Variations in speciated emissions from spark-ignition and compression-ignition motor vehicles in California's south coast air basin

The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.     

Ambient Ozone Concentration Patterns among Eastern U.S. Urban Areas Using Factor Analysis

Data on dally maximum ozone concentrations measured at ambient air monitoring stations operated by state and local air pollution control agencies in the Eastern United States were analyzed using principal factor analysis. Four orthogonal factors representing O₃ formation potentials were derived using the statistical package SPSS; these factors accounted for over two-thirds of the variations in 1978 summer O₃ levels at 21 urban-oriented stations. The analysis confirmed that O₃ variations are similar among stations within defined geographical areas; this confirmation supports the widely held theory that ambient O₃ formations are reglonwlde. The analysis suggested that trends analysis for determining general progress in improving O₃ air quality should be based on aggregate statistics from clusters of monitors rather than from a single monitoring station within areas associated with the derived factors.     

Odor Control In Los Angeles County

Abstract

Concentrations of 38 gas-phase organic air toxics were measured over a 2-yr period at four different sites in and around Pittsburgh, PA, to investigate spatial variations in health risks from chronic exposure. The sites were chosen to represent different exposure regimes: a downtown site with substantial mobile source emissions; two residential sites adjacent to one of the most heavily industrialized zones in Pittsburgh; and a regional background site. Lifetime cancer risks and non-cancer hazard quotients were estimated using a traditional and interactive risk models. Although study average concentrations of specific air toxics varied by as a much as a factor of 26 between the sites, the additive cancer risks of the gas-phase organic air toxics varied by less than a factor of 2, ranging from 6.1 × 10^-5 to 9.5 × 10^-5. The modest variation in risks reflects the fact that two regionally distributed toxics, formalde-hyde and carbon tetrachloride (CCl₄), contributed more than half of the cancer risk at all four sites. Benzene contributed substantial cancer risks at all sites, whereas trichloroethene and 1,4-dichlorobenzene only contributed substantial cancer risks at the downtown site. Only acrolein posed a non-cancer risk. Diesel particulate matter is estimated to pose a much greater cancer risk in Pittsburgh than other classes of air toxics including gas-phase organic, metals, polycyclic aromatic hydrocarbons, and coke oven emissions. Health risks of air toxics in Pittsburgh are comparable with those in other urban areas in the United States.     

Evaluation of Continuous Performance Monitoring Techniques for Hazardous Waste Incinerators

This paper discusses monitoring the waste destruction efficiency of hazardous waste incinerators. The particular problem is to ensure that incinerators do not release, without detection, significant quantities of waste as a result of operating fluctuations or equipment degradation. To detect these conditions, continuous, automated, and real-time source monitoring is required. Detection of degraded performance by monitoring and measuring waste compounds directly is not presently possible on a continuous basis. An alternative is to use commercially available continuous monitors to measure combustion intermediates (e.g., CO or hydrocarbons) and thereby infer waste destruction efficiency. Required, however, is a correlation between the emission of intermediates and the emission of waste. In this paper, the response of a number of these continuous monitors is compared with waste destruction efficiency measurements from a laboratory scale, liquid-spray incinerator operated on fuel oil doped with model waste compounds: benzene, chlorobenzene, acrylonitrile, and chloroform. Total hydrocarbon and CH₄ measurements are found to vary with waste emission in a nearly linear manner; however, a substantial increase in CO emission occurs before a significant amount of waste is released. These results suggest that CO may serve as an indicator of the approach of waste release, while total hydrocarbons may provide an indicator of immediate waste release.     

3D-QSAR of fungal quorum-sensing inhibiting analogs of farnesol

Thirty-four analogs with variable antifungal activity were selected to develop models for establishing three-dimensional quantitative structure-activity relationships (3D-QSAR). Comparative molecular field analysis (CoMFA) and comparative similarity indices analyses (CoMSIA) were conducted on the group of analogs to determine the structural requirements for selectivity and potency in inhibiting biofilm formation and fungal growth. The best CoMFA model predicted a q² = 0.5 and an r² = 0.991, and revealed that electrostatic properties play a significant role in potency and selectivity. The best CoMSIA model combined electrostatics, hydrogen bond acceptor and donor, and hydrophobic fields with a q² = 0.664 r² = 0.952, S = 0.099, and F = 139.892. The analyses of the contour maps from both models provide significant insight into the structural necessities for a potent compound. Therefore, manipulating various chemical properties of the substituted groups on the farnesol chain can be used to enhance the fungicidal properties of the target compound.     

Adsorption and breakdown of penicillin antibiotic in the presence of titanium oxide nanoparticles in water

The fate and transport of antibiotics in natural water systems is controlled in part by interactions with nanometer (10⁻⁹ m) metal oxide particles. Experiments were performed by mixing solutions of ampicillin (AMP), a common, penicillin-class human and veterinary antibiotic, with 25 nm-TiO₂ (anatase) nanoparticles at different pH conditions. Both sorption and degradation of AMP were observed in the AMP-nanoparticle solutions. For AMP concentrations from ∼3 μM to 2.9 mM the overall AMP removal from solution can be described by linear isotherms with removal coefficients (K_r) of 3028 (±267) L kg⁻¹ at pH 2, 11,533 (±823) L kg⁻¹ at pH 4, 12,712 (±672) L kg⁻¹ at pH 6, and 1941 (±342) L kg⁻¹ at pH 8. Mass spectral analysis of AMP solutions after removal of the solid nanoparticles yielded ions that indicate the presence of peniclloic acid, penilloic acid and related de-ammoniated by-products as possible compounds resulting from the degradation of AMP at the TiO₂ surface.     

Structuring sustainability science

It is urgent in science and society to address climate change and other sustainability challenges such as biodiversity loss, deforestation, depletion of marine fish stocks, global ill-health, land degradation, land use change and water scarcity. Sustainability science (SS) is an attempt to bridge the natural and social sciences for seeking creative solutions to these complex challenges. In this article, we propose a research agenda that advances the methodological and theoretical understanding of what SS can be, how it can be pursued and what it can contribute. The key focus is on knowledge structuring. For that purpose, we designed a generic research platform organised as a three-dimensional matrix comprising three components: core themes (scientific understanding, sustainability goals, sustainability pathways); cross-cutting critical and problem-solving approaches; and any combination of the sustainability challenges above. As an example, we insert four sustainability challenges into the matrix (biodiversity loss, climate change, land use changes, water scarcity). Based on the matrix with the four challenges, we discuss three issues for advancing theory and methodology in SS: how new synergies across natural and social sciences can be created; how integrated theories for understanding and responding to complex sustainability issues can be developed; and how theories and concepts in economics, gender studies, geography, political science and sociology can be applied in SS. The generic research platform serves to structure and create new knowledge in SS and is a tool for exploring any set of sustainability challenges. The combined critical and problem-solving approach is essential.     

Effects of Heating Season on Residential Indoor and Outdoor Polycyclic Aromatic Hydrocarbons, Black Carbon, and Particulate Matter in an Urban Birth Cohort

Exposure to air pollutants has been associated with adverse health effects. However, analyses of the effects of season and ambient parameters such as ozone have not been fully conducted. Residential indoor and outdoor air levels of polycyclic aromatic hydrocarbons (PAH), black carbon (measured as absorption coefficient [Abs]), and fine particulate matter <2.5 μm (PM)(2.5) were measured over two-weeks in a cohort of 5-6 year old children (n=334) living in New York City's Northern Manhattan and the Bronx between October 2005 and April 2010. The objectives were to: 1) characterize seasonal changes in indoor and outdoor levels and indoor/outdoor (I/O) ratios of PAH (gas + particulate phase; dichotomized into Σ(8)PAH(semivolatile) (MW 178-206), and Σ(8)PAH(nonvolatile) (MW 228-278)), Abs, and PM(2.5); and 2) assess the relationship between PAH and ozone. Results showed that heating compared to nonheating season was associated with greater Σ(8)PAH(nonvolatile) (p<0.001) and Abs (p<0.05), and lower levels of Σ(8)PAH(semivolatile) (p<0.001). In addition, the heating season was associated with lower I/O ratios of Σ(8)PAH(nonvolatile) and higher I/O ratios of Σ(8)PAH(semivolatile) (p<0.001) compared to the nonheating season. In outdoor air, Σ(8)PAH(nonvolatile) was correlated negatively with community-wide ozone concentration (p<0.001). Seasonal changes in emission sources, air exchanges, meteorological conditions and photochemical/chemical degradation reactions are discussed in relationship to the observed seasonal trends.     

Theory of planned behaviour, identity and intentions to engage in environmental activism

This study incorporated identity constructs into the theory of planned behaviour (TPB) to investigate intentions to engage in environmental activism. First year students and participants of a students of sustainability conference (n=169) were administered a questionnaire survey that measured standard TPB constructs as well as environmental group membership and self-identity as an environmental activist. Consistent with predictions, environmental group membership and self-identity were positive predictors of intentions. Thus, greater involvement in environmental groups and a stronger sense of the self as an environmental activist were associated with stronger intentions to engage in environmental activism. There was also evidence that self-identity was a stronger predictor of intentions for participants with low rather than high environmental group membership. In accordance with the standard TPB model, participants with more positive attitudes toward and a greater sense of normative support for environmental activism also had greater intentions to engage in the behaviour. The implications for groups seeking to harness support for activities to protect the environment are discussed.