCO₂ emission inventories were compared: Carbon Dioxide Information and Analysis Center (CDIAC), Emission Database for Global Atmospheric Research (EDGAR), Fossil Fuel Data Assimilation System (FFDAS), Open-source Data Inventory for Anthropogenic CO₂ (ODIAC), and Vulcan. The effects of using specific data and approaches in the creation of spatially explicit FFCO₂ emissions inventories, and the effect of resolution on data representation are analyzed using graphical, numerical, and cartographic approaches. We examined the effect of using top-down versus bottom-up approaches, nightlights versus population proxies, and the inclusion of large point sources. The results indicate that the approach used to distribute emissions in space creates distinct patterns in the distribution of emissions estimates and hence in the estimates of emissions in specific locations. The different datasets serve different purposes but collectively show the key role of large point sources and urban centers and the strong relationship between scale and uncertainty.     

Assessing Societal Impacts When Planning Restoration of Large Alluvial Rivers: A Case Study of the Sacramento River Project, California

Studies have shown that ecological restoration projects are more likely to gain public support if they simultaneously increase important human services that natural resources provide to people. River restoration projects have the potential to influence many of the societal functions (e.g., flood control, water quality) that rivers provide, yet most projects fail to consider this in a comprehensive manner. Most river restoration projects also fail to take into account opportunities for revitalization of large-scale river processes, focusing instead on opportunities presented at individual parcels. In an effort to avoid these pitfalls while planning restoration of the Sacramento River, we conducted a set of coordinated studies to evaluate societal impacts of alternative restoration actions over a large geographic area. Our studies were designed to identify restoration actions that offer benefits to both society and the ecosystem and to meet the information needs of agency planning teams focusing on the area. We worked with local partners and public stakeholders to design and implement studies that assessed the effects of alternative restoration actions on flooding and erosion patterns, socioeconomics, cultural resources, and public access and recreation. We found that by explicitly and scientifically melding societal and ecosystem perspectives, it was possible to identify restoration actions that simultaneously improve both ecosystem health and the services (e.g., flood protection and recreation) that the Sacramento River and its floodplain provide to people. Further, we found that by directly engaging with local stakeholders to formulate, implement, and interpret the studies, we were able to develop a high level of trust that ultimately translated into widespread support for the project.     

Synthesis of the two minor isomers, delta- and epsilon-1,2,5,6,9,10-hexabromocyclododecane, present in commercial hexabromocyclododecane

Hexabromocyclododecane (HBCD) is prepared commercially by bromination of cis,trans,trans-cyclododecatriene (ctt-CDT) and widely used as a flame retardant, particularly in polystyrene foams. Commercial HBCD consists largely of three diastereomers, alpha-, beta-, and gamma-HBCD, the structures of which have been known for many years. Recently, the presence in the mixture of small amounts of two minor diastereomers, delta- and epsilon-HBCD, has been reported. Bearing in mind the manner in which commercial HBCD is generated, it was anticipated that these components are probably formed by bromination of trans,trans,trans-cyclododecatriene (ttt-CDT), a common contaminant in commercial ctt-CDT. Indeed, when a sample of ttt-CDT was brominated it gave two products, the NMR spectra and LC/MS and GC/MS behaviour of which confirmed that they are identical to the minor components, delta- and epsilon-HBCD, present in commercial HBCD.     

Carbon management and biodiversity

International efforts to mitigate human-caused changes in the Earth's climate are considering a system of incentives (debits and credits) that would encourage specific changes in land use that can help to reduce the atmospheric concentration of carbon dioxide. The two primary land-based activities that would help to minimize atmospheric carbon dioxide are carbon storage in the terrestrial biosphere and the efficient substitution of biomass fuels and bio-based products for fossil fuels and energy-intensive products. These two activities have very different land requirements and different implications for the preservation of biodiversity and the maintenance of other ecosystem services. Carbon sequestration in living forests can be pursued on lands with low productivity, i.e. on lands that are least suitable for agriculture or intensive forestry, and are compatible with the preservation of biodiversity over large areas. In contrast, intensive harvest-and-use systems for biomass fuels and products generally need more productive land to be economically viable. Intensive harvest-and-use systems may compete with agriculture or they may shift intensive land uses onto the less productive lands that currently harbor most of the Earth's biodiversity. Win-win solutions for carbon dioxide control and biodiversity are possible, but careful evaluation and planning are needed to avoid practices that reduce biodiversity with little net decrease in atmospheric carbon dioxide. Planning is more complex on a politically subdivided Earth where issues of local interest, national sovereignty, and equity come into play.     

137Cs and excess 210Pb deposition patterns in estuarine and marine sediment in the central region of the Great Barrier Reef Lagoon, north-eastern Australia

This paper focuses on the distribution of 137Cs and 210Pb(xs) in 51 estuarine and marine sediment cores collected between the Upstart Bay and Rockingham Bay in the Great Barrier Reef Lagoon, north-eastern Australia. Historical records of 210Pb(xs) and 137Cs atmospheric deposition and present day terrestrial inventories in north-eastern Australia are presented. 210Pb(xs) and 137Cs fluxes measured on suspended sediments in the Burdekin River are considered to be a source of recent inputs of these nuclides to the nearshore region of this part of the Great Barrier Reef. Direct correlations between sediment nuclide inventories, maximum detectable depths, and sediment mass accumulation rates (MARs), calculated using both 137Cs and 210Pb(xs), are explored. In relation to inventories of 210Pb(xs), 60% of atmospheric fallout 137Cs appears to be missing from the sediments. The reasons for these differences in two tracers, primarily of atmospheric origin, are discussed in terms of the geochemical properties of these two nuclides. Evidence is presented to support the hypothesis that the 137Cs distribution in these cores can be a useful independent tracer which provides confirmation of MARs calculated from the decay of 210Pb(xs).     

A distributed approach to accounting for carbon in wood products

With an evolving political environment of commitments to limit emissions of greenhouse gases, and of markets to trade in emissions permits, there is growing scientific, political, and economic need to accurately evaluate carbon (C) stocks and flows—especially those related to human activities. One component of the global carbon cycle that has been contentious is the stock of carbon that is physically held in harvested wood products. The carbon stored in wood products has been sometimes overlooked, but the amount of carbon contained in wood products is not trivial, it is increasing with time, and it is significant to some Parties. This paper is concerned with accurate treatment of harvested wood products in inventories of CO₂ emissions to the atmosphere. The methodologies outlined demonstrate a flexible way to expand current methods beyond the assumption of a simple, first-order decay to include the use of more accurate and detailed data while retaining the simplicity of simple formulas. The paper demonstrates that a more accurate representation of decay time can have significant economic implications in a system where emissions are taxed or emissions permits are traded. The method can be easily applied using only data on annual production of wood products and two parameters to characterize their expected lifetime. These methods are not specific to wood products but can be applied to long-lived, carbon-containing products from sources other than wood, e.g. long-lived petrochemical products. A single unifying approach that is both simple and flexible has the potential to be both more accurate in its results, more efficient in its implementation, and economically important to some Parties.     

Household evacuation characteristics in American Samoa during the 2009 Samoa Islands tsunami

Tsunamis represent significant threats to human life and development in coastal communities. This quantitative study examines the influence of household characteristics on evacuation actions taken by 211 respondents in American Samoa who were at their homes during the 29 September 2009 M_w 8.1 Samoa Islands earthquake and tsunami disaster. Multiple logistic regression analysis of survey data was used to examine the association between evacuation and various household factors. Findings show that increases in distance to shoreline were associated with a slightly decreased likelihood of evacuation, whereas households reporting higher income had an increased probability of evacuation. The response in American Samoa was an effective one, with only 34 fatalities in a tsunami that reached shore in as little as 15 minutes. Consequently, future research should implement more qualitative study designs to identify event and cultural specific determinants of household evacuation behaviour to local tsunamis.