IMPACT OF 2000-2050 CLIMATE CHANGE ON GLOBAL ATMOSPHERIC TRANSPORT AND DEPOSITION OF MERCURY

Since it is very toxic and accumulates in organisms, particularly in fish, mercury is a very important pollutant and one of the most studies. And this concern over the toxicity and human health risks of mercury has prompted efforts to regulate anthropogenic emissions. As mercury pollution problem is getting increasingly serious, we are curious about how serious this problem will be in the future. What is more, how the climate change in the future will affect the mercury concentration in the atmosphere. So we investigate the impact of climate change on mercury concentration in the atmosphere. We focus on the comparison between the mercury data for year 2000 and for year 2050. The GEOS-Chem model shows that the mercury concentrations for all tracers (1 to 3), elemental mercury (Hg(0)), divalent mercury (Hg(II)) and primary particulate mercury (Hg(P)) have differences between 2000 and 2050 in most regions over the world. From the model results, we can see the climate change from 2000 to 2050 would decrease Hg(0) surface concentration in most of the world. The driving factors of Hg(0) surface concentration changes are natural emissions(ocean and vegetation) and the transformation reactions between Hg(0) and Hg(II). The climate change from 2000 to 2050 would increase Hg(II) surface concentration in most of mid-latitude continental parts of the world while decreasing Hg(II) surface concentration in most of high-latitude part of the world. The driving factors of Hg(II) surface concentration changes is deposition amount change (majorly wet deposition) from 2000 to 2050 and the transformation reactions between Hg(0) and Hg(II). Climate change would increase Hg(P) concentration in most of mid-latitude area of the world and meanwhile decrease Hg(P) concentration in most of high-latitude regions of the world. For the Hg(P) concentration changes, the major driving factor is the deposition amount change (mainly wet deposition) from 2000 to 2050.

Paleoenvironmental reconstructions from cave sediments of the Moravian Karst, Czech Republic / by Pavel Sroubek.

This thesis presents a paleoclimatic/paleoenvironmental study conducted on clastic cave sediments of the Moravian Karst, Czech Republic. The study is based on environmental magnetic techniques, yet a wide range of other scientific methods was used to obtain a clearer picture of the Quaternary climate. My thesis also presents an overview of the significance of cave deposits for paleoclimatic reconstructions, explains basic environmental magnetic techniques and offers background information on the study area – a famous karst region in Central Europe with a rich history. In Kulna Cave magnetic susceptibility variations and in particular variations in pedogenic susceptibility yield a detailed record of the palaeoenvironmental conditions during the Last Glacial Stage. The Kulna long-term climatic trends agree with the deep-sea SPECMAP record, while the short-term oscillations correlate with rapid changes in the North Atlantic sea surface temperatures. Kulna Cave sediments reflect the intensity of pedogenesis controlled by short-term warmer events and precipitation over the mid-continent and provide a link between continental European climate and sea surface temperatures in the North Atlantic during the Last Glacial Stage. Given the number of independent climate proxies determined from the entrance facies of the cave and their high resolution, Kulna is an extremely important site for studying Late Pleistocene climate. In the interior of Spiralka Cave, a five meter high section of fine grained sediments deposited during floods yields information on the climatic and environmental conditions of the last millenium. In the upper 1.5 meters of this profile, mineral magnetic and other non-magnetic data indicate that susceptibility variations are controlled by the concentration of magnetite and its magnetic grain size. Comparison of our susceptibility record to the instrumental record of winter temperature anomalies shows a remarkable correlation. This correlation is explained by coupling of the flooding events, cultivation of land and pedogenetic processes in the cave catchment area. A combination of mineral magnetic and geochemical proxies yields a detail picture of the rapidly evolving climate of the near past and tracks both natural and human induced environmental changes taking place in the broader region.

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.

INTEGRATED ASSESSMENT OF ANTHROPOGENIC, CLIMATE, AND POLICY INDUCED CHANGES OF PHOSPHORUS EXPORT IN THE UNITED STATES LAURENTIAN GREAT LAKES WATERSHEDS

Anthropogenic activities have increased phosphorus (P) loading in tributaries to the Laurentian Great Lakes resulting in eutrophication in small bays to most notably, Lake Erie. Changes to surface water quality from P loading have resulted in billions of dollars in damage and threaten the health of the world’s largest freshwater resource. To understand the factors affecting P delivery with projected increasing urban lands and biofuels expansion, two spatially explicit models were coupled. The coupled models predict that the majority of the basin will experience a significant increase in urban area P sources while the agriculture intensity and forest sources of P will decrease. Changes in P loading across the basin will be highly variable spatially. Additionally, the impacts of climate change on high precipitation events across the Great Lakes were examined. Using historical regression relationships on phosphorus concentrations, key Great Lakes tributaries were found to have future changes including decreasing total loads and increases to high-flow loading events. The urbanized Cuyahoga watersheds exhibits the most vulnerability to these climate-induced changes with increases in total loading and storm loading , while the forested Au Sable watershed exhibits greater resilience. Finally, the monitoring network currently in place for sampling the amount of phosphorus entering the U.S. Great Lakes was examined with a focus on the challenges to monitoring. Based on these interviews, the research identified three issues that policy makers interested in maintaining an effective phosphorus monitoring network in the Great Lakes should consider: first, that the policy objectives driving different monitoring programs vary, which results in different patterns of sampling design and frequency; second, that these differences complicate efforts to encourage collaboration; and third, that methods of funding sampling programs vary from agency to agency, further complicating efforts to generate sufficient long-term data to improve our understanding of phosphorus into the Great Lakes. The dissertation combines these three areas of research to present the potential future impacts of P loading in the Great Lakes as anthropogenic activities, climate and monitoring changes. These manuscripts report new experimental data for future sources, loading and climate impacts on phosphorus.

Evaluation of sugar maple dieback in the Upper Great Lakes region and development of a forest health youth education program

Acer saccharum Marsh., is one of the most valuable trees in the northern hardwood forests. Severe dieback was recently reported by area foresters in the western Upper Great Lakes Region. Sugar Maple has had a history of dieback over the last 100 years throughout its range and different variables have been identified as being the predisposing and inciting factors in different regions at different times. Some of the most common factors attributed to previous maple dieback episodes were insect defoliation outbreaks, inadequate precipitation, poor soils, atmospheric deposition, fungal pathogens, poor management, or a combination of these. The current sugar maple dieback was evaluated to determine the etiology, severity, and change in dieback on both industry and public lands. A network of 120 sugar maple health evaluation plots was established in the Upper Peninsula, Michigan, northern Wisconsin, and eastern Minnesota and evaluated annually from 2009-2012. Mean sugar maple crown dieback between 2009-2012 was 12.4% (ranging from 0.8-75.5%) across the region. Overall, during the sampling period, mean dieback decreased by 5% but individual plots and trees continued to decline. Relationships were examined between sugar maple dieback and growth, habitat conditions, ownership, climate, soil, foliage nutrients, and the maple pathogen sapstreak. The only statistically significant factor was found to be a high level of forest floor impacts due to exotic earthworm activity. Sugar maple on soils with lower pH had less earthworm impacts, less dieback, and higher growth rates than those on soils more favorable to earthworms. Nutritional status of foliage and soil was correlated with dieback and growth suggesting perturbation of nutrient cycling may be predisposing or contributing to dieback. The previous winter's snowfall totals, length of stay on the ground, and number of days with freezing temperatures had a significant positive relationship to sugar maple growth rates. Sapstreak disease, Ceratocystis virescens, may be contributing to dieback in some stands but was not related to the amount of dieback in the region. The ultimate goal of this research is to help forest managers in the Great Lakes Region prevent, anticipate, reduce, and/or salvage stands with dieback and loss in the future. An improved understanding of the complex etiology associated with sugar maple dieback in the Upper Great Lakes Region is necessary to make appropriate silvicultural decisions. Forest Health education helps increase awareness and proactive forest management in the face of changing forest ecosystems. Lessons are included to assist educators in incorporating forest health into standard biological disciplines at the secondary school curricula.