Mitigation of High Alkalinity in Leachates of Aged Steel Slag

Steel slag, an abundant by-product of the steel-making industry, after it is aged, has a huge potential for use as an aggregate in road construction. However, the high pH of steel slag seepage (pH≥12) is a major impediment in its beneficial use. Analyses on aged steel slag samples demonstrated that the alkalinity producing capacity of aged steel slag samples strongly correlated to Ca(OH)2 dissolution and that prolonged aging periods have marginal effects on overall alkalinity. Treatment methods that included bitumen-coating, bathing in Al(III) solutions and addition of an alum-based drinking water treatment residual (WTR) were evaluated based on reduction in pH levels and leachate alkalinity. 10% (wt./wt.) alum-based drinking water treatment residual (WTR) addition to slag was determined to be the most successful mitigation method, providing 65−70% reduction in alkalinity both in batch-type and column leach tests, but final leachate pH was only 0.5−1 units lower and leachates were contaminated by dissolved Al(+III) (≥3−4 mM). Based on the interpretation of calculated saturation indices and SEM and EDX analyses, formation of calcium sulfoaluminate phases (i.e., ettringite and monosulfate) was suggested as the mechanism behind alkalinity mitigation upon WTR-modification. The residual alkalinity in WTR-amended slag leachates was able to be completely eliminated utilizing a biosolids compost with high base neutralization capacity. In column leach tests, effluent pH levels below 7 were maintained for 58−74 pore volumes worth of WTR-amended slag leachate using 0.13 kg compost (dry wt.) per 1 kg WTR-amended slag on average; also, dissolved Al(+III) was strongly retained on the compost.

Balancing Belligerents or Feeding the Beast: Transforming Conflict Traps

Since the end of the Cold War, recurring civil conflicts have been the dominant form of violent armed conflict in the world, accounting for 70% of conflicts active between 2000-2013. Duration and intensity of episodes within recurring conflicts in Africa exhibit four behaviors characteristic of archetypal dynamic system structures. The overarching questions asked in this study are whether these patterns are robustly correlated with fundamental concepts of resiliency in dynamic systems that scale from micro-to macro levels; are they consistent with theoretical risk factors and causal mechanisms; and what are the policy implications. Econometric analysis and dynamic systems modeling of 36 conflicts in Africa between 1989 -2014 are combined with process tracing in a case study of Somalia to evaluate correlations between state characteristics, peace operations and foreign aid on the likelihood of observed conflict patterns, test hypothesized causal mechanisms across scales, and develop policy recommendations for increasing human security while decreasing resiliency of belligerents. Findings are that observed conflict patterns scale from micro to macro levels; are strongly correlated with state characteristics that proxy a mix of cooperative (e.g., gender equality) and coercive (e.g., security forces) conflict-balancing mechanisms; and are weakly correlated with UN and regional peace operations and humanitarian aid. Interactions between peace operations and aid interventions that effect conflict persistence at micro levels are not seen in macro level analysis, due to interdependent, micro-level feedback mechanisms, sequencing, and lagged effects. This study finds that the dynamic system structures associated with observed conflict patterns contain tipping points between balancing mechanisms at the interface of micro-macro level interactions that are determined as much by factors related to how intervention policies are designed and implemented, as what they are. Policy implications are that reducing risk of conflict persistence requires that peace operations and aid interventions (1) simultaneously increase transparency, promote inclusivity (with emphasis on gender equality), and empower local civilian involvement in accountability measures at the local levels; (2) build bridges to horizontally and vertically integrate across levels; and (3) pave pathways towards conflict transformation mechanisms and justice that scale from the individual, to community, regional, and national levels.

Characterization of Copper Covetic Bulk and Films: Copper with High Carbon Content

Incorporation of carbon nanostructures in metals is desirable to combine the strongly bonded electrons in the metal and the free electrons in carbon nanostructures that give rise to high ampacity and high conductivity, respectively. Carbon in copper has the potential to impact industries such as: building construction, power generation and transmission, and microelectronics. This thesis focuses on the structure and properties of bulk and thin films of a new material, Cu covetic, that contains carbon in concentrations up to 16 at.%. X-ray photoelectron spectroscopy (XPS) shows C 1s peak with both sp2 and sp3 bonded C measuring up to 3.5 wt.% (16 at.%). High resolution transmission electron microscopy and electron diffraction of bulk covetic samples show a modulated structure of ≈ 1.6 nm along several crystallographic directions in regions that have high C content suggesting that the carbon incorporates into the copper lattice forming a network. Electron energy loss spectra (EELS) from covetics reveal that the level of graphitization from the source material, activated carbon, is maintained in the covetic structure. Bulk Cu covetics have a slight increase in the lattice constant, as well as <111> texturing, or possibly a different structure, compared to pure Cu. Density functional theory calculations predict bonding between C and Cu at the edges and defects of graphene sheets. The electrical resistivity of bulk covetics first increases and then decreases with increasing C content. Cu covetic films were deposited using e-beam and pulsed laser deposition (PLD) at different temperatures. No copper oxide or any allotropes of carbon are present in the films. The e-beam films show enhanced electrical and optical properties when compared to pure Cu films of the same thickness even though no carbon was detected by XPS or EELS. They also have slightly higher ampacity than Cu metal films. EELS analysis of the C-K-edge in the PLD films indicate that graphitic carbon is transferred from the bulk into the films with uniform carbon distribution. PLD films exhibit flatter and higher transmittance curves and sheet resistance two orders of magnitude lower than e-beam films leading to a high figure of merit as transparent conductors.

Using landscape metrics to predict hydrologic connectivity patterns between forested wetlands and streams in a coastal plain watershed

Geographically isolated wetlands, those entirely surrounded by uplands, provide numerous ecological functions, some of which are dependent on the degree to which they are hydrologically connected to nearby waters. There is a growing need for field-validated, landscape-scale approaches for classifying wetlands based on their expected degree of connectivity with stream networks. During the 2015 water year, flow duration was recorded in non-perennial streams (n = 23) connecting forested wetlands and nearby perennial streams on the Delmarva Peninsula (Maryland, USA). Field and GIS-derived landscape metrics (indicators of catchment, wetland, non-perennial stream, and soil characteristics) were assessed as predictors of wetland-stream connectivity (duration, seasonal onset and offset dates). Connection duration was most strongly correlated with non-perennial stream geomorphology and wetland characteristics. A final GIS-based stepwise regression model (adj-R2 = 0.74, p < 0.0001) described wetland-stream connection duration as a function of catchment area, wetland area and number, and soil available water storage.