Identifying the Structure and Fate of Wastewater Derived Organic Micropollutants by High-resolution Mass Spectrometry

Human activities represent a significant burden on the global water cycle, with large and increasing demands placed on limited water resources by manufacturing, energy production and domestic water use. In addition to changing the quantity of available water resources, human activities lead to changes in water quality by introducing a large and often poorly-characterized array of chemical pollutants, which may negatively impact biodiversity in aquatic ecosystems, leading to impairment of valuable ecosystem functions and services. Domestic and industrial wastewaters represent a significant source of pollution to the aquatic environment due to inadequate or incomplete removal of chemicals introduced into waters by human activities. Currently, incomplete chemical characterization of treated wastewaters limits comprehensive risk assessment of this ubiquitous impact to water. In particular, a significant fraction of the organic chemical composition of treated industrial and domestic wastewaters remains uncharacterized at the molecular level. Efforts aimed at reducing the impacts of water pollution on aquatic ecosystems critically require knowledge of the composition of wastewaters to develop interventions capable of protecting our precious natural water resources.

The goal of this dissertation was to develop a robust, extensible and high-throughput framework for the comprehensive characterization of organic micropollutants in wastewaters by high-resolution accurate-mass mass spectrometry. High-resolution mass spectrometry provides the most powerful analytical technique available for assessing the occurrence and fate of organic pollutants in the water cycle. However, significant limitations in data processing, analysis and interpretation have limited this technique in achieving comprehensive characterization of organic pollutants occurring in natural and built environments. My work aimed to address these challenges by development of automated workflows for the structural characterization of organic pollutants in wastewater and wastewater impacted environments by high-resolution mass spectrometry, and to apply these methods in combination with novel data handling routines to conduct detailed fate studies of wastewater-derived organic micropollutants in the aquatic environment.

In Chapter 2, chemoinformatic tools were implemented along with novel non-targeted mass spectrometric analytical methods to characterize, map, and explore an environmentally-relevant “chemical space” in municipal wastewater. This was accomplished by characterizing the molecular composition of known wastewater-derived organic pollutants and substances that are prioritized as potential wastewater contaminants, using these databases to evaluate the pollutant-likeness of structures postulated for unknown organic compounds that I detected in wastewater extracts using high-resolution mass spectrometry approaches. Results showed that application of multiple computational mass spectrometric tools to structural elucidation of unknown organic pollutants arising in wastewaters improved the efficiency and veracity of screening approaches based on high-resolution mass spectrometry. Furthermore, structural similarity searching was essential for prioritizing substances sharing structural features with known organic pollutants or industrial and consumer chemicals that could enter the environment through use or disposal.

I then applied this comprehensive methodological and computational non-targeted analysis workflow to micropollutant fate analysis in domestic wastewaters (Chapter 3), surface waters impacted by water reuse activities (Chapter 4) and effluents of wastewater treatment facilities receiving wastewater from oil and gas extraction activities (Chapter 5). In Chapter 3, I showed that application of chemometric tools aided in the prioritization of non-targeted compounds arising at various stages of conventional wastewater treatment by partitioning high dimensional data into rational chemical categories based on knowledge of organic chemical fate processes, resulting in the classification of organic micropollutants based on their occurrence and/or removal during treatment. Similarly, in Chapter 4, high-resolution sampling and broad-spectrum targeted and non-targeted chemical analysis were applied to assess the occurrence and fate of organic micropollutants in a water reuse application, wherein reclaimed wastewater was applied for irrigation of turf grass. Results showed that organic micropollutant composition of surface waters receiving runoff from wastewater irrigated areas appeared to be minimally impacted by wastewater-derived organic micropollutants. Finally, Chapter 5 presents results of the comprehensive organic chemical composition of oil and gas wastewaters treated for surface water discharge. Concurrent analysis of effluent samples by complementary, broad-spectrum analytical techniques, revealed that low-levels of hydrophobic organic contaminants, but elevated concentrations of polymeric surfactants, which may effect the fate and analysis of contaminants of concern in oil and gas wastewaters.

Taken together, my work represents significant progress in the characterization of polar organic chemical pollutants associated with wastewater-impacted environments by high-resolution mass spectrometry. Application of these comprehensive methods to examine micropollutant fate processes in wastewater treatment systems, water reuse environments, and water applications in oil/gas exploration yielded new insights into the factors that influence transport, transformation, and persistence of organic micropollutants in these systems across an unprecedented breadth of chemical space.

Behavioral Ecology of the Western Atlantic Short-finned Pilot Whale (Globicephala macrorhynchus)

Social structure is a key determinant of population biology and is central to the way animals exploit their environment. The risk of predation is often invoked as an important factor influencing the evolution of social structure in cetaceans and other mammals, but little direct information is available about how cetaceans actually respond to predators or other perceived threats. The playback of sounds to an animal is a powerful tool for assessing behavioral responses to predators, but quantifying behavioral responses to playback experiments requires baseline knowledge of normal behavioral patterns and variation. The central goal of my dissertation is to describe baseline foraging behavior for the western Atlantic short-finnned pilot whales (Globicephala macrohynchus) and examine the role of social organization in their response to predators. To accomplish this I used multi-sensor digital acoustic tags (DTAGs), satellite-linked time-depth recorders (SLTDR), and playback experiments to study foraging behavior and behavioral response to predators in pilot whales. Fine scale foraging strategies and population level patterns were identified by estimating the body size and examining the location and movement around feeding events using data collected with DTAGs deployed on 40 pilot whales in summers of 2008-2014 off the coast of Cape Hatteras, North Carolina. Pilot whales were found to forage throughout the water column and performed feeding buzzes at depths ranging from 29-1176 meters. The results indicated potential habitat segregation in foraging depth in short-finned pilot whales with larger individuals foraging on average at deeper depths. Calculated aerobic dive limit for large adult males was approximately 6 minutes longer than that of females and likely facilitated the difference in foraging depth. Furthermore, the buzz frequency and speed around feeding attempts indicate this population pilot whales are likely targeting multiple small prey items. Using these results, I built decision trees to inform foraging dive classification in coarse, long-term dive data collected with SLTDRs deployed on 6 pilot whales in the summers of 2014 and 2015 in the same area off the coast of North Carolina. I used these long term foraging records to compare diurnal foraging rates and depths, as well as classify bouts with a maximum likelihood method, and evaluate behavioral aerobic dive limits (ADLB) through examination of dive durations and inter-dive intervals. Dive duration was the best predictor of foraging, with dives >400.6 seconds classified as foraging, and a 96% classification accuracy. There were no diurnal patterns in foraging depth or rates and average duration of bouts was 2.94 hours with maximum bout durations lasting up to 14 hours. The results indicated that pilot whales forage in relatively long bouts and the ADLB indicate that pilot whales rarely, if ever exceed their aerobic limits. To evaluate the response to predators I used controlled playback experiments to examine the behavioral responses of 10 of the tagged short-finned pilot whales off Cape Hatteras, North Carolina and 4 Risso’s dolphins (Grampus griseus) off Southern California to the calls of mammal-eating killer whales (MEK). Both species responded to a subset of MEK calls with increased movement, swim speed and increased cohesion of the focal groups, but the two species exhibited different directional movement and vocal responses. Pilot whales increased their call rate and approached the sound source, but Risso’s dolphins exhibited no change in their vocal behavior and moved in a rapid, directed manner away from the source. Thus, at least to a sub-set of mammal-eating killer whale calls, these two study species reacted in a manner that is consistent with their patterns of social organization. Pilot whales, which live in relatively permanent groups bound by strong social bonds, responded in a manner that built on their high levels of social cohesion. In contrast, Risso’s dolphins exhibited an exaggerated flight response and moved rapidly away from the sound source. The fact that both species responded strongly to a select number of MEK calls, suggests that structural features of signals play critical contextual roles in the probability of response to potential threats in odontocete cetaceans.

Meiofauna and the structure of the benthic community in the Iberian deep sea basin

1. On the cruises 3 and 15 of R.V. "Meteor" 6 grab samples, and 6 hauls with the 6 m Agassiztrawl were taken and at 2 stations the deep sea camera was lowered. This material gave quantitative results on the meiofauna and minimum counts of the macrofauna. 2. The nematodes constitute nearly 95% of the meiofauna, the copepoda only 2%. With increasing sediment depth the density of animals decrease gradually. In the uppermost centimeter of sediment 42.6% of the meiofauna are found while only 3.7% live in layer 6-7 cm. Meiofauna weight ranges from 0.6-5.7 mg/25 m**2 surface i.e. 0.24-2.8 g/m**2. 3. Mean numbers of individuals and weights show standard errors of 20-30 %. As an approximate average values for further considerations the weight of the meiofauna in the area was taken as 1 g/m**2 4. Quantitative information on the macrofauna is derived from the trawls and the photographs for the actinia Chitonanthus abyssorum only, which is found in the rate of 1 individual/36-72 m**2, but seems to be less abundant generally. 5. Animal density does not decrease steadily from nearshore to offshore biocoenoses, i.e. generally with increasing depth. The decrease is more pronounced for macro- than for meiofauna. For the deep sea the weight proportion of macrofauna : meiofauna is of the order of 1 : 1. 6. With the assumption, that adaptation of metabolism to deep sea conditions is similar in macro- and meiofauna total metabolism of invertebrates is ascribed to meiofauna to more than 80%. 7. The structure of the biocoenosis of the deep sea floor is characterized by the meiofauna living on and in the sediment and by the dominance of sediment feeders in the macrofauna. 8. Considering the large numbets and high partition rates of bacteria a comparative large part of the metabolism in the deep sea sediment must be ascribed to bacteria. This favours the hypothesis, that with increasing depth and decreasing addition of organic material to the sediment, the importance of meiofauna and microorganisms for total metabolism increases. 9. Considering the different modes of food transport to the deep sea environment, i.e. sinking of dead particles, transport by vertical migration of organisms, aggregation of organic particles, adsorption of dissoloved organic substance to inorganic particles, and heterotrophy, the sediment may be assumed to contain more food for invertebrates than the water above the bottom. 10. Suspensions feeders of macrofauna are fixed to hard substrates in the sediment surface. Some of them are shown to bend themselves down to the bottom in underwater photographs. This suggests the idea that some deep sea suspension feeders partly depend on food from the sediment surface, on which they feed directly.

Effect of enhanced pCO2 levels on the production of dissolved organic carbon and transparent exopolymer particles in short-term bioassay experiments

It has been proposed that increasing levels of pCO2 in the surface ocean will lead to more partitioning of the organic carbon fixed by marine primary production into the dissolved rather than the particulate fraction. This process may result in enhanced accumulation of dissolved organic carbon (DOC) in the surface ocean and/or concurrent accumulation of transparent exopolymer particles (TEPs), with important implications for the functioning of the marine carbon cycle. We investigated this in shipboard bioassay experiments that considered the effect of four different pCO2 scenarios (ambient, 550, 750 and 1000 µatm) on unamended natural phytoplankton communities from a range of locations in the northwest European shelf seas. The environmental settings, in terms of nutrient availability, phytoplankton community structure and growth conditions, varied considerably between locations. We did not observe any strong or consistent effect of pCO2 on DOC production. There was a significant but highly variable effect of pCO2 on the production of TEPs. In three of the five experiments, variation of TEP production between pCO2 treatments was caused by the effect of pCO2 on phytoplankton growth rather than a direct effect on TEP production. In one of the five experiments, there was evidence of enhanced TEP production at high pCO2 (twice as much production over the 96 h incubation period in the 750 ?atm treatment compared with the ambient treatment) independent of indirect effects, as hypothesised by previous studies. Our results suggest that the environmental setting of experiments (community structure, nutrient availability and occurrence of phytoplankton growth) is a key factor determining the TEP response to pCO2 perturbations.

The Pico de Navas slump (Burgos, Spain): a large rocky landslide caused by underlying clayey sand fluidification

The Pico de Navas landslide was a large-magnitude rotational movement, affecting 50x106m3 of hard to soft rocks. The objectives of this study were: (1) to characterize the landslide in terms of geology, geomorphological features and geotechnical parameters; and (2) to obtain an adequate geomechanical model to comprehensively explain its rupture, considering topographic, hydro-geological and geomechanical conditions. The rupture surface crossed, from top to bottom: (a) more than 200 m of limestone and clay units of the Upper Cretaceous, affected by faults; and (b) the Albian unit of Utrillas facies composed of silty sand with clay (Kaolinite) of the Lower Cretaceous. This sand played an important role in the basal failure of the slide due to the influence of fine particles (silt and clay), which comprised on average more than 70% of the sand, and the high content presence of kaolinite (>40%) in some beds. Its geotechnical parameters are: unit weight (δ) = 19-23 KN/m3; friction angle (φ) = 13º-38º and cohesion (c) = 10-48 KN/m2. Its microstructure consists of accumulations of kaolinite crystals stuck to terrigenous grains, making clayey peds. We hypothesize that the presence of these aggregates was the internal cause of fluidification of this layer once wet. Besides the faulted structure of the massif, other conditioning factors of the movement were: the large load of the upper limestone layers; high water table levels; high water pore pressure; and the loss of strength due to wet conditions. The 3D simulation of the stability conditions concurs with our hypothesis. The landslide occurred in the Recent or Middle Holocene, certainly before at least 500 BC and possibly during a wet climate period. Today, it appears to be inactive. This study helps to understand the frequent slope instabilities all along the Iberian Range when facies Utrillas is present.

Ecophysiology of Adonis distorta, a high-mountain species endemic of the Central Apennines

Morphological, anatomical and physiological plant and leaf traits of A. distorta, an endemic species of the Central Apennines on the Majella Massif, growing at 2,675 m a.s.l, were analyzed. The length of the phenological cycle starts immediately after the snowmelt at the end of May, lasting 128 ± 10 days. The low A. distorta height  (Hmax= 64 ± 4 mm) and total leaf area (TLA= 38 ± 9 cm2) associated to a high leaf mass area (LMA =11.8±0.6 mg cm−2) and a relatively high leaf tissue density (LTD = 124.6±14.3 mg cm−3) seem to be adaptive traits to the stress factors of the environment where it grows. From a physiological point of view, the high A. distorta photosynthetic rates (PN =19.6 ± 2.3 µmol m−2 s−1) and total chlorophyll content (Chla+b = 0.88 ± 0.13 mg g−1) in July are justified by the favorable temperature. PN decreases by 87% in September at the beginning of plant senescence. Photosynthesis and leaf respiration (RD) variations allow A. distorta to maintain a positive carbon balance during the growing season becoming indicative of the efficiency of plant carbon use. The results could be an important tool for conservation programmes of the A. distorta wild populations.

Energy levels and radiative rates for transitions in Cr-like Co IV and Ni V

We report calculations of energy levels and radiative rates (A-values) for transitions in Cr-like Co IV and Ni V. The quasi-relativistic Hartree-Fock (QRHF) code is adopted for calculating the data although grasp (general-purpose relativistic atomic structure package) and flexible atomic code (fac) have also been employed for comparison purposes. No radiative rates are available in the literature to compare with our results, but our calculated energies are in close agreement with those compiled by NIST for a majority of the levels. However, there are discrepancies for a few levels of up to 3%. The A-values are listed for all significantly contributing E1, E2 and M1 transitions, and the corresponding lifetimes reported, although unfortunately no previous theoretical or experimental results exist to compare with our data.

Benchmarking a modified version of the civ3 nonrelativistic atomic-structure code within Na-like-tungsten R -matrix calculations

In this work we explore the validity of employing a modified version of the nonrelativistic structure code civ3 for heavy, highly charged systems, using Na-like tungsten as a simple benchmark. Consequently, we present radiative and subsequent collisional atomic data compared with corresponding results from a fully relativistic structure and collisional model. Our motivation for this line of study is to benchmark civ3 against the relativistic grasp0 structure code. This is an important study as civ3 wave functions in nonrelativistic R-matrix calculations are computationally less expensive than their Dirac counterparts. There are very few existing data for the W LXIV ion in the literature with which we can compare except for an incomplete set of energy levels available from the NIST database. The overall accuracy of the present results is thus determined by the comparison between the civ3 and grasp0 structure codes alongside collisional atomic data computed by the R-matrix Breit-Pauli and Dirac codes. It is found that the electron-impact collision strengths and effective collision strengths computed by these differing methods are in good general agreement for the majority of the transitions considered, across a broad range of electron temperatures.

REIT Capital Structure Choices: Preparation Matters

Sun, Titman, and Twite (2015) find that capital structure risks, namely high leverage and a high share of short-term debt, reduced the cumulative total return of US REITs in the 2007-2009 financial crisis. We find that mitigating capital structure risks ahead of the crisis by reducing leverage and extending debt maturity in 2006, was associated with a significantly higher cumulative total return 2007-2009, after controlling for the levels of those variables at the start of the financial crisis. We further identify two systematic cross-sectional differences between those REITs that reduced capital structure risks prior to the financial crisis and those that did not: the exposure to capital structure risks and the strength of corporate governance. On balance, our findings are consistent with the interpretation of risk-reducing adjustments to capital structure ahead of the crisis as a component of managerial skill and discipline with significant implications for firm value during the crisis.

The Effect of Water Consumption on Schoolchildren's Fine Motor Skills, Cognitive Function and Mood

Previous research has suggested that dehydration may have a negative effect on some aspects of mood, cognitive performance and motor skills (Benton, 2011). Furthermore, a large proportion of children arrive at school in a dehydrated state (Baron, Courbebaisse, Lepicard, & Friedlander, 2015). The present work investigated whether supplementing children with water may, as a consequence of reducing dehydration, improve their cognitive performance and motor skills. In studies 1, 2, 3 and 5, it was found that tasks that predominantly tested motor skills, were improved in children who had a drink, compared to those who did not. Furthermore, study 3 showed that this effect was moderated by hydration status. One theoretical explanation for the poorer performance of dehydrated children is that they may lack the neurological resources to sustain their effort and thus performance does not improve over time. In support of this, these studies showed that, when re-hydrated, performance on these tasks improves to the level of non-dehydrated children. Study 2 showed that the number of errors increased in a StopSignal task in children that had high self-rated levels of thirst, compared to low levels: and hydration status did not moderate this effect. A possible explanation for the increased number of errors in children with high self-rated thirst is that the thirst sensation diverts attention away from the task, causing task performance to deteriorate. In study 4, it was observed that there was a large variation in intra-individual and inter-individual hydration scores throughout the day, which was not related to volume drank or levels of thirst. Further studies should use imaging techniques to study brain activity during dehydration and rehydration, and during periods of high thirst, to help to further elucidate the mechanism underlying the negative effect of dehydration on motor performance, and the effect of self-rated thirst on attention.

Au deçà de la Cité de Dieu

La Cité de Dieu a été rédigée dans une perspective polémique vis-à-vis les païens. La prise de Rome, en 410, a entraîné en Afrique du Nord la venue d’une élite cultivée, revivaliste et admirative du vieux polythéisme. Contre cette mouvance nostalgique, tributaire des anciens majoritairement sur le plan intellectuel et livresque, Augustin s’en prend à la bibliothèque des nouveaux arrivants. La Cité de Dieu peut, le cas échéant, être lue par la négative, c’est-à-dire par le biais de la critique qu’élabore Augustin de trois auteurs choisis, Varron, Cicéron et Salluste, qui résument et représentent conjointement l’essence de la culture classique. Tant chez les païens que chez l’évêque d’Hippone – leur détracteur –, Varron incarne la fine pointe de la théologie romano-hellénistique, Salluste est celui qui a mené à sa perfection la discipline de l’histoire, Cicéron a écrit le parachèvement des oeuvres sur la République, et chacun préconise sa structure idéologique propre, les trois domaines formant pourtant un ensemble systémique. Tout en louant ses illustres prédécesseurs, Augustin leur porte une critique générale et c’est à cette critique que seront consacrées nos analyses.

Air Pollution and High Density Lipoprotein Structure and Function

Thesis (Ph.D.)--University of Washington, 2016-06