A study of methods used to analyze total oil and polycyclic aromatic hydrocarbons in produced water: steps towards the validation of molecularly imprinted polymers for use in marine environmetns

Produced water is a by-product of offshore oil and gas production, and is released in large volumes when platforms are actively processing crude oil. Some pollutants are not typically removed by conventional oil/water separation methods and are discharged with produced water. Oil and grease can be found dispersed in produced water in the form of tiny droplets, and polycyclic aromatic hydrocarbons (PAHs) are commonly found dissolved in produced water. Both can have acute and chronic toxic effects in marine environments even at low exposure levels. The analysis of the dissolved and dispersed phases are a priority, but effort is required to meet the necessary detection limits. There are several methods for the analysis of produced water for dispersed oil and dissolved PAHs, all of which have advantages and disadvantages. In this work, EPA Method 1664 and APHA Method 5520 C for the determination of oil and grease will be examined and compared. For the detection of PAHs, EPA Method 525 and PAH MIPs will be compared, and results evaluated. APHA Method 5520 C Partition-Infrared Method is a liquid-liquid extraction procedure with IR determination of oil and grease. For analysis on spiked samples of artificial seawater, extraction efficiency ranged from 85 – 97%. Linearity was achieved in the range of 5 – 500 mg/L. This is a single-wavelength method and is unsuitable for quantification of aromatics and other compounds that lack sp³-hybridized carbon atoms. EPA Method 1664 is the liquid-liquid extraction of oil and grease from water samples followed by gravimetric determination. When distilled water spiked with reference oil was extracted by this procedure, extraction efficiency ranged from 28.4 – 86.2%, and %RSD ranged from 7.68 – 38.0%. EPA Method 525 uses solid phase extraction with analysis by GC-MS, and was performed on distilled water and water from St. John’s Harbour, all spiked with naphthalene, fluorene, phenanthrene, and pyrene. The limits of detection in harbour water were 0.144, 3.82, 0.119, and 0.153 g/L respectively. Linearity was obtained in the range of 0.5-10 g/L, and %RSD ranged from 0.36% (fluorene) to 46% (pyrene). Molecularly imprinted polymers (MIPs) are sorbent materials made selective by polymerizing functional monomers and crosslinkers in the presence of a template molecule, usually the analytes of interest or related compounds. They can adsorb and concentrate PAHs from aqueous environments and are combined with methods of analysis including GC-MS, LC-UV-Vis, and desorption electrospray ionization (DESI)- MS. This work examines MIP-based methods as well as those methods previously mentioned which are currently used by the oil and gas industry and government environmental agencies. MIPs are shown to give results consistent with other methods, and are a low-cost alternative improving ease, throughput, and sensitivity. PAH MIPs were used to determine naphthalene spiked into ASTM artificial seawater, as well as produced water from an offshore oil and gas operation. Linearity was achieved in the range studied (0.5 – 5 mg/L) for both matrices, with R² = 0.936 for seawater and R² = 0.819 for produced water. The %RSD for seawater ranged from 6.58 – 50.5% and for produced water, from 8.19 – 79.6%.

Acting on impulse: using the neuroscience of impulse control to improve the law

This thesis investigates the potential legal utility of neurotechnologies which measure correlates of impulsive behaviors. Chapter 1 explains my philosophical position and how this position compares to others in the field. Chapter 2 explores some of the technical concepts which must be understood for the discussion of neurotechnologies and their applications to be fruitful. These chapters will be important for both explaining the capabilities of a neuroscientific approach to neural abnormalities as well as how they relate to the kind of regulation in which the law is engaged. The purpose of Chapter 3 will be a descriptive account of Canadian law where I will begin to explore how to apply ideas and experiments from neuroscience to specific areas of law. Chapter 3 will look at actual examples of Canadian criminal law and will span topics from the creation of law to the construction of appropriate sentences. Chapter 4 will debate if and how we should apply the neuroscientific perspective to the law given the ethical concerns surrounding the applications described in Chapter 3. The thrust of the chapter is that the development of the law does not occur in a vacuum and any alteration either to the laws themselves, how they are interpreted, or the technologies used to provide evidence, must have an ethical justification, that is, a way in which the proposed change will better meet the needs of society and the ethical objectives of the law. Sometimes these justifications can be drawn directly from constitutional documents, such as the Charter, or from the Criminal Code, while at other times these justifications depend upon arguments about furthering meaningful responsibility and therapeutic outcomes.

Independent Projects Environmental Studies 2010: From Climate Change Laggard to Leader: Policy recommedations for Newfoundland and Labrador

Dyer, along with many others reflecting international consensus in the scientific community, argues that countries must be carbon neutral by 2050 to avoid the worst impacts of climate change (Dyer, 2008, p. xii). to accomplish this by 2050, we need to act now: governments need to cooperate with the scientific community to ensure our society makes the changes to combat climate change. How is Canada reacting to this situation? As describes by the Sierra Club of Canada, "federal government continues to drag its feet, and delay any action to reduce emissions" (2008, p. 18). Given this federal reluctance, individual provinces must act to reduce emissions. While some provinces take a required action, primarily Quebec and British Columbia, others, like Newfoundland and Labrador, contribute little in terms of emissions reductions. Newfoundland and Labrador is ranked as "poor"-among the worst performers regarding climate change policy in the country-by the David Suzuki Foundation in a cross Canada evaluation of various provincial climate change policies (David Suzuki Foundation, 2008, p. 9). The Province of Newfoundland is not doing enough to address climate change. In this paper I argue that to improve this situation, the province could follow the example of the two leading jurisdictions, Quebec and British Columbia, to refine and introduce its own hybrid policy that directly affects decision making processes. But, this can be complicated when convincing the government that it is important to accept stronger policy. The government must consider what climate change impacts Newfoundland and Labrador experiences and willconinue to experience and what Newfoundland and Labrador is contributing to the problem of climate change. To evaluate these issues of climate change, I first survey the positive policies Newfoundland and Labrador is currently implementing/ discussing and then outline action taken by the provincial environment leaders, Quebec and British Columbia.Then I describe the strong pieces in the Quebec and British Columbia climate change action plan that Newfoundland and Labrador can emulate. Finally, I consider if thes polices are politically feasible for the government of Newfoundland and labrador. Hence, this paper aims to give a blueprint of what Newfoundland and Labrador has to act on to make itself an environmental leader.

Last glacial maximum sediment record of the southern Weddell Sea shelf

Abstract: The history of grounded ice-sheet extent on the southern Weddell Sea shelf during the Last Glacial Maximum (LGM) and the timing of post-LGM ice-sheet retreat are poorly constrained. Several glaciological models reconstructed widespread grounding and major thickening of the Antarctic Ice Sheet in the Weddell Sea sector at the LGM. In contrast, recently published onshore data and modelling results concluded only very limited LGM-thickening of glaciers and ice streams feeding into the modern Filchner and Ronne ice shelves. These studies concluded that during the LGM ice shelves rather than grounded ice covered the Filchner and Ronne troughs, two deep palaeo-ice stream troughs eroded into the southern Weddell Sea shelf. Here we review previously published and unpublished marine geophysical and geological data from the southern Weddell Sea shelf. The stratigraphy and geometry of reflectors in acoustic sub-bottom profiles are similar to those from other West Antarctic palaeo-ice stream troughs, where grounded ice had advanced to the shelf break at the LGM. Numerous cores from the southern Weddell Sea shelf recovered sequences with properties typical for subglacially deposited tills or subglacially compacted sediments. These data sets give evidence that grounded ice had advanced across the shelf during the past, thereby grounding in even the deepest parts of the Filchner and Ronne troughs. Radiocarbon dates from glaciomarine sediments overlying the subglacial deposits are limited, but indicate that the ice grounding occurred at the LGM and that ice retreat started before ~15.1 corrected 14C kyrs before present (BP) on the outer shelf and before ~7.7 corrected 14C kyrs BP on the inner shelf, which is broadly synchronous with ice retreat in other Antarctic sectors. The apparent mismatch between the ice-sheet reconstructions from marine and terrestrial data can be attributed to ice streams with very low surface profiles (similar to those of "ice plains") that had advanced through Filchner Trough and Ronne Trough at the LGM. Considering the global sea-level lowstand of ~130 metres below present, a low surface slope of the expanded LGM-ice sheet in the southern Weddell Sea can reconcile grounding-line advance to the shelf break with limited thickening of glaciers and ice streams in the hinterland. This scenario implies that ice-sheet growth in the Weddell Sea sector during the LGM and ice-sheet drawdown throughout the last deglaciation could only have made minor contributions to the major global sea-level fluctuations during these times.

Doing Research with Vulnerable Populations: The Case of Intravenous Drug Users

Article

Epitaxial growth of visible to infra-red transparent conducting In2O3 nanodot dispersions and reversible charge storage as a Li-ion battery anode

Unique bimodal distributions of single crystal epitaxially grown In2O3 nanodots on silicon are shown to have excellent IR transparency greater than 87% at IR wavelengths up to 4 μm without sacrificing transparency in the visible region. These broadband antireflective nanodot dispersions are grown using a two-step metal deposition and oxidation by molecular beam epitaxy, and backscattered diffraction confirms a dominant (111) surface orientation. We detail the growth of a bimodal size distribution that facilitates good surface coverage (80%) while allowing a significant reduction in In2O3 refractive index. This unique dispersion offers excellent surface coverage and three-dimensional volumetric expansion compared to a thin film, and a step reduction in refractive index compared to bulk active materials or randomly porous composites, to more closely match the refractive index of an electrolyte, improving transparency. The (111) surface orientation of the nanodots, when fully ripened, allows minimum lattice mismatch strain between the In2O3 and the Si surface. This helps to circumvent potential interfacial weakening caused by volume contraction due to electrochemical reduction to lithium, or expansion during lithiation. Cycling under potentiodynamic conditions shows that the transparent anode of nanodots reversibly alloys lithium with good Coulombic efficiency, buffered by co-insertion into the silicon substrate. These properties could potentially lead to further development of similarly controlled dispersions of a range of other active materials to give transparent battery electrodes or materials capable of non-destructive in situ spectroscopic characterization during charging and discharging.

An examination of the role of the sports and exercise medicine specialist in Ireland- from epidemiology to treatment

The expansion of the specialty of sports and exercise medicine (SEM) is a relatively recent development in the medical community and the role of the SEM specialist continues to evolve and develop. The SEM specialist is ideally placed to care for all aspects of physical activity not only in athletes but also in the general population. As an advocate for physical activity the SEM specialist plays a broad role in advising safe effective sports and recreation participation; screening for disease related to sports participation; examining and contributing to the evidence behind treatment strategies and evaluating any potential negative impact of sports injury prevention measures. In this thesis I will demonstrate the breadth of the role the Sports and Exercise Medicine Specialist from epidemiology to in-depth examination of treatment strategies. In Chapter 2, I examined the epidemiology of sports and recreation related injury (SRI) in Ireland, an area that has previously been poorly studied. We report on 3,172 SRI (14% of total presentations) presentations to the ED over 6 months. Paediatric patients (4-16 yrs) were over represented comprising 39.9% of all SRI presentation compared to 16% of total ED presentations and 18% of the general population. These injuries were serious (32% fractures) and though 49% of injuries occurred during organised competition/practice, 41.5% occurred during recreation-most often at home. In Chapter 3, I examined risk factors associated with hand injury in hurling. The previous chapter highlighted the importance of a firm evidence base underpinning treatment strategies. When measures to improve welfare are introduced not only must potential benefits be measured, so too must potential unwanted adverse outcomes. In this study I examined a cohort of adult hurlers who had presented to the ED with a hurling related injury in order to highlight the variables associated with hand injury in this population. I found the athletes who wore a helmet were far more likely (OR 3.15 95% CI (1.51-6.56) p= 0.002) to suffer a hand injury than athletes who did not. Very few of those interviewed (4.9%) used hand protection compared to 65% who used helmet and faceguard. The introduction of the helmet and faceguard in hurling has undeniably decreased the incidence of head and face injury in hurling. However in tandem with this intervention several observational studies have demonstrated an increase in the occurrence of hurling related hand injuries. This study highlights the importance of being cognisant of unanticipated or unintended consequences when implementing a new treatment or intervention. In Chapter 4, I examined the role of population screening as applied to sport and exercise. This is a controversial area –cardiac screening in the exercising population has been the subject of much debate. Specifically I define the prevalence of exercise induced bronchoconstriction (EIB) using a specifically designed sports specific field-testing protocol. In this study I found almost a third (29%) of a full international professional rugby squad had confirmed asthma or EIB, as compared with 12-15% of the general population. Despite regular medical screening, 5 ‘new’ untreated cases (12%) were elicited by the challenge test and in the group already on treatment for asthma/EIB; over 50% still displayed EIB. In Chapter 5, I examined the evidence supporting current treatment options for iliotibial band friction syndrome (ITBFS). The practice of sports medicine has traditionally been ‘eminence based’ rather than ‘evidence based’. This may be problematic as some of these practices are based upon flawed principles- for example the treatment of iliotibial band friction syndrome (ITBFS). In this chapter, using cadaveric and biomechanical studies I expand upon the growing base of evidence clarifying the anatomy and biomechanics of the area-thereby re-examining the principles on which current treatments are based. The role of the SEM specialist is broad; we chose to examine specific examples of some of the roles that they execute. An understanding of the epidemiology of SRI presenting to the ED has implications for individual patients, sports governing bodies and health resource utilisation. Population screening is an important tool in health promotion and disease prevention in the general population. Screening in SEM may have similar less well-recognised benefits. The SEM specialist needs to be conversant in screening for medical conditions concerning physical activity. A comprehensive understanding of the pathophysiology of a disease is required for its diagnosis and treatment. Due to the ongoing evolution of SEM many treatments are eminence-based rather than evidence‐based practice. Continued re-examination of the fundamentals of current practice is essential. An awareness of potential unwanted side effects is essential prior to the introduction of any new treatment or intervention. The SEM specialist is ideally placed to advise sports governing bodies on these issues prior to and during their implementation.

Doing Research with Vulnerable Populations: The Case of Intravenous Drug Users

Article

Chlorine Contribution to Quantitative Structure and Activity Relationship Models of Disinfection By-Products' Quantum Chemical Descriptors and Toxicities

Quantitative Structure-Activity Relationship (QSAR) has been applied extensively in predicting toxicity of Disinfection By-Products (DBPs) in drinking water. Among many toxicological properties, acute and chronic toxicities of DBPs have been widely used in health risk assessment of DBPs. These toxicities are correlated with molecular properties, which are usually correlated with molecular descriptors. The primary goals of this thesis are: 1) to investigate the effects of molecular descriptors (e.g., chlorine number) on molecular properties such as energy of the lowest unoccupied molecular orbital (ELUMO) via QSAR modelling and analysis; 2) to validate the models by using internal and external cross-validation techniques; 3) to quantify the model uncertainties through Taylor and Monte Carlo Simulation. One of the very important ways to predict molecular properties such as ELUMO is using QSAR analysis. In this study, number of chlorine (NCl) and number of carbon (NC) as well as energy of the highest occupied molecular orbital (EHOMO) are used as molecular descriptors. There are typically three approaches used in QSAR model development: 1) Linear or Multi-linear Regression (MLR); 2) Partial Least Squares (PLS); and 3) Principle Component Regression (PCR). In QSAR analysis, a very critical step is model validation after QSAR models are established and before applying them to toxicity prediction. The DBPs to be studied include five chemical classes: chlorinated alkanes, alkenes, and aromatics. In addition, validated QSARs are developed to describe the toxicity of selected groups (i.e., chloro-alkane and aromatic compounds with a nitro- or cyano group) of DBP chemicals to three types of organisms (e.g., Fish, T. pyriformis, and P.pyosphoreum) based on experimental toxicity data from the literature. The results show that: 1) QSAR models to predict molecular property built by MLR, PLS or PCR can be used either to select valid data points or to eliminate outliers; 2) The Leave-One-Out Cross-Validation procedure by itself is not enough to give a reliable representation of the predictive ability of the QSAR models, however, Leave-Many-Out/K-fold cross-validation and external validation can be applied together to achieve more reliable results; 3) ELUMO are shown to correlate highly with the NCl for several classes of DBPs; and 4) According to uncertainty analysis using Taylor method, the uncertainty of QSAR models is contributed mostly from NCl for all DBP classes.

Geochemistry in the mid Atlantic Ocean ridge basalts

The main objective of Leg 82 of the Glomar Challenger was to document mantle heterogeneity in the vicinity of, and away from, a so-called hot spot: the Azores Triple Junction. One of the geochemical tools that permits, at least in part, the recognition of mantle heterogeneities uses hygromagmaphile elements, those elements that have an affinity for the liquid. This tool is presented in terms of an extended Coryell-Masuda plot, which incorporates within the rare earth elements the hygromagmaphile transition elements Th, Ta, Zr, Hf, Ti, Y, and V. The extended Coryell-Masuda plot is used to summarize our knowledge of mantle heterogeneity along the ridge axis at zero-age. It is also used by choosing those hygromagmaphile elements that can be analyzed on board by X-ray fluorescence spectrometry to give preliminary information on the enriched or depleted character of recovered samples. Shore-based results, which include analyses of most of the hygromagmaphile elements measured either by X-ray spectrometry or neutron activation analysis, confirm the shipboard data. From the point of view of comparative geochemistry, the variety of basalts recovered during Leg 82 provides a good opportunity to test and verify the classification of the hygromagmaphile elements. Analyses from Leg 82 provide new data about the relationship between extended rare earth patterns (enriched or depleted) that can be estimated either by La/Sm ratio or Nb/Zr (or Ta/Hf) ratios: samples from Hole 556 are depleted (low Nb/Zr ratio) but have a high 206Pb/ 204Pb (19.5) ratio; in Hole 558 a moderately enriched basalt unit with a La/Sm (= Nb/Zr) ratio (chondrite normalized) of 2 has a high 206Pb/204Pb (20) ratio. One of the most interesting results of Leg 82 lies in the crossing patterns of extended Coryell-Masuda plots for basalts from the same hole. This result enhances the notion of local mantle heterogeneity versus regional mantle heterogeneity and is confirmed by isotope data; it also favors a model of short-lived, discrete magma chambers. The data tend to confirm the Hayes Fracture Zone as a southern limit for the influence of Azores-type mantle. Nevertheless, north of the Hayes Fracture Zone, the influence of a plumelike mantle source is not simple and probably requires an explanation more complex than a contribution from a single fixed hot spot.

Pollen records of five sediment cores from northern Germany

Within a larger program research work is being done on the history of settlement and landscape of the 'Siedlungskammer' Flögeln and the adjacent area. The 'Siedlungskammer' consists of an isolated pleistocene sand ground (Geest-island) surroundet by bogs. Starting from the edge of the Geest, near which large-scale archaeological excavations are carried out, three raised bog profiles were taken at 300, 500 and 4000 m off the prehistoric settlement. They were investigated by means of pollen analysis, and reflect in a decreasing way the activities of man on the Geestisland. Another pollen diagram from the nearby fen peat was worked out for comparison. At the same time it helped to date back a prehistoric sand path to the Roman period. The pollen diagrams cover the vegetational history without gaps from the early Atlantic period to modern times. The vegetation was decisively determined by the poor soils of this area. T'he pollen diagrams give evidence of the activity of settlers since the Neolithic age, with some gaps in the beginning, but later continuously from the middle of the Bronze age until the early migration period. The influence of the nearby settlement, which existed from the Birth of Christ to the 4/5th century, comes out distinctly. Among the cereals which were then cultivated here, there also was rye, at least in the 4/5th century, but most probably already during the Roman period. Besides that people cultivated barley, oats, and flax. The settlement break during the so-called dark ages between the 4/5th century and the time about 800 A.D. was confirmed by pollen analysis. During this time the area was once more covered by forests. The fluctuations of man's activities during the late Middle Ages and modern times, as they are made visible by pollen analysis, correspond to historically wellknown developments.

Analysis of Evidence from Core Sample Fractures in Stewardson Lake Uranium Prospect

This study was performed to characterize evidence of potential unconformity-type U mineralizing fluids in drill core fractures from the Stewardson Lake prospect, in the Athabasca Basin, located in Northern Saskatchewan and Alberta, Canada. Fractures were visually classified into eight varieties. This classification scheme was improved with the use of mineralogical characterization through SEM (Scanning Electron Microscope) and XRD analyses of the fracture fills and resulted in the identification of various oxides, hydroxides, sulfides, and clays or clay-sized minerals. Fractures were tallied to a total of ten categories with some commonalities in color. The oxidative, reductive or mixed nature of the fluids interacting with each fracture was determined based on its fill mineralogy. The measured Pb isotopic signature of samples was used to distinguish fractures affected solely by fluids emanating from a U mineralization source, from those affected by mixed fluids. Anomalies in U and U-pathfinder elements detected in fractures assisted with attributing them to the secondary dispersion halo of potential mineralization. Three types of fracture functions (chimney, composite and drain) were defined based on their interpreted flow vector and history. A secondary dispersion halo boundary with a zone of dominance of infiltrating fluids was suggested for two boreholes. The control of fill mineralogy on fracture color was investigated and the indicative and non-indicative colors and minerals, with respect to a secondary dispersion halo, were formally described. The fracture colors and fills indicative of proximity to the basement host of the potential mineralization were also identified. In addition, three zones of interest were delineated in the boreholes with respect to their geochemical dynamics and their relationship to the potential mineralization: a shallow barren overburden zone, a dispersion and alteration zone at intermediate depth, and a second deeper zone of dispersion and alteration.

Children’s access to beneficial information in Arab states: Implementation of Article 17 of the Convention on the Rights of the Child in Egypt, Morocco and the United Arab Emirates

In theory, the multiple platforms and transnational nature of digital media, along with a related proliferation of diverse forms of content, make it easier for children’s right to access socially and culturally beneficial information and material to be realised, as required by Article 17 of the UN Convention on the Rights of the Child (CRC). Drawing on data collected during research on children’s screen content in the Arab world, combined with scrutiny of documents collated by the Committee on the Rights of the Child, which monitors compliance with the CRC, this paper explores how three Arab countries, Egypt, Morocco and the United Arab Emirates, presented their efforts to implement Article 17 as part of their periodic reporting on their overall performance in putting the CRC into effect. It uncovers tensions over the relationship between provision, participation and protection in relation to media, reveals that Article 17 is liable to get less attention than it deserves in contexts where governments keep a tight grip on media, and that, by appearing to give it a lower priority, all parties neglect the intersection between human rights in relation to media and children’s rights.

Contar la crisis: materiales narrativos en la semántica social de la crisis

Basado en la evidencia proporcionada por 9 grupos de discusión, este trabajo aborda la semántica social de la crisis en el marco de la hipótesis propuesta por Janet Roitman. En consecuencia propone retratar distintas estrategias narrativas que permiten dar cuenta de la experiencia de la crisis según cuatro ejes de contraposiciones: agencia/paciencia, moralización/poder, coyuntura/cronicidad, destrucción/creación. En su parte final, propone fijar los rasgos fundamentales de los sujetos que aparecen en seno de las tramas narrativas propuestas.

The Continuous Plankton Recorder survey: How can long-term phytoplankton datasets contribute to the assessment of Good Environmental Status?

Phytoplankton are crucial to marine ecosystem functioning and are important indicators of environmental change. Phytoplankton data are also essential for informing management and policy, particularly in supporting the new generation of marine legislative drivers, which take a holistic ecosystem approach to management. The Marine Strategy Framework Directive (MSFD) seeks to achieve Good Environmental Status (GES) of European seas through the implementation of such a management approach. This is a regional scale directive which recognises the importance of plankton communities in marine ecosystems; plankton data at the appropriate spatial, temporal and taxonomic scales are therefore required for implementation. The Continuous Plankton Recorder (CPR) survey is a multidecadal, North Atlantic basin scale programme which routinely records approximately 300 phytoplankton taxa. Because of these attributes, the survey plays a key role in the implementation of the MSFD and the assessment of GES in the Northeast Atlantic region. This paper addresses the role of the CPR's phytoplankton time-series in delivering GES through the development and informing of MSFD indicators, the setting of targets against a background of climate change and the provision of supporting information used to interpret change in non-plankton indicators. We also discuss CPR data in the context of other phytoplankton data types that may contribute to GES, as well as explore future possibilities for the use of new and innovative applications of CPR phytoplankton datasets in delivering GES. Efforts must be made to preserve long-term time series, such as the CPR, which supply vital ecological information used to informed evidence-based environmental policy.