Organic aerosol characterization by complementary measurements of chemical bonds and molecular fragments

Organic aerosol chemical markers from normalized concentrations of independent measurements of mass fragments (using Aerosol Mass Spectrometry, AMS) are compared to bond-based functional groups (from Fourier Transform Infrared spectroscopy, FTIR) during eight field projects in the western hemisphere. Several field projects show weak correlations between alcohol group fractions and m/z 60 fractions, consistent with the organic hydroxyl groups and the fragmentation of saccharides, but the weakness of the correlations indicate chemical differences among the relationships for ambient aerosols in different regions. Carboxylic acid group fractions and m/z 44 fractions are correlated weakly for three projects, with correlations expected for aerosols dominated by di-acid compounds since their fragmentation is typically dominated by m/z 44. Despite differences for three projects with ratios of m/z 44 to m/z 57 fragments less than 10, five projects showed a linear trend between the project-average m/z 44 to m/z 57 ratio and the ratio of acid and alkane functional groups. While this correlation explains only a fraction of the fragment and bond variability measured, the consistency of this relationship at multiple sites indicates a general agreement with the interpretation of the relative amount of m/z 44 as a carboxylic acid group marker and m/z 57 as an alkane group marker.     

Factors affecting the direct mineralization of CO2 with olivine

Olivine, one of the most abundant minerals existing in nature, is explored as a CO2 carbonation agent for direct carbonation of CO2 in flue gas. Olivine based CO2 capture is thermodynamically favorable and can form a stable carbonate for long-term storage. Experimental results have shown that water vapor plays an important role in improving CO2 carbonation rate and capacities. Other operation conditions including reaction temperature, initial CO2 concentration, residence time corresponding to the flow rate of CO2 gas stream, and water vapor concentration also considerably affect the performance of the technology.     

Estimating carbon in savanna ecosystems: rational distribution of effort

Minimising the cost of repeatedly estimating C (C) stocks is crucial to the financial viability of projects that seek to sell C credits. Depending on the price of C, this may imply less or more sampling effort than would be applied for science objectives. In systems with heterogeneous C pools, such as savannas, this translates into a variable-effort sampling strategy that maximises the marginal additional C that can be claimed per incremental unit of effort expended. Analysis of a savanna in north-eastern South Africa indicates relatively modest returns per hectare due to the small C quantities and low sequestration rates. Under these conditions, areas in excess of 1,000 ha and infrequent sampling frequencies of 5–10 years are required to make such projects financially viable. For such projects the sample variance, number of samples, cost per sample and establishment costs have negligible impacts on financial viability. It was also found that the soil-C pool contributes up to three times the net returns of the aboveground C pool and provides a strong argument to monitor soil C for certification and market trading. The financial viability estimates, however, do not include the management or opportunity costs incurred in changing the land use. The economies of scale identified in this study combined with the massive area covered by savannas indicate that these additional costs can be covered. Further research is recommended to quantify these costs and interrogate the feasibility of large scale (in excess of 10,000 ha) C-sink projects in savanna systems.     

Evaluation of Vegetation Near Coal-burning Power Plants in Southwestern Pennsylvania. II. Ozone Injury on Foliage of Hybrid Poplar

The objective of this study was to determine if the incidence or severity of foliar injury induced by regional, ambient ozone was influenced by local emissions from a complex of coal-burning power plants in southwestern Pennsylvania. Plantings of an ozonesensitive hybrid poplar clone {Populus maximowizii x trichocarpa, clone NE 388) were established in 1972 at various distances and directions from the power plants. Foliar injury caused by ambient ozone was evaluated annually from 1973 to 1990 in early to mid- August. Data are presented for the 12-year period, 1979 to 1990 inclusive, for which the most complete data sets were available. Injury from ambient ozone varied spatially and temporally, but with little relationship to power plant location. There was an apparent negative relationship between emission trends and ozone-induced symptoms, but only for one power plant. The correlation between annual mean levels of ozone-induced stipple and frequency of days (per year) with a 1-hr ozone maximum exceeding 0.04 ppm was weak, but significant. Ozone-induced bifacial necrosis was not observed on the foliage of the hybrid poplar during the drought year of 1988 in spite of record high levels of ozone; however, ozoneinduced stipple was observed.     

Analysis of a Summertime PM2.5 and Haze Episode in the Mid-Atlantic Region

Abstract

Observations of the mass and chemical composition of particles less than 2.5 μm in aerodynamic diameter (PM_2.5), light extinction, and meteorology in the urban Baltimore-Washington corridor during July 1999 and July 2000 are presented and analyzed to study summertime haze formation in the mid-Atlantic region. The mass fraction of ammoniated sulfate (SO₄ ^2-) and carbonaceous material in PM_2.5 were each ～50% for cleaner air (PM_2.5 < 10 μg/m³) but changed to ～60% and ～20%, respectively, for more polluted air (PM_2.5 > 30 μg/m³). This signifies the role of SO₄ ^2- in haze formation. Comparisons of data from this study with the Interagency Monitoring of Protected Visual Environments network suggest that SO₄ ^2? is more regional than carbonaceous material and originates in part from upwind source regions. The light extinction coefficient is well correlated to PM_2.5 mass plus water associated with inorganic salt, leading to a mass extinction efficiency of 7.6 ± 1.7 m²/g for hydrated aerosol. The most serious haze episode occurring between July 15 and 19, 1999, was characterized by westerly transport and recirculation slowing removal of pollutants. At the peak of this episode, 1-hr PM_2.5 concentration reached ～45 μg/m³, visual range dropped to ～5 km, and aerosol water likely contributed to ～40% of the light extinction coefficient.     

A free-enzyme catalyst for the bioremediation of environmental atrazine contamination

Herbicide contamination from agriculture is a major issue worldwide, and has been identified as a threat to freshwater and marine environments in the Great Barrier Reef World Heritage Area in Australia. The triazine herbicides are of particular concern because of potential adverse effects, both on photosynthetic organisms and upon vertebrate development. To date a number of bioremediation strategies have been proposed for triazine herbicides, but are unlikely to be implemented due to their reliance upon the release of genetically modified organisms. We propose an alternative strategy using a free-enzyme bioremediant, which is unconstrained by the issues surrounding the use of live organisms. Here we report an initial field trial with an enzyme-based product, demonstrating that the technology is technically capable of remediating water bodies contaminated with the most common triazine herbicide, atrazine.     

Organizational justice,voluntary learning behavior,and job performance: A test of the mediating effects of identification and leader‐member exchange

This paper presents and tests an integrative model of voluntary learning behavior. Drawing on social exchange theory, we argue that individuals are more likely to pursue learning activities when they identify with their employing organization and have a high quality leader–member exchange (LMX) relationship with their supervisor. We further argue that organizational identification is enhanced by both distributive and procedural fairness, whereas LMX quality is enhanced by interpersonal and informational fairness. Moreover, we contend that effective learning behavior improves job performance. The model was tested with a sample of 398 employees from a large automobile dealership. Results supported most predictions. Copyright © 2009 John Wiley & Sons, Ltd.     

Emission Strength Validation Using Four-Dimensional Data Assimilation: Application to Primary Aerosol and Precursors to Ozone and Secondary Aerosol

ABSTRACT

Three-dimensional air quality models (AQMs) represent the most powerful tool to follow the dynamics of air pollutants at urban and regional scales. Current AQMs can account for the complex interactions between gas-phase chemistry, aerosol growth, cloud and scavenging processes, and transport. However, errors in model applications still exist due in part to limitations in the models themselves and in part to uncertainties in model inputs. Four-dimensional data assimilation (FDDA) can be used as a top-down tool to validate several of the model inputs, including emissions inventories, based on ambient measurements. Previously, this FDDA technique was used to estimate adjustments in the strength and composition of emissions of gas-phase primary species and O₃ precursors.

In this paper, we present an extension to the FDDA technique to incorporate the analysis of particulate matter (PM) and its precursors. The FDDA approach consists of an iterative optimization procedure in which an AQM is coupled to an inverse model, and adjusting the emissions minimizes the difference between ambient measurements     

Integrated Assessment Modeling of Atmospheric Pollutants in the Southern Appalachian Mountains. Part I: Hourly and Seasonal Ozone

Abstract

Recently, a comprehensive air quality modeling system was developed as part of the Southern Appalachians Mountains Initiative (SAMI) with the ability to simulate meteorology, emissions, ozone, size- and composition-resolved particulate matter, and pollutant deposition fluxes. As part of SAMI, the RAMS/EMS-95/URM-1ATM modeling system was used to evaluate potential emission control strategies to reduce atmospheric pollutant levels at Class I areas located in the Southern Appalachians Mountains. This article discusses the details of the ozone model performance and the methodology that was used to scale discrete episodic pollutant levels to seasonal and annual averages. The daily mean normalized bias and error for 1-hr and 8-hr ozone were within U.S. Environment Protection Agency guidance criteria for urban-scale modeling. The model typically showed a systematic overestimation for low ozone levels and an underestimation for high levels. Because SAMI was primarily interested in simulating the growing season ozone levels in Class I areas, daily and seasonal cumulative ozone exposure, as characterized by the W126 index, were also evaluated. The daily ozone W126 performance was not as good as the hourly ozone performance; however, the seasonal ozone W126 scaled up from daily values was within 17% of the observations at two typical Class I areas of the SAMI region. The overall ozone performance of the model was deemed acceptable for the purposes of SAMI’s assessment.