This dissertation employed a mixed-methods approach to examine the relationship between spatial reasoning ability and understanding of chemistry content for both middle school students and their science teachers. Spatial reasoning has been linked to success in learning STEM subjects (Wai, Lubinski, & Benbow, 2009). Previous studies have shown a correlation between understanding of chemistry content and spatial reasoning ability (e.g., Pribyl & Bodner, 1987; Wu & Shah, 2003: Stieff, 2013), raising the importance of developing the spatial reasoning ability of both teachers and students. Few studies examine middle school students’ or in-service middle school teachers’ understanding of chemistry concepts or its relation to spatial reasoning ability. The first paper in this dissertation addresses the quantitative relationship between mental rotation, a type of spatial reasoning ability, and understanding a fundamental concept in chemistry, the particulate nature of matter. The data showed a significant, positive correlation between scores on the Purdue Spatial Visualization Test of Rotations (PSVT; Bodner & Guay, 1997) and the Particulate Nature of Matter Assessment (ParNoMA; Yezierski, 2003) for middle school students prior to and after chemistry instruction. A significant difference in spatial ability among students choosing different answer choices on ParNoMA questions was also found. The second paper examined the ways in which students of different spatial abilities talked about matter and chemicals differently. Students with higher spatial ability tended to provide more of an explanation, though not necessarily in an articulate matter. In contrast, lower spatial ability students tended to use any keywords that seemed relevant, but provided little or no explanation. The third paper examined the relationship between mental reasoning and understanding chemistry for middle school science teachers. Similar to their students, a significant, positive correlation between scores on the PSVT and the ParNoMA was observed. Teachers who used consistent reasoning in providing definitions and examples for matter and chemistry tended to have higher spatial abilities than those teachers who used inconsistent reasoning on the same questions. This is the first study to explore the relationship between spatial reasoning and understanding of chemistry concepts at the middle school level. Though we are unable to infer cause and effect relationship from correlational data, these results illustrate a need to further investigate this relationship as well as identify the relationship between different spatial abilities (not just mental rotation) and other chemistry concepts.

Cyanobacteria are widely distributed in marine, freshwater and terrestrial habitats. Some cyanobacterial genera can convert di-nitrogen gas (N2) to bioavailable ammonium, i.e. perform nitrogen (N) fixation, and are therefore of profound significance for N cycling. N fixation by summer blooms of cyanobacteria is one of the largest sources of new N for the Baltic Sea. This thesis investigated N fixation by cyanobacteria in the Baltic Sea and explored the fate of fixed N at different spatial and temporal scales. In Paper I, we measured cell-specific N fixation by Aphanizomenon sp. at 10 ºC, early in the season. Fixation rates were high and comparable to those in late summer, indicating that Aphanizomenon sp. is an important contributor to N fixation already in its early growth season. In Paper II, we studied fixation and release of N by Aphanizomenon sp. and found that about half of the fixed N was rapidly released and transferred to other species, including autotrophic and heterotrophic bacteria, diatoms and copepods. In Paper III, we followed the development of a cyanobacterial bloom and related changes in dissolved and particulate N pools in the upper mixed surface layer. The bloom-associated total N (TN) increase was mainly due to higher particulate organic N (PON) concentrations, but also to increases in dissolved organic nitrogen (DON). About half the PON-increase could be explained by the sum of N-fixing cyanobacteria, other phytoplankton (&gt;2µm) and zooplankton, indicating that production was stimulated by the N fixation. In Paper IV, we used a growth model based on measured photosynthesis–irradiance relationships to explore the production potential of Aphanizomenon sp. The model included data on irradiance, biomass, temperature and light attenuation (1999–2013). Until the bloom peak, the modelled production matched the measured biomass, indicating low production losses. Over the whole season, the modelled production could explain a substantial part of the summer TN increase, assuming that plausible losses (such as grazing or cell lysis) are retained within the upper mixed layer. Complementing the other data, we also investigated the nutrient content (Paper I) and varying cell width (Paper IV) of Aphanizomenon sp. By a combination of approaches, this thesis has contributed new information on cyanobacterial N fixation rates, the transfer of fixed N to other organisms in the food web and shown the potential for fixed N to stimulate summer primary and secondary production in the Baltic Sea. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Manuscript.</p>

Direct fuel injection technology is increasingly being applied to the spark ignition internal combustion engine as one of the many actions required to reduce the CO2 emissions from road transport. Whilst the potential for CO2 reductions is compelling, the technology is not without disadvantages. Early examples typically emitted over an order of magnitude more Particulate Matter (PM) than vehicles with conventional spark ignition engines. Consequently, future revisions to European and North American exhaust emissions legislation are likely to regulate the particulate emissions from vehicles with direct injection gasoline engines. This thesis undertakes to investigate a) instrumentation capable of simultaneously resolving the number concentration and size distribution of particles in the 5-1000 nm size range and b) the factors affecting the PM emissions from spark ignition engines with direct fuel injection. The first objective is achieved by evaluation and comparison of a differential mobility spectrometer; photo-acoustic soot sensor; condensation particle counter and electrical low pressure impactor. To address the second question, a differential mobility spectrometer is applied to quantify the PM emissions from a number of direct injection gasoline engines, together with investigation of their dependence on various calibratable parameters, operating temperature and fuel composition. The differential mobility spectrometer showed good agreement with the other more established instruments tested. Moreover, it exhibited a faster time response and finer resolution in particle size. The number weighted size distribution of the PM emitted was typically lognormal with either one or two modes located between 20 and 100 nm. Chemical analysis of PM samples showed the presence of elemental carbon, volatile organic material and sulphates. Transient PM measurements enabled short time-scale events such as mode switching between homogeneous and stratified mixture preparation to be identified. PM number concentrations in stratified mode exceeded those in homogeneous mode by a factor of 10-100. Dynamometer based experiments showed that PM emissions increase for rich air fuel ratios, retarded fuel injection and advanced ignition events. They also demonstrated a strong dependence on fuel composition: the highest PM emissions were measured with an aromatic fuel, whereas blending alcohols such as methanol or ethanol tended to suppress PM emissions, particularly in the accumulation mode size range. These measurements are amongst the first of their kind and demonstrate the applicability of the differential mobility spectrometer to the measurement of ultra-fine particulate emissions from engines with direct fuel injection systems. Numerous explanations are put forward to describe the data obtained, together with suggestions for future work on PM control and abatement.

Even at low concentrations, the criteria air pollutant particulate matter (PM) is an environmental and public health hazard. Emissions levels legislated for modern diesel vehicles are so low (~90% lower than 2003) that it has become difficult to accurately measure PM by the regulatory metric: the mass of particles collected on a filter (i.e., the gravimetric method). Additionally, gravimetric analysis cannot measure real-time emission rates, and therefore is unable to characterize high-emitting transient events (e.g., engine starts, stop-and-go driving). By an alternate method, PM can be estimated by measuring the number-weighted particle size distribution (PSD) and calculating mass with a combination of theoretical and empirical constants (e.g., particle effective density). This integrated particle size distribution (IPSD) method is capable of high measurement sensitivity and real-time resolution. Real-time measurements by the IPSD method require fast-sizing spectrometers, such as the TSI Engine Exhaust Particle Sizer (EEPS), which sizes (between 5.6-560 nm) and counts particles based on their electrical mobility. The EEPS utilizes a unipolar charger to quickly charge particles for sizing and counting, however this mechanism has been shown to produce a less predictable charge distribution than bipolar chargers used in Scanning Mobility Particle Sizer (SMPS) systems – the gold standard 'slow-sizing' spectrometer. Several evaluations have shown deficiencies in EEPS PSD measurements due to charging differences (associated with particle morphology) unaccounted for in the transfer function matrix used to calibrate the EEPS. Specifically, the unipolar charger multiply charges a higher percentage of soot agglomerates (fractal-like particles common in diesel engine exhaust) than bipolar chargers. Because inaccurate PSDs are a primary reason for reported discrepancies between IPSD calculated mass and the gravimetric method, it is important to correct this deficiency in EEPS measurements. Recently, TSI has released additional EEPS calibration matrices ('soot' and 'Compact') which have shown better agreement with SMPS measurements under preliminary test conditions. This study further evaluates the performance of these new matrices relative to the original 'Default' matrix for diesel and biodiesel exhaust particles. Steady-state (75% engine load) emissions were generated by a light-duty diesel engine operating on (1) ultra-low sulfur diesel (ULSD) and (2) 100% soybean biodiesel. Raw EEPS data processed with each matrix were compared to simultaneously collected reference measurements from an SMPS. PSDs were evaluated based on their shape – i.e., multimodal fits of geometric mean diameter (GMD) and geometric standard deviation (GSD) – and concentration at peak particle diameter. For both fuels, all measurements agreed well in terms of the shape of the PSD: primary mode (accumulation) GMD ± 10nm, GSD ± 0.3. For ULSD, EEPS Default, Soot, and Compact concentrations were higher than the SMPS by factors of 1.9, 1.3, and 2.5, respectively. For biodiesel, EEPS Default, Soot, and Compact concentrations were higher than the SMPS by factors of 2.1, 1.7, and 2.4, respectively. Based on these results, the Soot matrix produced acceptable agreement between EEPS and SMPS measurements of ULSD exhaust particles. However, based on the factor of ~2 difference observed here, an additional calibration matrix may be necessary for the EEPS to accurately measure biodiesel exhaust particles. The IPSD method for estimating PM mass was applied to available data sets with corresponding gravimetric measurements (one ULSD transient cycle test and the same biodiesel steady-state test used for PSD evaluation). Real-time PSDs from each of the three EEPS matrices were used in combination with three sets of values assumed for size-dependent particle effective density (representing a range of potential conditions), resulting in nine IPSD estimates of PM mass corresponding to each gravimetric sample (one ULSD, one biodiesel). For the transient ULSD test, a widely used effective density distribution for fractal-like soot agglomerates resulted in good agreement between IPSD estimated mass and the gravimetric measurement (within 9% and 6% for Soot and Compact matrices, respectively). For the steady-state biodiesel test, assuming unit density (1g/cm³ for all particles) resulted in good agreement between IPSD estimated mass and the gravimetric measurement (within 7% and 2% for Soot and Compact matrices, respectively). These results support previous findings that the Soot matrix is currently the best available option for measurement of ULSD exhaust particles by the EEPS and that particle effective density distributions similar to the "fractal-like" one used here are an accurate estimate for ULSD exhaust particles under many conditions. However, based on the discrepancies between the EEPS and SMPS measured biodiesel exhaust PSDs observed here, as well as a current lack of information on the effective density of biodiesel exhaust particles, it is clear that additional research is necessary in order to understand the properties of biodiesel exhaust particles, especially as they relate to electrical mobility measurements and IPSD estimation of PM mass.

Investigating linkages between the compositions of suspended (seston) and benthic particulate matter is important to the understanding of organic matter (OM) cycling and nutrient retention in aquatic systems. We compared the quantity and quality of the truly suspended (TS) and settleable (SB) fractions of seston as well as benthic particulate matter in the tidal freshwater James River, Virginia. The mass of seston and OM was consistently higher in the TS fraction compared to the SB fraction. OM was preferentially retained in the TS fraction relative to seston. The proportional contribution of OM constituents (chlorophyll a, particulate organic carbon and nitrogen) to the two fractions was consistent across observed concentrations whereas increases in seston concentration resulted in decreased proportions in the TS fraction. Benthic constituent reservoirs were large relative to the SB fraction but the higher proportion of OM in the SB fraction suggests that the settleable material was more labile.

Rivers are a significant source of particulate and dissolved organic carbon (POC, DOC) into inland waters and coastal systems and provide a fundamental linkage between the terrestrial, oceanic, and atmospheric carbon reservoirs. Recent studies have examined the relationship between the quantity and form (POC vs. DOC) of carbon delivered to the aquatic system; however, little is known about the age of POC and DOC exported and how the radiocarbon age may vary with latitude, topographic gradient, vegetation, and land use. I provide the first global synthesis of published radiocarbon values of POC and DOC (∆14C). Inclusion of DOC and POC parameters (µM, δ13C, ∆14C) reveal significant driving forces of DOC (µM), latitude, and elevation (m) as capable of explaining 25% of the variability in DO14C in rivers and POC (µM) and latitude accounting for 15% of the variability in PO14C. When δ13C of DOC and POC and latitude were incorporated with ∆14C of DOC observations, 61% of the variability in DOC age was explained revealing the necessity to include dissolved and particulate fractions of organic carbon to yield the most robust predictive models. This study found a global trend of increasing age of DOC and increasing δ13C of DOC and POC with increasing latitude. My study suggests future research should incorporate both particulate and dissolved OC parameters along with elevation, vegetation, land cover, and climate zones to increase understanding of what drives the age of carbon exported in riverine systems.

Background: During August 2003 and July 2006 there were observed records of high temperature and high concentrations of pollutants across Europe. The effect of heat waves led to significant increases in total mortality, respiratory mortality and cardiovascular mortality. This study evaluates the association between exposure to the heat waves and daily non- accidental mortality, respiratory mortality and cardiovascular mortality in Prague, the Czech Republic. Methods: The effect of heat waves in summer 2003 and 2006 on mortality was investigated using the negative binomial regression (type of the Poisson model). Counts of death were regressed on temperature, long-term trends, season, day of week and concentrations of pollutants (O3 levels, PM10 levels, NO2 levels, SO2 levels, CO levels). We used one day lag. Results: We found an association between the heat waves in summer 2003 and 2006 and daily mortality and mortality on respiratory and cardiovascular diseases. No statistically significant association was detected. The effect of the heat wave was more significant in women. Conclusions: The effect of the heat wave in August 2003 and July 2006 caused adverse effect on the mortality in Prague, though lower as compared to many other cities in Europe. Keywords: heat wave, mortality, temperature, ozone,...

Master of Science / Department of Biological and Agricultural Engineering / Ronaldo G. Maghirang / Military installations in the United States may be large sources of fugitive dust emissions. Off-road vehicle training can contribute to air quality degradation resulting from increased wind erosion events as a result of soil disruption; however, limited information exists regarding the impacts of off-road vehicle maneuvering. This study was conducted to determine the effects of soil texture and intensity of training with off-road vehicles on fugitive dust emission potential due to wind erosion at military training installations. Multi-pass trafficking experiments, involving wheeled and tracked military vehicles (i.e., M1A1 Abrams tank, M925A1 water tanker and various HMMWV models), were conducted at three military training facilities with different climate and soil texture (i.e., Fort Riley, KS; Fort Benning, GA; and Yakima Training Center, WA). Dust emissions were measured on site using a Portable In-Situ Wind Erosion Laboratory (PI-SWERL) coupled with a DustTrak™ dust monitor. In addition, a top layer of soil was collected in trays and tested in a laboratory wind tunnel for dust emission potential. In wind tunnel testing, the amount of emitted dust was measured using glass-fiber filters through high-volume samplers. Also, the particle size distribution and concentration of the emitted dust were measured using a GRIMM aerosol spectrometer. Comparison of the PI-SWERL (with DustTrak™ dust monitor) and wind tunnel test (with GRIMM aerosol spectrometer) results showed significant difference and little correlation. Also, comparison of the filter and GRIMM aerosol spectrometer data showed significant difference but high correlation. The dust emission potential (as measured with the GRIMM spectrometer) was significantly influenced by soil texture, vehicle type and number of passes. For the light-wheeled vehicle, total dust emissions increased from 66 mg m-2 for undisturbed soil to 304 mg m-2 (357%) and 643 mg m-2 (868%) for 10 and 50 passes, respectively. For the tracked vehicle, an average increase in total dust emission of 569% was observed between undisturbed conditions and 1 pass, with no significant increase in emissions potential beyond 1 pass. For the heavy-wheeled vehicle, emissions increased from 75 mg m-2 for undisturbed soil to 1,652 mg m-2 (1,369%) and 4,023 mg m-2 (5,276%) for 10 and 20 passes, respectively. Soil texture also played an important role in dust emission potential. For all treatment effects, there was a 1,369% difference in emissions between silty clay loam soil and loamy sand soil.

Dry abrasive blasting is one of the most widely used methods of surface preparation. Air emissions from this process include particulate matter (PM) and metals. Spent abrasive generated from this process may be hazardous in nature. With increasing concern on health effects due to silica emissions from sand, use of alternative materials is suggested by health and regulatory agencies. The objective of this research was to evaluate performance of expendable abrasives and determine PM emission factors. Dry abrasive blasting was performed in an enclosed chamber and total PM samples were collected. Three commonly used expendable abrasives, coal slag, copper slag and specialty sand, were used to evaluate cleaner alternatives. Blast pressure and abrasive feed rate, two important process conditions were varied to study their effect on performance of an abrasive. Productivity, consumption and emission factors (performance parameters) were calculated and their variation with pressure and feed rate was evaluated. Two dimensional and three dimensional predicted models were developed to estimate the performance at intermediate blast pressure and feed rate conditions. Performance of the three abrasives was compared with respect to emission potential, productivity and consumption. Emission factors developed in this research will help in accurate estimation of total PM emissions and to select cleaner abrasives and optimum process conditions that will results in minimum emissions and reduced health risk. The productivity and consumption models will help is estimating life cycle costs including material cost, equipment cost, energy cost, labor costs, waste disposal cost, and compliance costs. Consumption models will also help in determining the quantity of spent abrasive generated, identify abrasives with lower material consumption, and identify process conditions that generate minimum spent abrasives. In addition, these models will help industries in making environmentally preferable purchasing (EPP), which results in pollution prevention and cost reduction.

Dry abrasive blasting is a commonly used surface preparation operation by many process industries to clean up metallic surfaces and achieve surface finishes suitable for future adhesion. Abrasives used in this process can be recyclable or expendable. This study was undertaken to evaluate the performance of three recyclable abrasives: garnet, barshot and steel grit/shot in terms of productivity (area cleaned per unit time), consumption (amount of abrasive used per unit area cleaned) and uncontrolled total particulate matter (TPM) emission factors (in terms of mass of pollutant emitted per unit area cleaned and mass of pollutant emitted per unit mass of abrasive consumed). Though there have been various attempts in the past to evaluate the performance of these abrasives, there has not been a streamlined approach to evaluate these parameters in the commonly used range of process conditions, or to identify and model the influences of key process variables on these performance parameters. The first step in this study was to evaluate the performance of these three abrasives in blasting painted steel panels under enclosed blasting conditions and using USEPA recommended protocols. The second step was to model the influences of blast pressure and abrasive feed rate, two most critical parameters on productivity, consumption and emission factors. Two and three dimensional models were obtained using multiple linear regression techniques to express productivity, consumption and TPM emission factors in terms of blast pressure and abrasive feed rate. Barshot was found to have high productivities over all and steel grit/shot demonstrated the least emission potential at almost all of the tested pressure and feed rate conditions. The data will help fill the gaps in literature currently available for dry abrasive blasting performance. The models obtained will help industries, the research community and the regulatory agencies to make accurate estimates of the performance parameters. Estimating productivity and consumption will help industries identify best management practices by optimizing the process conditions to achieve high productivity and low consumption rates. Emission factor determination will help in reducing the emissions to the atmosphere by choosing process conditions corresponding to minimum emissions. The performance parameters once optimized can result in reduction in material, labor, energy, emission and disposal costs, lower resource utilization and hence reduction in overall life cycle costs of dry abrasive process. The developed models will help industries in making environmentally preferable purchases thereby promoting source reduction options. PM emissions estimated using the models presented here will aid studies on health risk associated with inhalation of atmospheric PM.