Perioperative cerebrospinal fluid and plasma inflammatory markers after orthopedic surgery.

BACKGROUND: Postoperative delirium is prevalent in older patients and associated with worse outcomes. Recent data in animal studies demonstrate increases in inflammatory markers in plasma and cerebrospinal fluid (CSF) even after aseptic surgery, suggesting that inflammation of the central nervous system may be part of the pathogenesis of postoperative cognitive changes. We investigated the hypothesis that neuroinflammation was an important cause for postoperative delirium and cognitive dysfunction after major non-cardiac surgery. METHODS: After Institutional Review Board approval and informed consent, we recruited patients undergoing major knee surgery who received spinal anesthesia and femoral nerve block with intravenous sedation. All patients had an indwelling spinal catheter placed at the time of spinal anesthesia that was left in place for up to 24 h. Plasma and CSF samples were collected preoperatively and at 3, 6, and 18 h postoperatively. Cytokine levels were measured using ELISA and Luminex. Postoperative delirium was determined using the confusion assessment method, and cognitive dysfunction was measured using validated cognitive tests (word list, verbal fluency test, digit symbol test). RESULTS: Ten patients with complete datasets were included. One patient developed postoperative delirium, and six patients developed postoperative cognitive dysfunction. Postoperatively, at different time points, statistically significant changes compared to baseline were present in IL-5, IL-6, I-8, IL-10, monocyte chemotactic protein (MCP)-1, macrophage inflammatory protein (MIP)-1α, IL-6/IL-10, and receptor for advanced glycation end products in plasma and in IFN-γ, IL-6, IL-8, IL-10, MCP-1, MIP-1α, MIP-1β, IL-8/IL-10, and TNF-α in CSF. CONCLUSIONS: Substantial pro- and anti-inflammatory activity in the central neural system after surgery was found. If confirmed by larger studies, persistent changes in cytokine levels may serve as biomarkers for novel clinical trials.

Dynamic Life Cycle Assessment Modeling Approaches for Transboundary Energy Feedstocks

The rise of the twenty-first century has seen the further increase in the industrialization of Earth’s resources, as society aims to meet the needs of a growing population while still protecting our environmental and natural resources. The advent of the industrial bioeconomy – which encompasses the production of renewable biological resources and their conversion into food, feed, and bio-based products – is seen as an important step in transition towards sustainable development and away from fossil fuels. One sector of the industrial bioeconomy which is rapidly being expanded is the use of biobased feedstocks in electricity production as an alternative to coal, especially in the European Union.

As bioeconomy policies and objectives increasingly appear on political agendas, there is a growing need to quantify the impacts of transitioning from fossil fuel-based feedstocks to renewable biological feedstocks. Specifically, there is a growing need to conduct a systems analysis and potential risks of increasing the industrial bioeconomy, given that the flows within it are inextricably linked. Furthermore, greater analysis is needed into the consequences of shifting from fossil fuels to renewable feedstocks, in part through the use of life cycle assessment modeling to analyze impacts along the entire value chain.

To assess the emerging nature of the industrial bioeconomy, three objectives are addressed: (1) quantify the global industrial bioeconomy, linking the use of primary resources with the ultimate end product; (2) quantify the impacts of the expaning wood pellet energy export market of the Southeastern United States; (3) conduct a comparative life cycle assessment, incorporating the use of dynamic life cycle assessment, of replacing coal-fired electricity generation in the United Kingdom with wood pellets that are produced in the Southeastern United States.

To quantify the emergent industrial bioeconomy, an empirical analysis was undertaken. Existing databases from multiple domestic and international agencies was aggregated and analyzed in Microsoft Excel to produce a harmonized dataset of the bioeconomy. First-person interviews, existing academic literature, and industry reports were then utilized to delineate the various intermediate and end use flows within the bioeconomy. The results indicate that within a decade, the industrial use of agriculture has risen ten percent, given increases in the production of bioenergy and bioproducts. The underlying resources supporting the emergent bioeconomy (i.e., land, water, and fertilizer use) were also quantified and included in the database.

Following the quantification of the existing bioeconomy, an in-depth analysis of the bioenergy sector was conducted. Specifically, the focus was on quantifying the impacts of the emergent wood pellet export sector that has rapidly developed in recent years in the Southeastern United States. A cradle-to-gate life cycle assessment was conducted in order to quantify supply chain impacts from two wood pellet production scenarios: roundwood and sawmill residues. For reach of the nine impact categories assessed, wood pellet production from sawmill residues resulted in higher values, ranging from 10-31% higher.

The analysis of the wood pellet sector was then expanded to include the full life cycle (i.e., cradle-to-grave). In doing to, the combustion of biogenic carbon and the subsequent timing of emissions were assessed by incorporating dynamic life cycle assessment modeling. Assuming immediate carbon neutrality of the biomass, the results indicated an 86% reduction in global warming potential when utilizing wood pellets as compared to coal for electricity production in the United Kingdom. When incorporating the timing of emissions, wood pellets equated to a 75% or 96% reduction in carbon dioxide emissions, depending upon whether the forestry feedstock was considered to be harvested or planted in year one, respectively.

Finally, a policy analysis of renewable energy in the United States was conducted. Existing coal-fired power plants in the Southeastern United States were assessed in terms of incorporating the co-firing of wood pellets. Co-firing wood pellets with coal in existing Southeastern United States power stations would result in a nine percent reduction in global warming potential.

Advanced Aerogel Composites for Oil Remediation and Recovery

Oil spills in marine environments often damage marine and coastal life if not remediated rapidly and efficiently. In spite of the strict enforcement of environmental legislations (i.e., Oil Pollution Act 1990) following the Exxon Valdez oil spill (June 1989; the second biggest oil spill in U.S. history), the Macondo well blowout disaster (April 2010) released 18 times more oil. Strikingly, the response methods used to contain and capture spilled oil after both accidents were nearly identical, note that more than two decades separate Exxon Valdez (1989) and Macondo well (2010) accidents.

The goal of this dissertation was to investigate new advanced materials (mechanically strong aerogel composite blankets-Cabot® Thermal Wrap™ (TW) and Aspen Aerogels® Spaceloft® (SL)), and their applications for oil capture and recovery to overcome the current material limitations in oil spill response methods. First, uptake of different solvents and oils were studied to answer the following question: do these blanket aerogel composites have competitive oil uptake compared to state-of-the-art oil sorbents (i.e., polyurethane foam-PUF)? In addition to their competitive mechanical strength (766, 380, 92 kPa for Spaceloft, Thermal Wrap, and PUF, respectively), our results showed that aerogel composites have three critical advantages over PUF: rapid (3-5 min.) and high (more than two times of PUF’s uptake) oil uptake, reusability (over 10 cycles), and oil recoverability (up to 60%) via mechanical extraction. Chemical-specific sorption experiments showed that the dominant uptake mechanism of aerogels is adsorption to the internal surface, with some contribution of absorption into the pore space.

Second, we investigated the potential environmental impacts (energy and chemical burdens) associated with manufacturing, use, and disposal of SL aerogel and PUF to remove the oil (i.e., 1 m3 oil) from a location (i.e., Macondo well). Different use (single and multiple use) and end of life (landfill, incinerator, and waste-to-energy) scenarios were assessed, and our results demonstrated that multiple use, and waste-to-energy choices minimize the energy and material use of SL aerogel. Nevertheless, using SL once and disposing via landfill still offers environmental and cost savings benefits relative to PUF, and so these benefits are preserved irrespective of the oil-spill-response operator choices.

To inform future aerogel manufacture, we investigated the different laboratory-scale aerogel fabrication technologies (rapid supercritical extraction (RSCE), CO2 supercritical extraction (CSCE), alcohol supercritical extraction (ASCE)). Our results from anticipatory LCA for laboratory-scaled aerogel fabrication demonstrated that RSCE method offers lower cumulative energy and ecotoxicity impacts compared to conventional aerogel fabrication methods (CSCE and ASCE).

The final objective of this study was to investigate different surface coating techniques to enhance oil recovery by modifying the existing aerogel surface chemistries to develop chemically responsive materials (switchable hydrophobicity in response to a CO2 stimulus). Our results showed that studied surface coating methods (drop casting, dip coating, and physical vapor deposition) were partially successful to modify surface with CO2 switchable chemical (tributylpentanamidine), likely because of the heterogeneous fiber structure of the aerogel blankets. A possible solution to these non-uniform coatings would be to include switchable chemical as a precursor during the gel preparation to chemically attach the switchable chemical to the pores of the aerogel.

Taken as a whole, the implications of this work are that mechanical deployment and recovery of aerogel composite blankets is a viable oil spill response strategy that can be deployed today. This will ultimately enable better oil uptake without the uptake of water, potential reuse of the collected oil, reduced material and energy burdens compared to competitive sorbents (e.g., PUF), and reduced occupational exposure to oiled sorbents. In addition, sorbent blankets and booms could be deployed in coastal and open-ocean settings, respectively, which was previously impossible.