Modeling Evidence of Incloud Transformation Of Sulfur Dioxide to Sulfate

Methylene chloride (CH₂Cl₂) is presently under study by the U.S. EPA and other agencies to determine if the compound presents an unreasonable risk to human health and to determine if regulatory action is needed to reduce the risk. This paper describes one portion of the study which required the development and validation of a method of sampling and analysis for source emission measurements.

Prior to source sampling, laboratory experiments were conducted to determine the best sample container in which to collect an integrated sample. It was found that CH₂Cl₂ remained stable in Tedlar bags for at least four weeks. The analytical method selected was gas chromatography with flame ionization detection (GC/FID). During the field portion of the study, both manufacturer and user emission sources of CH₂Cl₂ were tested. Multiple sets of simultaneous quadruplicate bag samples were collected to determine the precision of both sampling and analysis in the field. All samples were analyzed at the test site after collection and then returned to Research Triangle Park. Samples were subsequently reanalyzed in the laboratories of Radian and the U.S. EPA using three GC/FID instruments and two types of GC columns. The range of concentrations from the sources was 100 ppm to 27,000 ppm CH₂Cl₂. A statistical analysis of samples collected simultaneously showed no difference in the samples, proving good precision In both sampling and analysis. Some of the sample bags returned from the test sites developed leaks indicating that immediate on-site analysis is best. A comparison of results obtained in the field and the two laboratories showed that interand intra-laboratory precision was within 10 percent.     

A Strategy and Methodology for Defensibly Correlating Spilled Oil to Source Candidates

The source of crude oils and petroleum products released into navigable waterways and shipping lanes is not always known. Thus, the defensible identification of spilled crude oils and petroleum products and their correlation to suspected sources is a critical part of many oil spill assessments. Quantitative "fingerprinting" analysis, when evaluated using straightforward statistical and numerical analyses, provides a defensible means to differentiate among qualitatively similar oils and provides the best assessment of the source(s) for spilled oils. Polycyclic aromatic hydrocarbon (PAH) and petroleum biomarker concentration data are a particularly useful quantitative measure that can benefit most oil spill investigations. In this paper the strategy and methodology for correlation analysis that relies upon quantitative gas chromatography/mass spectrometry operated in the selected ion monitoring mode (GC/MS-SIM) is demonstrated in a case study involving 66 candidate sources for a heavy fuel oil spill of unknown origin. The strategy includes identification of 19 chemical indices (out of 45 evaluated) based upon PAH's and biomarkers that were (1) independent of weathering; and (2) precisely measured, both of which are determined by statistical analysis of the data. The 19 chemical indices meeting these criteria are subsequently analysed using principal component analysis (PCA), which helps to determine defensibly the "prime suspects" for the oil spill under investigation. The strategy and methodology described, which combines statistical and numerical analysis of quantitative chemical data, can be adapted and applied to other environmental forensic investigations with the objective of correlating any form of contamination to its suspected sources.     

Effect of Interfacial Modifiers on Mechanical and Physical Properties of the PHB Composite with High Wood Flour Content

To explore the commercial viability of Polyhydroxybutyrate (PHB)/wood flour (WF) composites, systems were produced at industry-standard levels of fiber loading. Further, four interfacial modifiers were selected to improve the mechanical properties of PHB/WF composites, including maleated PHB (PHB-g-MA), a low molecular weight epoxy, a low molecular weight polyester, and polymethylene-diphenyl-diisocyante (pMDI). Results showed that all modifiers resulted in improvements in tensile strength and modulus, however, pMDI showed the highest improvements. The pMDI modifier also improved water uptake of the composites. Study of the fracture surfaces showed signs of improved fiber bonding, as did morphological studies by dynamic mechanical analysis (DMA), and differential scanning calorimetry (DSC). Interpretation of the DSC and DMA results indicate possible reactions with lubricant, and interactions between PHB and wood fibers with the addition of pMDI.     

Implications of cation exchange on clay release and colloid-facilitated transport in porous media

Column experiments were conducted to study chemical factors that influence the release of clay (kaolinite and quartz minerals) from saturated Ottawa sand of different sizes (710,360, and 240 microm). A relatively minor enhancement of clay release occurred when the pH was increased (5.8 to 10) or the ionic strength (IS) was decreased to deionized (DI) water. In contrast, clay release was dramatically enhanced when monovalent Na+ was exchanged for multivalent cations (e.g., Ca2+ and Mg2+) on the clay and sand and then the solution IS was reduced to DI water. This solution chemistry sequence decreased the adhesive force acting on the clay as a result of an increase in the magnitude of the clay and sand zeta potential with cation exchange, and expansion of the double layer thickness with a decrease in IS to DI water. The amount of clay release was directly dependent on the Na+ concentration of the exchanging solution and on the initial clay content of the sand (0.026-0.054% of the total mass). These results clearly demonstrated the importance of the order and magnitude of the solution chemistry sequence on clay release. Column results and scanning electron microscope (SEM) images also indicated that the clay was reversibly retained on the sand, despite predictions of irreversible interaction in the primary minimum. One plausible explanation is that adsorbed cations increased the separation distance between the clay-solid interfaces as a result of repulsive hydration forces. A cleaning procedure was subsequently developed to remove clay via cation exchange and IS reduction; SEM images demonstrated the effectiveness of this approach. The transport of Cu2+ was then shown to be dramatically enhanced by an order of magnitude in peak concentration by adsorption on clays that were released following cation exchange and IS reduction.     

Understanding vulnerability in southern Africa: comparative findings using a multiple-stressor approach in South Africa and Malawi

Within southern Africa, many households are facing increasing pressures as they deal with multiple challenges such as low employment, high levels of disease, environmental resources under pressure and changing political landscapes. To respond to the needs of different individuals and households, it is important to define the nature of their vulnerability. An increasing amount of theoretical and empirical work on the concept of ‘vulnerability’ has led to a range of definitions, indicators and measurement tools, which have come to characterise this field of study. As a result, there is no one general consensus. This paper presents the results from the latest in a series of applied studies conducted since 2004 by a network of scientists working in southern Africa, aimed at refining the definition and application of the concept of vulnerability. The study employed a recently developed multiple-stressor model to guide the collection and analysis of data from three sites in South Africa and Malawi. In this paper, we identify and explore five key ‘symptoms’ of vulnerability emerging from our multi-country data and reflect on the usefulness of the model employed.     

Emission Factors for High-Emitting Vehicles Based on On-Road Measurements of Individual Vehicle Exhaust with a Mobile Measurement Platform

ABSTRACT

Fuel-based emission factors for 143 light-duty gasoline vehicles (LDGVs) and 93 heavy-duty diesel trucks (HDDTs) were measured in Wilmington, CA using a zero-emission mobile measurement platform (MMP). The frequency distributions of emission factors of carbon monoxide (CO), nitrogen oxides (NO_x), and particle mass with aerodynamic diameter below 2.5 μm (PM_2.5) varied widely, whereas the average of the individual vehicle emission factors were comparable to those reported in previous tunnel and remote sensing studies as well as the predictions by Emission Factors (EMFAC) 2007 mobile source emission model for Los Angeles County. Variation in emissions due to different driving modes (idle, low- and high-speed acceleration, low- and high-speed cruise) was found to be relatively small in comparison to intervehicle variability and did not appear to interfere with the identification of high emitters, defined as the vehicles whose emissions were more than 5 times the fleet-average values. Using this definition, approximately 5% of the LDGVs and HDDTs measured were high emitters. Among the 143 LDGVs, the average emission factors of NO_x, black carbon (BC), PM_2.5, and ultrafine particle (UFP) would be reduced by 34%, 39%, 44%, and 31%, respectively, by removing the highest 5% of emitting vehicles, whereas CO emission factor would be reduced by 50%. The emission distributions of the 93 HDDTs measured were even more skewed: approximately half of the NO_x and CO fleet-average emission factors and more than 60% of PM_2.5, UFP, and BC fleet-average emission factors would be reduced by eliminating the highest-emitting 5% HDDTs. Furthermore, high emissions of BC, PM_2.5, and NO_x tended to cluster among the same vehicles.

IMPLICATIONS This study presents the characterization of on-road vehicle emissions in Wilmington, CA, by sampling individual vehicle plumes. Approximately 5% of the vehicles were high emitters, whose emissions were more than 5 times the fleet-average values. These high emitters were responsible for 30% and more than 50% of the average emission factors of LDGVs and HDDVs, respectively. It is likely that as the overall fleet becomes cleaner due to more stringent regulations, a small fraction of the fleet may contribute a growing and disproportionate share of the overall emissions. Therefore, long-term changes in on-road emissions need to be monitored.     

History of mercury use and environmental contamination at the Oak Ridge Y-12 Plant

Between 1950 and 1963 approximately 11 million kilograms of mercury (Hg) were used at the Oak Ridge Y-12 National Security Complex (Y-12 NSC) for lithium isotope separation processes. About 3% of the Hg was lost to the air, soil and rock under facilities, and East Fork Poplar Creek (EFPC) which originates in the plant site. Smaller amounts of Hg were used at other Oak Ridge facilities with similar results. Although the primary Hg discharges from Y-12 NSC stopped in 1963, small amounts of Hg continue to be released into the creek from point sources and diffuse contaminated soil and groundwater sources within Y-12 NSC. Mercury concentration in EFPC has decreased 85% from ∼2000 ng/L in the 1980s. In general, methylmercury concentrations in water and in fish have not declined in response to improvements in water quality and exhibit trends of increasing concentration in some cases.     

First detection of an NSAID, flunixin, in sheep's wool using GC-MS

Exposure to the nonsteroidal anti-inflammatory drug (NSAID) diclofenac resulted in the near extinction of three species of Gyps vultures on the Indian subcontinent. Other NSAIDs present in the environment, including flunixin, may pose a similar risk. In the course of a study to determine the feasibility of detecting NSAIDs in keratinous matrices (i.e., hair, nails and feathers) using GC-MS, wool opportunistically collected from a sheep treated with flunixin was analysed for residues. Flunixin was detected qualitatively in external wool wash and extract samples. While residues of veterinary agents and pesticides have previously been found in sheep’s wool, our preliminary investigation provides the first instance of an NSAID being detected in this matrix. Here we provide the sample preparation methods and GC-MS parameters used to enable further refinement as part of ongoing conservation and consumer quality control measures.     

Earth stewardship: Shaping a sustainable future through interacting policy and norm shifts

Transformation toward a sustainable future requires an earth stewardship approach to shift society from its current goal of increasing material wealth to a vision of sustaining built, natural, human, and social capital—equitably distributed across society, within and among nations. Widespread concern about earth’s current trajectory and support for actions that would foster more sustainable pathways suggests potential social tipping points in public demand for an earth stewardship vision. Here, we draw on empirical studies and theory to show that movement toward a stewardship vision can be facilitated by changes in either policy incentives or social norms. Our novel contribution is to point out that both norms and incentives must change and can do so interactively. This can be facilitated through leverage points and complementarities across policy areas, based on values, system design, and agency. Potential catalysts include novel democratic institutions and engagement of non-governmental actors, such as businesses, civic leaders, and social movements as agents for redistribution of power. Because no single intervention will transform the world, a key challenge is to align actions to be synergistic, persistent, and scalable.     

Nesting Success of a Neotropical Migrant in a Multiple-Use, Forested Landscape

Abstract: We studied the nesting success of an individually marked population of Kentucky Warblers ( Oporornis formosus ), a species that nests in disturbed and undisturbed forests, in a heterogeneous, managed forest site in the Shawnee National Forest in southern Illinois from 1992 to 1995. We examined the effects of forest stand type (clearcuts of various ages, tree plantations, and older forest) and distance from habitat edges on rates of nest predation and brood parasitism by Brown-headed Cowbirds (   Molothrus ater ). Brood parasitism levels gradually decreased from 60% to 3% ( nests) over a distance of 2 km from an agricultural edge proximal to a known cowbird foraging site (a pig feedlot), but they did not vary with distance from any other kinds of edges or with forest stand type. Rates of nest predation ( nests) did not vary with distance from any edges, but they were significantly lower in older forest than within even-aged clearcuts, a tree plantation, and in successional vegetation adjacent to a residential facility. These results suggest that, even in fragmented landscapes with high overall levels of parasitism and nest predation, management practices within and immediately adjacent to forest tracts can affect the nesting success of some species, but not necessarily as a simple function of distance from edge. For the Kentucky Warbler, our results suggest that a management strategy that avoids even-age silviculture and leaves core stands of older forest far from cowbird feeding areas can increase nesting success to levels similar to those measured in more forested landscapes.