Trichloroethylene fate and transport studies and biodegradation kinetics in the saturated zone

Permeable reactive barriers (PRB) are constructed from soil solid amendments to support the growth of bacteria that are capable of degrading organic contaminants. The objective of this study was to identify low-cost soil solid amendments that could retard the movement of trichloroethylene (TCE) while serving as long-lived carbon sources to foster its biodegradation in shallow groundwater through the use of a PRB. The natural amendments high in organic carbon content such as eucalyptus mulch, compost, wetland peat, organic humus were compared based on their geophysical characteristics, such as pHw, porosity and total organic carbon (TOC), and as well as TCE sorption potentials. The pHw values were within neutral range except for pine bark mulch and wetland peat. All other geophysical characteristics of the amendments showed suitability for use in a PRB. While the Freundlich model showed better fit for compost and pine bark mulch, the linear sorption model was adequate for eucalyptus mulch, wetland peat and Everglades muck within the concentration range studied (0.2-0.8 mg/L TCE). According to these results, two composts and eucalyptus mulch were selected for laboratory column experiments to evaluate their effectiveness at creating and maintaining conditions suitable for TCE anaerobic dechlorination. The columns were monitored for pH, ORP, TCE degradation, longevity of nutrients and soluble TOC to support TCE dechlorination. Native bacteria in the columns had the ability to convert TCE to DCEs; however, the inoculation with the TCE-degrading culture greatly increased the rate of biodegradation. This caused a significant increase in by-product concentration, mostly in the form of DCEs and VC followed by a slow degradation to ethylene. Of the tested amendments eucalyptus mulch was the most effective at supporting the TCE dechlorination. The experimental results of TCE sequential dechlorination took place in eucalyptus mulch and commercial compost from Savannah River Site columns were then simulated using the Hydrus-1D model. The simulations showed good fit with the experimental data. The results suggested that sorption and degradation were the dominant fate and transport mechanisms for TCE and DCEs in the column, supporting the use of these amendments in a permeable reactive barrier to remediate the TCE.

Comparative study of dissolved organic matter from groundwater and surface water in the Florida coastal Everglades using multi-dimensional spectrofluorometry combined with multivariate statistics

Dissolved organic matter (DOM) in groundwater and surface water samples from the Florida coastal Everglades were studied using excitation–emission matrix fluorescence modeled through parallel factor analysis (EEM-PARAFAC). DOM in both surface and groundwater from the eastern Everglades S332 basin reflected a terrestrial-derived fingerprint through dominantly higher abundances of humic-like PARAFAC components. In contrast, surface water DOM from northeastern Florida Bay featured a microbial-derived DOM signature based on the higher abundance of microbial humic-like and protein-like components consistent with its marine source. Surprisingly, groundwater DOM from northeastern Florida Bay reflected a terrestrial-derived source except for samples from central Florida Bay well, which mirrored a combination of terrestrial and marine end-member origin. Furthermore, surface water and groundwater displayed effects of different degradation pathways such as photodegradation and biodegradation as exemplified by two PARAFAC components seemingly indicative of such degradation processes. Finally, Principal Component Analysis of the EEM-PARAFAC data was able to distinguish and classify most of the samples according to DOM origins and degradation processes experienced, except for a small overlap of S332 surface water and groundwater, implying rather active surface-to-ground water interaction in some sites particularly during the rainy season. This study highlights that EEM-PARAFAC could be used successfully to trace and differentiate DOM from diverse sources across both horizontal and vertical flow profiles, and as such could be a convenient and useful tool for the better understanding of hydrological interactions and carbon biogeochemical cycling.

Evidence for the removal of CFC-11, CFC-12, and CFC-113 at the groundwater–surface water interface in the Everglades

Poor agreement between 3H/3He ages and CFC-11 and CFC-12 ages suggests that CFCs may not be conservative tracers in the Everglades National Park. 3H/3He ages were used to calculate the expected concentration of CFC-11 and CFC-12 in groundwater from wells 2 to 73 m deep. The expected concentrations of CFCs were compared to the measured concentrations and plots of the % CFC-12 and CFC-11 remaining offered no evidence that significant CFC removal was occurring in the groundwater at depths ≥2 m, suggesting that CFC removal occurs at shallower depths. Except where CFC contamination was suspected, CFC-11, CFC-12 and CFC-113 concentrations in fresh surface water were nearly always below solubility equilibrium with the atmosphere. Measurements of CFC-11, CFC-12 and CFC-113 in pore water indicate a 50–90% decrease in concentration 5 cm below the groundwater–surface water (GW–SW) interface. In the same 5 cm interval CH4 concentrations increased by 300–1000%. This suggested that CFCs were removed at the GW–SW interface, possibly by methane-producing bacteria. CFC derived recharge ages should therefore be viewed with caution when recharging water percolates through anoxic methanogenic sediments.

An Investigation on Biocompatibility of Bio-Absorbable Polymer Coated Magnesium Alloys

Advances in biomaterials have enabled medical practitioners to replace diseased body parts or to assist in the healing process. In situations where a permanent biomaterial implant is used for a temporary application, additional surgeries are required to remove these implants once the healing process is complete, which increases medical costs and patient morbidity. Bio-absorbable materials dissolve and are metabolized by the body after the healing process is complete thereby negating additional surgeries for removal of implants. Magnesium alloys as novel bio-absorbable biomaterials, have attracted great attention recently because of their good mechanical properties, biocompatibility and corrosion rate in physiological environments. However, usage of Mg as biodegradable implant has been limited by its poor corrosion resistance in the physiological solutions. An optimal biodegradable implant must initially have slow degradation to ensure total mechanical integrity then degrade over time as the tissue heals. The current research focuses on surface modification of Mg alloy (MZC) by surface treatment and polymer coating in an effort to enhance the corrosion rate and biocompatibility. It is envisaged that the results obtained from this investigation would provide the academic community with insights for the utilization of bio-absorbable implants particularly for patients suffering from atherosclerosis. The alloying elements used in this study are zinc and calcium both of which are essential minerals in the human metabolic and healing processes. A hydrophobic biodegradable co-polymer, polyglycolic-co-caprolactone (PGCL), was used to coat the surface treated MZC to retard the initial degradation rate. Two surface treatments were selected: (a) acid etching and (b) anodization to produce different surface morphologies, roughness, surface energy, chemistry and hydrophobicity that are pivotal for PGCL adhesion onto the MZC. Additionally, analyses of biodegradation, biocompatibility, and mechanical integrity were performed in order to investigate the optimum surface modification process, suitable for biomaterial implants. The study concluded that anodization created better adhesion between the MZC and PGCL coating. Furthermore, PGCL coated anodized MZC exhibited lower corrosion rate, good mechanical integrity, and better biocompatibility as compared with acid etched.

Surfactant solubilization and subsequent bioavailability of phenanthrene

Contamination of soil, sediment and groundwater by hydrophobic organic compounds (HOCs) is a matter of growing concern because groundwater is a valuable and limited resource, and because such contamination is difficult to address. This investigation involved an experimental evaluation of the addition of several surfactant solutions to aqueous and soil-water systems contaminated with phenanthrene, a selected HOC. The results are presented in terms of: * phenanthrene solubilization achieved through surfactant addition * observed effects of surfactant addition on the mineralization of phenanthrene * estimation of relative toxicities of various surfactants using toxicity assays * literature-reported biodegradability/persistence of selected surfactants * surfactant sorption/precipitation onto soil and its impacts on proposed use of surfactant-amended remediation Surfactants were observed to facilitate the transfer of phenanthrene from the soil-sorbed phase to the aqueous pseudophase, however, surfactant solubilization did not translate into enhanced phenanthrene biodegradation.

Distribution of planktic foraminifera in surface sediments of the Atlantic Ocean

We present a data set of 738 planktonic foraminiferal species counts from sediment surface samples of the eastern North Atlantic and the South Atlantic between 87°N and 40°S, 35°E and 60°W including published Climate: Long-Range Investigation, Mapping, and Prediction (CLIMAP) data. These species counts are linked to Levitus's [1982] modern water temperature data for the four caloric seasons, four depth ranges (0, 30, 50, and 75 m), and the combined means of those depth ranges. The relation between planktonic foraminiferal assemblages and sea surface temperature (SST) data is estimated using the newly developed SIMMAX technique, which is an acronym for a modern analog technique (MAT) with a similarity index, based on (1) the scalar product of the normalized faunal percentages and (2) a weighting procedure of the modern analog's SSTs according to the inverse geographical distances of the most similar samples. Compared to the classical CLIMAP transfer technique and conventional MAT techniques, SIMMAX provides a more confident reconstruction of paleo-SSTs (correlation coefficient is 0.994 for the caloric winter and 0.993 for caloric summer). The standard deviation of the residuals is 0.90°C for caloric winter and 0.96°C for caloric summer at 0-m water depth. The SST estimates reach optimum stability (standard deviation of the residuals is 0.88°C) at the average 0- to 75-m water depth. Our extensive database provides SST estimates over a range of -1.4 to 27.2°C for caloric winter and 0.4 to 28.6°C for caloric summer, allowing SST estimates which are especially valuable for the high-latitude Atlantic during glacial times.

Distribution of Upper Cretaceous deep water agglutinated foraminifera in sediments of the North Atlantic and its marginal seas (Tab. 1)

The stratigraphic and biogeographic distribution of more than 170 species of deep-water agglutinated benthic foraminifers (DWAF) from the North Atlantic and adjacent marginal seas has been compared with paleoenvironmental data (e.g. paleobathymetry, oxygenation of the bottom waters, amount of terrigenous input and substrate disturbance). Six general types of assemblages, in which deep water agglutinated taxa occur, are defined from the Turonian to Maastrichtian times: 1. High latitude slope assemblages 2. Low to mid latitude slope assemblages 3. Flysch-type assemblages 4. Deep water limestone assemblages (,,Scaglia,,-type) 5. Abyssal mixed calcareous-agglutinated assemblages 6. Abyssal purely agglutinated assemblages Latitudinal differences in faunal composition are observed, the most important of which is the lack or extreme paucity of calcareous forms in high latitude assemblages. East-to-west differences appear to be of comparatively minor importance. Most DWAF species occur in all studied regions and are thus considered as cosmopolitan. Biostratigraphic turnovers in the taxonomic content of assemblages are observed in the lowermost Turonian, mid-Campanian and in the upper Maastrichtian to lowermost Paleocene. These datum levels correspond to inter-regional and time-constant paleooceanographic events, which probably also affected the deep-water benthic biota. This allows us to use deep-water agglutinated foraminifers for biostratigraphy in the North Atlantic sequences deposited below CCD and to geographically extend the currently used zonal schemes which have been established in the Carpathian and Alpine areas.

Bovine serum albumin as the dominant form of dietary protein reduces subcutaneous fat mass, plasma leptin and plasma corticosterone in high fat-fed C57/BL6J mice

Acknowledgements The authors thank Harriett Schellekens from the University College Cork and Paula O’Connor from Teagasc Moorepark Food Research Centre for their assistance in procuring laboratory space and equipment. The present study was funded by Teagasc. B. L. M. was funded by the Walsh Fellowship Program. J. R. S. was supported by a 1000-talents professorship from the Chinese government. The funding bodies had no input on the design of the study or in the interpretation of the data.

Does attendance affect grade? An analysis of first year economics students in Ireland

This paper examines the relationship between attendance and grade, controlling for other factors, in first year economics courses in University College Cork. Determinants of both class attendance and grade are specified and estimated. We find that attendance is low, at least by comparison with US evidence. Hours worked and travel time are among the factors affecting class attendance. Class attendance, and especially tutorial attendance has a positive and diminishing marginal effect on grade, while hours worked in a part-time job have a significant negative effect on grade.

A Viking Age maritime haven: a reassessment of the island settlement at Beginish, Co. Kerry

The results of O'Kelly’s excavations on Beginish Island are reassessed and it is proposed that there was a long-lived settlement there that functioned as a Viking-age maritime way-station. This re-evaluation is conducted in the light of recent scholarship on the nature of Scandinavian and Hiberno-Scandinavian settlement in Ireland and, in part, is based on the finds that have emerged on Beginish since the conclusion of the excavations there. The site is considered in the context of its location on the sea route that joined Hiberno-Scandinavian Cork with Limerick, and it is suggested that other such way-stations await.

Self-cutting and prospective repetition of self-harm: studies of emergency department presentations in Ireland

Background Self-harm places an individual at increased risk of future self-harm and suicide, and indicates distress and maladaptive coping. Those who present to hospital with self-cutting form a significant minority of self-harm patients who are at increased risk of prospective repetition of self-harm and suicide compared with those presenting with intentional overdose. In addition to increased risk, there is emerging evidence of demographic, psychological, clinical, and social differences between those presenting with self-cutting and those presenting with overdose. Aim and Key Objectives The aim of the current doctoral work was to examine in detail the association between presenting with self-cutting and risk of prospective repetition. The objectives were: to identify evidence-based risk factors for repetition of self-harm among those presenting to emergency departments with self-harm; to compare demographic and presentation characteristics and prospective repetition across presentations of self-cutting only, self-cutting plus intentional overdose, and intentional overdose only; to compare prospective repetition and other characteristics within self-cutting presentations based on the type of treatment received; to compare self-cutting and intentional overdose patients on psychological risk and protective factors for repetition; and to examine the lived experience of engaging in repeated overdose and self-cutting. Methods The current doctoral work used a mixed-methods approach and is comprised of one systematic review and four empirical studies. The empirical studies were two registry-based prospective studies of Irish hospital presentations of self-harm, one prospective structured interview study, and one qualitative study using Interpretative Phenomenological Analysis. Results The systematic review identified several consistent and emerging risk factors for repetition of self-harm, compared to which self-cutting had a medium-sized effect. The registry studies demonstrated that the involvement of self-cutting, particularly less medically severe selfcutting, confers an increased risk of 1-month and 12-month repetition among Irish index selfharm presentations. The structured psychological study detected higher hopelessness and lower non-reactivity to inner experience among those presenting with self-cutting, and higher depression among those who repeated self-harm. Repeaters had lower baseline levels of protective psychological factors than non-repeaters and continued to have higher depression and hopelessness at follow-up. Finally, the qualitative study indicated that self-harm is a purposeful action taken in response to an overwhelming situation and is evaluated afterwards in terms of personal and social effects. Chosen method of self-harm seemed to be influenced by the desired outcome of the self-harm act, capability, accessibility and previous experience. Conclusion Despite limitations in terms of recruitment rates, the work presented in this thesis is innovative in examining the issue of the association between self-cutting and repetition from multiple perspectives. No one factor can reliably predict all repetition but self-cutting represents one consistent and easily detected risk factor for repetition. Those who present with self-cutting exhibit significant differences on demographic, clinical, and psychological variables compared with those presenting with intentional overdose, and seem to exhibit a more vulnerable profile. However, those who present with self-cutting do not form a discrete or homogenous group, and self-harm methods and levels of suicidal intent are liable to fluctuate over time.

Leader's reflections on knowledge, knowing and not knowing: an analysis of change over time

One commonality across the leadership and knowledge related literature is the apparent neglect of the leaders own knowledge. This thesis sought to address this issue through conducting exploratory research into the content of leader’s personal knowledge and the process of knowing it. The empirical inquiry adopted a longitudinal approach, with interviews conducted at two separate time periods with an extended time-interval between each. The findings from this research contrast with images of leadership which suggest leaders are in control of what they know, that they own their own knowledge. The picture that emerges is one of individuals struggling to keep abreast of the knowledge required to deal with the dynamics and uncertainties of organisational life. Much knowledge is tacit, provisional and perishable and the related process of knowing more organic, evolutionary and informal than any structured or orchestrated approach. The collective nature of knowing is a central feature, with these leaders embedded in networks of uncontrollable relationships. In view of the indeterminate nature of knowing, the boundary between what is known and what one needs to know is both amorphous and ephemeral, and the likelihood of knowledge-absences is escalated. A significant finding in this regard is the identification of two critical points where not-knowing is most likely (entry and exit from role) and the differing implications of each. Overtime the knowledge that is legitimised or prioritised is significantly altered as these leaders replace the dogmas that were previously held in high esteem with the lessons from their own experience. This experience brings increased self-knowledge and a deeper appreciation of the values and morals instilled in their early lives. In view of the above findings, this study makes theoretical contribution to a number of core literatures: authentic leadership, role transition and knowledge-absences. In terms of leadership development, the findings point to the necessity to prepare leaders for the challenges they will encounter at the pivotal stages of the leadership role.