Characterization of products formed in the reaction of ozone with alpha-pinene: case for organic peroxides

The generation of reactive oxygen species (ROS) and their subsequent induced pulmonary and systemic oxidative stress has been implicated as an important molecular mechanism of PM-mediated toxicity. However, recent work has shown that there is significant ROS associated with ambient PM. In order to understand the formation mechanisms as well as understand the potential health effects of particle-bound oxidative species, the alpha-pinene-O(3) oxidation chemical system was studied to elucidate the structures of reaction products using liquid chromatography-multiple stage mass spectrometry (LC-MS(n)). The classes of compounds identified based on their multiple stage-MS fragmentation patterns, mechanistic considerations of alpha-pinene-O(3) oxidation, and general fragmentation rules, of the products from this reaction system were highly oxygenated species, predominantly containing hydroperoxide and peroxide functional groups. The oxidant species observed were clearly stable for the 1-3 h that elapsed during aerosol collection and analysis, and probably for much longer, thus rendering it possible for these species to bind onto particles forming fine particulate organic peroxides that concentrate on the particles and could deliver concentrated doses of ROS in vivo to tissue.     

Assessment of Integrated Pedestrian Protection Systems with Autonomous Emergency Braking (AEB) and Passive Safety Components

Objective: Autonomous emergency braking (AEB) systems fitted to cars for pedestrians have been predicted to offer substantial benefit. On this basis, consumer rating programs—for example, the European New Car Assessment Programme (Euro NCAP)—are developing rating schemes to encourage fitment of these systems. One of the questions that needs to be answered to do this fully is how the assessment of the speed reduction offered by the AEB is integrated with the current assessment of the passive safety for mitigation of pedestrian injury. Ideally, this should be done on a benefit-related basis.

The objective of this research was to develop a benefit-based methodology for assessment of integrated pedestrian protection systems with AEB and passive safety components. The method should include weighting procedures to ensure that it represents injury patterns from accident data and replicates an independently estimated benefit of AEB.

Methods: A methodology has been developed to calculate the expected societal cost of pedestrian injuries, assuming that all pedestrians in the target population (i.e., pedestrians impacted by the front of a passenger car) are impacted by the car being assessed, taking into account the impact speed reduction offered by the car's AEB (if fitted) and the passive safety protection offered by the car's frontal structure. For rating purposes, the cost for the assessed car is normalized by comparing it to the cost calculated for a reference car.

The speed reductions measured in AEB tests are used to determine the speed at which each pedestrian in the target population will be impacted. Injury probabilities for each impact are then calculated using the results from Euro NCAP pedestrian impactor tests and injury risk curves. These injury probabilities are converted into cost using “harm”-type costs for the body regions tested. These costs are weighted and summed. Weighting factors were determined using accident data from Germany and Great Britain and an independently estimated AEB benefit. German and Great Britain versions of the methodology are available. The methodology was used to assess cars with good, average, and poor Euro NCAP pedestrian ratings, in combination with a current AEB system. The fitment of a hypothetical A-pillar airbag was also investigated.

Results: It was found that the decrease in casualty injury cost achieved by fitting an AEB system was approximately equivalent to that achieved by increasing the passive safety rating from poor to average. Because the assessment was influenced strongly by the level of head protection offered in the scuttle and windscreen area, a hypothetical A-pillar airbag showed high potential to reduce overall casualty cost.

Conclusions: A benefit-based methodology for assessment of integrated pedestrian protection systems with AEB has been developed and tested. It uses input from AEB tests and Euro NCAP passive safety tests to give an integrated assessment of the system performance, which includes consideration of effects such as the change in head impact location caused by the impact speed reduction given by the AEB.     

Conceptual Models as Hypotheses in Monitoring Urban Landscapes

Many problems and challenges of ecosystem management currently are driven by the rapid pace and spatial extent of landscape change. Parks and reserves within areas of high human population density are especially challenged to meet the recreational needs of local populations and to preserve valued environmental resources. The complex problem of managing multiple objectives and multiple resources requires an enormous quantity of information, and conceptual models have been proposed as tools for organizing and interpreting this information. Academics generally prefer a bottom-up approach to model construction that emphasizes ecologic theory and process, whereas managers often use a top-down approach that takes advantage of existing information to address more pragmatic objectives. The authors propose a formal process for developing, applying, and testing conceptual models to be used in landscape monitoring that reconciles these seemingly opposing perspectives. The four-step process embraces the role of hypothesis testing in the development of models and evaluation of their utility. An example application of the process to a network of national parks in and around Washington, DC illustrates the ability of the approach to systematically identify monitoring data that would both advance ecologic theory and inform management decisions.     

Application of Zoning and “Limits of Acceptable Change” to Manage Snorkelling Tourism

Zoning and applying Limits of Acceptable Change (LAC) are two promising strategies for managing tourism in Marine Protected Areas (MPAs). Typically, these management strategies require the collection and integration of ecological and socioeconomic data. This problem is illustrated by a case study of Koh Chang National Marine Park, Thailand. Biophysical surveys assessed coral communities in the MPA to derive indices of reef diversity and vulnerability. Social surveys assessed visitor perceptions and satisfaction with conditions encountered on snorkelling tours. Notably, increased coral mortality caused a significant decrease in visitor satisfaction. The two studies were integrated to prescribe zoning and “Limits of Acceptable Change” (LAC). As a biophysical indicator, the data suggest a LAC value of 0.35 for the coral mortality index. As a social indicator, the data suggest that a significant fraction of visitors would find a LAC value of under 30 snorkellers per site as acceptable. The draft zoning plan prescribed four different types of zones: (I) a Conservation Zone with no access apart from monitoring or research; (II) Tourism Zones with high tourism intensities at less vulnerable reefs; (III) Ecotourism zones with a social LAC standard of <30 snorkellers per site, and (IV) General Use Zones to meet local artisanal fishery needs. This study illustrates how ecological and socioeconomic field studies in MPAs can be integrated to craft zoning plans addressing multiple objectives.     

Controlled Exposures of Volunteers to Respirable Carbon and Sulf uric Acid Aerosols

Respirable carbon or fly ash particles are suspected to increase the respiratory toxicity of coexisting acidic air pollutants, by concentrating acid on their surfaces and so delivering it efficiently to the lower respiratory tract. To investigate this issue, we exposed 15 healthy and 15 asthmatic volunteers in a controlled- environment chamber (21°C, 50 percent relative humidity) to four test atmospheres: (i) clean air; (ii) 0.5-μm H2SO4 aerosol at =100 μg/m³, generated from water solution; (iii) 0,5-μm carbon aerosol at =250 μg/m³, generated from highly pure carbon black with specific surface area comparable to ambient pollution particles; and (iv) carbon as in (iii) plus =100 μg/m³ of ultrafine H2SO4 aerosol generated from fuming sulfuric acid. Electron microscopy showed that nearly all acid in (iv) became attached to carbon particle surfaces, and that most particles remained in the sub-μm size range. Exposures were performed double-blind, 1 week apart. They lasted 1 hr each, with alternate 10-min periods of heavy exercise (ventilation =50 L/min) and rest. Subjects gargled citrus juice before exposure to suppress airway ammonia. Lung function and symptoms were measured pre-exposure, after initial exercise, and at endexposure. Bronchial reactivity to methacholine was measured after exposure. Statistical analyses tested for effects of H₂SO₄ or carbon, separate or interactive, on health measures. Group data showed no more than small equivocal effects of any exposure on any health measure. One individual's responses were consistent with a clinically significant excess airway constriction from H₂SO₄ plus carbon, and 2-3 others showed slight excess responses to the combined pollutants, but all these observations might have reflected chance variations. We conclude that coexisting carbon aerosol did not increase respiratory irritancy of H₂SO₄, in most healthy and asthmatic subjects exposed for 1 hr under simulated "worst-case" ambient conditions.     

Radionuclides in deer and elk from Los Alamos National Laboratory and the doses to humans from the ingestion of muscle and bone.

This paper summarizes radionuclide concentrations (3H, 90Sr, 137Cs, 238Pu, 239,240Pu, 241Am, and totU) in muscle and bone tissue of mule deer (Odocoileus hemionus) and Rocky Mountain elk (Cervus elaphus) collected from Los Alamos National Laboratory (LANL), Los Alamos, New Mexico, lands from 1991 through 1998. Also, the committed effective dose equivalent (CEDE) and the risk of excess cancer fatalities (RECF) to people who ingest muscle and bone from deer and elk collected from LANL lands were estimated. Most radionuclide concentrations in muscle and bone from individual deer (n = 11) and elk (n = 22) collected from LANL lands were either at less than detectable quantities (where the analytical result was smaller than two counting uncertainties) and/or within upper (95%) level background (BG) concentrations. As a group, most radionuclides in muscle and bone of deer and elk from LANL lands were not significantly higher (p < 0.10) than in similar tissues from deer (n = 3) and elk (n = 7) collected from BG locations. Also, elk that had been radio collared and tracked for two years and spent an average time of 50% of LANL lands were not significantly different in most radionuclides from road kill elk that have been collected as part of the environmental surveillance program. Overall, the upper (95%) level net CEDEs (the CEDE plus two sigma for each radioisotope minus background) at the most conservative ingestion rate (50 lbs of muscle and 13 lbs of bone) were as follows: deer muscle = 0.22 mrem y-1 (2.2 microSv y-1), deer bone = 3.8 mrem y-1 (38 microSv y-1), elk muscle = 0.12 mrem y-1 (1.2 microSv y-1), and elk bone = 1.7 mrem y-1 (17 microSv y-1). All CEDEs were far below the International Commission on Radiological Protection guideline of 100 mrem y-1 (1000 microSv y-1), and the highest muscle plus bone net CEDE corresponded to a RECF of 2E-06, which is far below the Environmental Protection Agency upper level guideline of 1E-04.     

Designing the Masoala National Park in Madagascar Based on Biological and Socioeconomic Data

Abstract: Conservation biologists have developed powerful tools for reserve selection and design over the past two decades, yet seldom are protected areas actually designed on scientific grounds. Using fundamental biological and socioeconomic principles of conservation science, we designed a new protected area and its multiple-use zone on the Masoala Peninsula in the humid forest zone of Madagascar. The explicit design criteria determined the data gathered for the work, which included (1) spatial distribution and quality of habitat, (2) the areas and species at greatest risk, (3) the relationship between environmental gradients and species distributions, (4) current and predicted human settlement and land and resource use, and (5) the economic potential of natural forest management as an alternative to deforestation. We used a geographic information system to integrate these data layers and applied the design criteria to develop a park proposal that balanced human and wildlife needs. The proposal won the approval of local residents, and a national decree in 1997 designated 2100 km² of rainforest and three satellite marine reserves as the Masoala National Park, with a surrounding multiple-use zone of approximately 1000 km². The new park is Madagascar's largest protected area and protects more lowland (<400 m) humid forest habitat than the entire reserve system combined, a significant step forward in conserving a globally important ecoregion. Consideration of local needs and the national economy was a key element in gaining approval for the Masoala Park. Such an approach toward reserve design could be applied elsewhere to improve chances of establishing and maintaining protected areas over the long term.     

Using variance components to estimate power in a hierarchically nested sampling design

We used variance components to assess allocation of sampling effort in a hierarchically nested sampling design for ongoing monitoring of early life history stages of the federally endangered Devils Hole pupfish (DHP) (Cyprinodon diabolis). Sampling design for larval DHP included surveys (5 days each spring 2007–2009), events, and plots. Each survey was comprised of three counting events, where DHP larvae on nine plots were counted plot by plot. Statistical analysis of larval abundance included three components: (1) evaluation of power from various sample size combinations, (2) comparison of power in fixed and random plot designs, and (3) assessment of yearly differences in the power of the survey. Results indicated that increasing the sample size at the lowest level of sampling represented the most realistic option to increase the survey’s power, fixed plot designs had greater power than random plot designs, and the power of the larval survey varied by year. This study provides an example of how monitoring efforts may benefit from coupling variance components estimation with power analysis to assess sampling design.