TERPENE AND TERPENOID EMISSIONS AND SECONDARY ORGANIC AEROSOL PRODUCTION

Approximately 90% of fine aerosol in the Midwestern United States has a regional component with a sizable fraction attributed to secondary production of organic aerosol (SOA). The Ozark Forest is an important source of biogenic SOA precursors like isoprene (> 150 mg m-2 d-1), monoterpenes (10-40 mg m-2 d-1), and sesquiterpenes (10-40 mg m-2d-1). Anthropogenic sources include secondary sulfate and nitrate and biomass burning (51-60%), vehicle emissions (17-26%), and industrial emissions (16-18%). Vehicle emissions are an important source of volatile and vapor-phase, semivolatile aliphatic and aromatic hydrocarbons that are important anthropogenic sources of SOA precursors. The short lifetime of SOA precursors and the complex mixture of functionalized oxidation products make rapid sampling, quantitative processing methods, and comprehensive organic molecular analysis essential elements of a comprehensive strategy to advance understanding of SOA formation pathways. Uncertainties in forecasting SOA production on regional scales are large and related to uncertainties in biogenic emission inventories and measurement of SOA yields under ambient conditions. This work presents a bottom-up approach to develop a conifer emission inventory based on foliar and cortical oleoresin composition, development of a model to estimate terpene and terpenoid signatures of foliar and bole emissions from conifers, development of processing and analytic techniques for comprehensive organic molecular characterization of SOA precursors and oxidation products, implementation of the high-volume sampling technique to measure OA and vapor-phase organic matter, and results from a 5 day field experiment conducted to evaluate temporal and diurnal trends in SOA precursors and oxidation products. A total of 98, 115, and 87 terpene and terpenoid species were identified and quantified in commercially available essential oils of Pinus sylvestris, Picea mariana, and Thuja occidentalis, respectively, by comprehensive, two-dimensional gas chromatography with time-of-flight mass spectrometric detection (GC × GC-ToF-MS). Analysis of the literature showed that cortical oleoresin composition was similar to foliar composition of the oldest branches. Our proposed conceptual model for estimation of signatures of terpene and terpenoid emissions from foliar and cortical oleoresin showed that emission potentials of the foliar and bole release pathways are dissimilar and should be considered for conifer species that develop resin blisters or are infested with herbivores or pathogens. Average derivatization efficiencies for Methods 1 and 2 were 87.9 and 114%, respectively. Despite the lower average derivatization efficiency of Method 1, distinct advantages included a greater certainty of derivatization yield for the entire suite of multi- and poly-functional species and fewer processing steps for sequential derivatization. Detection limits for Method 1 using GC × GC- ToF-MS were 0.09-1.89 ng μL-1. A theoretical retention index diagram was developed for a hypothetical GC × 2GC analysis of the complex mixture of SOA precursors and derivatized oxidation products. In general, species eluted (relative to the alkyl diester reference compounds) from the primary column (DB-210) in bands according to n and from the secondary columns (BPX90, SolGel-WAX) according to functionality, essentially making the GC × 2GC retention diagram a Carbon number-functionality grid. The species clustered into 35 groups by functionality and species within each group exhibited good separation by n. Average recoveries of n-alkanes and polyaromatic hydrocarbons (PAHs) by Soxhlet extraction of XAD-2 resin with dichloromethane were 80.1 ± 16.1 and 76.1 ± 17.5%, respectively. Vehicle emissions were the common source for HSVOCs [i.e., resolved alkanes, the unresolved complex mixture (UCM), alkylbenzenes, and 2- and 3-ring PAHs]. An absence of monoterpenes at 0600-1000 and high concentrations of monoterpenoids during the same period was indicative of substantial losses of monoterpenes overnight and the early morning hours. Post-collection, comprehensive organic molecular characterization of SOA precursors and products by GC × GC-ToFMS in ambient air collected with ~2 hr resolution is a promising method for determining biogenic and anthropogenic SOA yields that can be used to evaluate SOA formation models.

INCORPORATING STIMULATING QUICK-WRITE PROMPTS WITHIN A SECONDARY SCIENCE CLASSROOM: A CASE STUDY IN LESOTHO

The use of intriguing open-ended quick-write prompts within the Basotho science classroom could potentially provide a way for secondary teachers in Lesotho to have a time-efficient alternative to stimulate student thinking and increase critical thinking or application of scientific principles. Writing can be used as a powerful means to improve the achievement of students across many subject areas, including the sciences (Moore, 1993; Rivard, 1994; Rillero, Zambo, Cleland, and Ryan, 1996; Greenstein, 2013). This study focuses on the use of a non-traditional nor extensively studied writing method that could potentially support learning in science. A quasi-experimental research design, with a control and experimental group, was applied. The study was conducted at two schools, with one experimental classroom in one school and a second control group classroom in the second school for a period of 4 weeks. 51 Form B (US Grade 9 equivalent) students participated as the experimental group and 43 Form B students as the control group. In an effort to assess learning achievement, a 1 hour (35 mark) pre-test evaluation was made by and given to students by Basotho teachers at the beginning of this study to have an idea of student’s previous knowledge. Topics covered were Static Electricity, Current Electricity, Electromagnetic Waves, and Chemistry of Water. After the experimental trial period, an almost completely identical post-test evaluation was given to students in the same fashion to observe and compare gains in achievement. Test data was analyzed using an inferential statistics procedure that compared means and gains in knowledge made by the experimental and control groups. Difference between the gains of mean pre-test and post-test scores were statistically significant within each group, but were not statistically significant when the control and experimental groups were compared. Therefore, there was no clear practical effect. Qualitative data from teachers’ journals and students’ written feedback provides insight on the assessments, incorporation of the teaching method, and the development of participating students. Both mid and post-study student feedback shows that students had an overall positive and beneficial experience participating in this activity. Assessments and teacher journals showed areas of strength and weaknesses in student learning and on differences in teaching styles. They also helped support some feedback claims made by students. Areas of further research and improvement of the incorporation of this teaching method in the Basotho secondary science classroom are explored.