Development of measurement and modeling techniques to quantify atmospheric deposition of persistent, bioaccumulative and toxic chemicals in the Great Lakes

Measurement and modeling techniques were developed to improve over-water gaseous air-water exchange measurements for persistent bioaccumulative and toxic chemicals (PBTs). Analytical methods were applied to atmospheric measurements of hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Additionally, the sampling and analytical methods are well suited to study semivolatile organic compounds (SOCs) in air with applications related to secondary organic aerosol formation, urban, and indoor air quality. A novel gas-phase cleanup method is described for use with thermal desorption methods for analysis of atmospheric SOCs using multicapillary denuders. The cleanup selectively removed hydrogen-bonding chemicals from samples, including much of the background matrix of oxidized organic compounds in ambient air, and thereby improved precision and method detection limits for nonpolar analytes. A model is presented that predicts gas collection efficiency and particle collection artifact for SOCs in multicapillary denuders using polydimethylsiloxane (PDMS) sorbent. An approach is presented to estimate the equilibrium PDMS-gas partition coefficient (Kpdms) from an Abraham solvation parameter model for any SOC. A high flow rate (300 L min-1) multicapillary denuder was designed for measurement of trace atmospheric SOCs. Overall method precision and detection limits were determined using field duplicates and compared to the conventional high-volume sampler method. The high-flow denuder is an alternative to high-volume or passive samplers when separation of gas and particle-associated SOCs upstream of a filter and short sample collection time are advantageous. A Lagrangian internal boundary layer transport exchange (IBLTE) Model is described. The model predicts the near-surface variation in several quantities with fetch in coastal, offshore flow: 1) modification in potential temperature and gas mixing ratio, 2) surface fluxes of sensible heat, water vapor, and trace gases using the NOAA COARE Bulk Algorithm and Gas Transfer Model, 3) vertical gradients in potential temperature and mixing ratio. The model was applied to interpret micrometeorological measurements of air-water exchange flux of HCB and several PCB congeners in Lake Superior. The IBLTE Model can be applied to any scalar, including water vapor, carbon dioxide, dimethyl sulfide, and other scalar quantities of interest with respect to hydrology, climate, and ecosystem science.

An Ecological and Chemical Assessment of Copper Contaminated Streams in the Keweenaw Peninsula

The copper mining boom in Michigan's Upper Peninsula ended in the mid-1960s, but the historical mining still affects the region to this day. Earlier studies conducted in the Keweenaw have shown that trace metals in the sediments negatively affect benthic macroinvertebrate populations. However, because the concentrations of trace metals that are observed to be toxic often differ significantly between the laboratory and the environment, a better method for determining toxic levels of trace metals in the natural environment is desirable in order to establish surface water quality guidelines that effectively protect aquatic life. There were four research objectives for this research project. First, to determine if trace-level concentrations of copper can result in detectable ecological impacts even in the presence of high dissolved organic carbon (DOC). Second, to determine if there is a "safe" concentration of total dissolved copper below which there is little to no ecological impairment. Third, to establish which streams in the Keweenaw Peninsula have been most impacted by elevated levels of total dissolved copper. Fourth, to use this information to evaluate revisions to the water quality criterion for copper that were recently proposed by the Michigan Department of Environmental Quality (MDEQ). In order to collect water quality and macroinvertebrate data, two sampling surveys of approximately 50 streams were completed in the spring and summer of 2012. Our findings demonstrate that negative ecological impacts can be detected even in the presence of high concentrations of DOC. The majority of surveyed streams showed evidence of total dissolved copper concentrations that were elevated above background levels. Our findings suggest that there are detectable negative impacts below the current water quality standard for copper in many Keweenaw streams. The diversity of benthic macroinvertebrates and the number of species present has been reduced as a result of exposure to copper. Additionally, the multimetric approach used by MDEQ is unable to detect copper impairment in local streams due to the use of several insensitive metrics. The proposed changes to the copper criterion would increase the amount of total dissolved copper allowable despite the fact that approximately 25% of streams sampled have aquatic chemistries that would leave them vulnerable to high levels of copper ions.

THERMAL CHARACTERIZATION OF COMBUSTION CHAMBER COMPONENTS IN A GASOLINE TURBOCHARGED DIRECT INJECTION (GTDI) ENGINE

This report is a PhD dissertation proposal to study the in-cylinder temperature and heat flux distributions within a gasoline turbocharged direct injection (GTDI) engine. Recent regulations requiring automotive manufacturers to increase the fuel efficiency of their vehicles has led to great technological achievements in internal combustion engines. These achievements have increased the power density of gasoline engines dramatically in the last two decades. Engine technologies such as variable valve timing (VVT), direct injection (DI), and turbocharging have significantly improved engine power-to-weight and power-to-displacement ratios. A popular trend for increasing vehicle fuel economy in recent years has been to downsize the engine and add VVT, DI, and turbocharging technologies so that a lighter more efficient engine can replace a larger, heavier one. With the added power density, thermal management of the engine becomes a more important issue. Engine components are being pushed to their temperature limits. Therefore it has become increasingly important to have a greater understanding of the parameters that affect in-cylinder temperatures and heat transfer. The proposed research will analyze the effects of engine speed, load, relative air-fuel ratio (AFR), and exhaust gas recirculation (EGR) on both in-cylinder and global temperature and heat transfer distributions. Additionally, the effect of knocking combustion and fuel spray impingement will be investigated. The proposed research will be conducted on a 3.5 L six cylinder GTDI engine. The research engine will be instrumented with a large number of sensors to measure in-cylinder temperatures and pressures, as well as, the temperature, pressure, and flow rates of energy streams into and out of the engine. One of the goals of this research is to create a model that will predict the energy distribution to the crankshaft, exhaust, and cooling system based on normalized values for engine speed, load, AFR, and EGR. The results could be used to aid in the engine design phase for turbocharger and cooling system sizing. Additionally, the data collected can be used for validation of engine simulation models, since in-cylinder temperature and heat flux data is not readily available in the literature..

AN INVESTIGATION OF VARIABLE VALVE TIMING EFFECTS ON HCCI ENGINE PERFORMANCE

The Homogeneous Charge Compression Ignition (HCCI) engine is a promising combustion concept for reducing NOx and particulate matter (PM) emissions and providing a high thermal efficiency in internal combustion engines. This concept though has limitations in the areas of combustion control and achieving stable combustion at high loads. For HCCI to be a viable option for on-road vehicles, further understanding of its combustion phenomenon and its control are essential. Thus, this thesis has a focus on both the experimental setup of an HCCI engine at Michigan Technological University (MTU) and also developing a physical numerical simulation model called the Sequential Model for Residual Affected HCCI (SMRH) to investigate performance of HCCI engines. The primary focus is on understanding the effects of intake and exhaust valve timings on HCCI combustion. For the experimental studies, this thesis provided the contributions for development of HCCI setup at MTU. In particular, this thesis made contributions in the areas of measurement of valve profiles, measurement of piston to valve contact clearance for procuring new pistons for further studies of high geometric compression ratio HCCI engines. It also consists of developing and testing a supercharging station and the setup of an electrical air heater to extend the HCCI operating region. The HCCI engine setup is based on a GM 2.0 L LHU Gen 1 engine which is a direct injected engine with variable valve timing (VVT) capabilities. For the simulation studies, a computationally efficient modeling platform has been developed and validated against experimental data from a single cylinder HCCI engine. In-cylinder pressure trace, combustion phasing (CA10, CA50, BD) and performance metrics IMEP, thermal efficiency, and CO emission are found to be in good agreement with experimental data for different operating conditions. Effects of phasing intake and exhaust valves are analyzed using SMRH. In addition, a novel index called Fuel Efficiency and Emissions (FEE) index is defined and is used to determine the optimal valve timings for engine operation through the use of FEE contour maps.