A New Method for Computing the Eccentric Connectivity Index of Fullerenes

ACM Computing Classification System (1998): G.2.2, G.2.3.

delta Deuterium of alkenone and BIT index of sediment core 64PE304-80 samples

Reconstructing past ocean salinity is important for assessing paleoceanographic change and therefore past climatic dynamics. Commonly, sea water salinity reconstruction is based on foraminifera oxygen isotope ratio values combined with sea surface temperature reconstruction. However, the approach relies on multiple proxies, resulting in relatively large uncertainty and, consequently, relatively low accuracy of salinity estimates. An alternative tool for past ocean salinity reconstruction is the hydrogen isotope composition of long chain (C37) alkenones (dDalkenone). Here, we applied dDalkenone to a 39 ka long coastal sediment record from the Eastern South African continental shelf in the Mozambique Channel, close to the Zambezi River mouth. Despite changes in global sea water dD related to glacial - interglacial ice volume effects, no clear changes were observed in the dDalkenone record throughout the entire 39 ka. The BIT index record from the same core showed high BIT values during the glacial and low values during the Holocene. This indicates a more pronounced freshwater influence at the core location during the glacial, resulting in alkenones depleted in deuterium during that time and, thereby, explains the lack of a clear glacial-interglacial alkenone dD shift. Correlation between the BIT index and dDalkenone during the glacial period suggests that increased continental runoff potentially changed the growth conditions of the alkenone producing haptophytes, promoting coastal haptophyte species with generally more enriched dDalkenone values. We therefore suggest that the application of dDalkenone for reconstructing past salinity in coastal settings may be complicated by changes in the alkenone producing haptophyte community.

Building an index of well-being for children living in Ireland: conceptual, measurement and policy considerations

This study conceptualised and measured children’s well-being in Ireland and considered how such conceptualisations and approaches to the measurement of well-being might inform social policy for children and families living in Ireland. This research explored what is meant by children’s well-being and how it can be conceptualised and measured so as to reflect the multi-dimensionality of the concept. The study developed an index of well-being that was both theoretically and methodologically robust and could be meaningfully used to inform social policy developments for children and their families. For the first time, an index of well-being for children was developed using an explicitly articulated unifying theory of children’s well-being. Moreover, for the first time an index of wellbeing was developed for 13-year old children living in Ireland using data from Wave 2 of the national longitudinal study of children. The Structural Model of Child Well-being (SMCW), the theoretical framework that underpins the development of this study’s index, offers a comprehensive understanding of well-being. The SMCW builds on, and integrates, a range of already-established theories concerning children’s development, their agency, rights and capabilities into a unifying theory that explains well-being in its entirety. This conceptualisation of well-being moves beyond the narrow focus on child development adopted in some recent studies of children’s well-being and which perpetuate individualised and self-responsibilising conceptualisations of well-being. This study found that the SMCW can be meaningfully applied, both theoretically and operationally, to the construction of an index of well-being for children. While it was not the purpose of this study to validate the SMCW, in the process of developing the index, I concluded that there was a theoretical ‘fit’ between the conceptual orientation of the SMCW and the wider children’s well-being literature. The ‘nested’ structure of the SMCW facilitated the identification of domains, sub-domains and indicators of well-being reflecting typical conventions of index construction. The findings from the resulting index, in both its categorical and continuous forms, demonstrated how a comprehensive theory of well-being can be used to illustrate how children are faring and which children are experiencing poorer or better well-being. Furthermore, this study demonstrated how the SMCW and the resultant index can be meaningfully used to support the implementation and review of the national policy framework for children and young people in Ireland.

Dissolution index of Globigerina bulloides in recent and Last Glacial Maximum sediments

The modern Atlantic Ocean, dominated by the interactions of North Atlantic Deep Water (NADW) and Antarctic Bottom Water (AABW), plays a key role in redistributing heat from the Southern to the Northern Hemisphere. In order to reconstruct the evolution of the relative importance of these two water masses, the NADW/AABW transition, reflected by the calcite lysocline, was investigated by the Globigerina bulloides dissolution index (BDX?). The depth level of the Late Glacial Maximum (LGM) calcite lysocline was elevated by several hundred metres, indicating a more corrosive water mass present at modern NADW level. Overall, the small range of BDX? data and the gradual decrease in preservation below the calcite lysocline point to a less stratified Atlantic Ocean during the LGM. Similar preservation patterns in the West and East Atlantic demonstrate that the modern west-east asymmetry did not exist due to an expansion of southern deep waters compensating for the decrease in NADW formation.

Stable isotope record and aklenonen index of MIS 11 sediments

The interglacial known as Marine Isotope Stage 11 has been proposed to be analogous to the Holocene, owing to similarities in the amplitudes of orbital forcing. It has been difficult to compare the periods, however, because of the long duration of Stage 11 and a lack of detailed knowledge of any extreme climate events that may have occurred. Here we use the distinctive phasing between seasurface temperatures and the oxygen-isotope records of benthic foraminifera in the southeast Atlantic Ocean to stratigraphically align the Holocene interglacial with the first half of the Marine Isotope Stage 11 interglacial optimum. This alignment suggests that the second half of Marine Isotope Stage 11 should not be used as a reference for 'pre-anthropogenic' greenhouse-gas emissions. By compiling benthic carbon-isotope records from sites in the Atlantic Ocean on a single timescale, we also find that meridional overturning circulation strengthened about 415,000 years ago, at a time of high orbital obliquity. We propose that this mechanism transported heat to the high northern latitudes, inhibiting significant ice-sheet build-up and prolonging interglacial conditions. We suggest that this mechanism may have also prolonged other interglacial periods throughout the past 800,000 years.

G. bulloides dissolution index of surface sediments

The Atlantic is regarded as a huge carbonate depocenter due to an on average deep calcite lysocline. However, calculations and models that attribute the calcite lysocline to the critical undersaturation depth (hydrographic or chemical lysocline) and not to the depth at which significant calcium carbonate dissolution is observed (sedimentary calcite lysocline) strongly overestimate the preservation potential of calcareous deep-sea sediments. Significant calcium carbonate dissolution is expected to begin firstly below 5000 m in the deep Guinea and Angola Basin and below 4400 m in the Cape Basin. Our study that is based on different calcium carbonate dissolution stages of the planktic foraminifera Globigerina bulloides clearly shows that it starts between 400 and 1600 m shallower depending on the different hydrographic settings of the South Atlantic Ocean. In particular, coastal areas are severely affected by increased supply of organic matter and the resultant production of metabolic CO2 which seems to create microenvironments favorable for dissolution of calcite well above the hydrographic lysocline.

Calcite saturation and dissolution index of core-top sediment samples from the Ontong Java Plateau, Mid-Atlantic Ridge, the Caribbean and the Ceara Rise, the Indian Ocean, the Ninety-East Ridge and from the east of Madagascar

X-ray computed tomography (CT) provides an insight into the progression of dissolution in the tests of planktonic foraminifera. Four species of foraminifera (G. ruber [white], G. sacculifer, N. dutertrei and P. obliquiloculata) from Pacific, Atlantic and Indian Ocean core-top samples were examined by CT and SEM. Inner chamber walls began to dissolve at Delta[CO3**2-] values of 12-14 µmol/kg. Close to the calcite saturation horizon, dissolution and precipitation of calcite may occur simultaneously. Inner calcite of G. sacculifer, N. dutertrei and P. obliquiloculata from such sites appeared altered or replaced, whereas outer crust calcite was dense with no pores. Unlike the other species, there was no distinction between inner and outer calcite in CT scans of G. ruber. Empty calcite crusts of N. dutertrei and P. obliquiloculata were most resistant to dissolution and were present in samples where Delta[CO3**2-] ~ -20 µmol/kg. Five stages of preservation were identified in CT scans, and an empirical dissolution index, XDX, was established. XDX appears to be insensitive to initial test mass. Mass loss in response to dissolution was similar between species and sites at ~ 0.4 µg/µmol/kg. We provide calibrations to estimate Delta[CO3**2-] and initial test mass from XDX.

Usage-Based versus Measure-Based Unit Pricing: Is There a Better Index of Value?

In many product categories, unit prices facilitate price comparisons across brands and package sizes; this enables consumers to identify those products that provide the greatest value. However in other product categories, unit prices may be confusing. This is because there are two types of unit pricing, measure-based and usage-based. Measure-based unit prices are what the name implies; price is expressed in cents or dollars per unit of measure (e.g. ounce). Usage-based unit prices, on the other hand, are expressed in terms of cents or dollars per use (e.g., wash load or serving). The results of this study show that in two different product categories (i.e., laundry detergent and dry breakfast cereal), measure-based unit prices reduced consumers’ ability to identify higher value products, but when a usage-based unit price was provided, their ability to identify product value was increased. When provided with both a measure-based and a usage-based unit price, respondents did not perform as well as when they were provided only a usage-based unit price, additional evidence that the measure-based unit price hindered consumers’ comparisons. Finally, the presence of two potential moderators, education about the meaning of the two measures and having to rank order the options in the choice set in terms of value before choosing, did not eliminate these effects.

Developing an index of dietary estimation of fermentable carbohydrate to allow dietary analysis for epidemiological studies

It has been proposed that long-term consumption of diets rich in non-digestible carbohydrates (NDCs), such as cereals, fruit and vegetables might protect against several chronic diseases, however, it has been difficult to fully establish their impact on health in epidemiology studies. The wide range properties of the different NDCs may dilution their impact when they are combined in one category for statistical comparisons in correlations or multivariate analysis. Several mechanisms have been suggested to explain the protective effects of NDCs, including increased stool bulk, dilution of carcinogens in the colonic lumen, reduced transit time, lowering pH, and bacterial fermentation to short chain fatty acids (SCFA) in the colon. However, it is very difficult to measure SCFA in humans in vivo with any accuracy, so epidemiological studies on the impact of SCFA are not feasible. Most studies use dietary fibre (DF) or Non-Starch Polysaccharides (NSP) intake to estimate the levels, but not all fibres or NSP are equally fermentable. It has been proposed that long-term consumption of diets rich in non-digestible carbohydrates (NDCs), such as cereals, fruit and vegetables might protect against several chronic diseases, however, it has been difficult to fully establish their impact on health in epidemiology studies. The wide range properties of the different NDCs may dilution their impact when they are combined in one category for statistical comparisons in correlations or multivariate analysis. Several mechanisms have been suggested to explain the protective effects of NDCs, including increased stool bulk, dilution of carcinogens in the colonic lumen, reduced transit time, lowering pH, and bacterial fermentation to short chain fatty acids (SCFA) in the colon. However, it is very difficult to measure SCFA in humans in vivo with any accuracy, so epidemiological studies on the impact of SCFA are not feasible. Most studies use dietary fibre (DF) or Non-Starch Polysaccharides (NSP) intake to estimate the levels, but not all fibres or NSP are equally fermentable. The first aim of this thesis was the development of the equations used to estimate the amount of FC that reaches the human colon and is fermented fully to SCFA by the colonic bacteria. Therefore, several studies were examined for evidence to determine the different percentages of each type of NDCs that should be included in the final model, based on how much NDCs entered the colon intact and also to what extent they were fermented to SCFA in vivo. Our model equations are FC-DF or NSP$ 1: 100 % Soluble + 10 % insoluble + 100 % NDOs¥ + 5 % TS** FC-DF or NSP 2: 100 % Soluble + 50 % insoluble + 100 % NDOs + 5 % TS FC-DF* or NSP 3: 100 % Soluble + 10 % insoluble + 100 % NDOs + 10 % TS FC-DF or NSP 4: 100 % Soluble + 50 % insoluble + 100 % NDOs + 10 % TS *DF: Dietary fibre; **TS: Total starch; $NSP: non-starch polysaccharide; ¥NDOs: non-digestible oligosaccharide The second study of this thesis aimed to examine all four predicted FC-DF and FC-NSP equations developed, to estimate FC from dietary records against urinary colonic NDCs fermentation biomarkers. The main finding of a cross-sectional comparison of habitual diet with urinary excretion of SCFA products, showed weak but significant correlation between the 24 h urinary excretion of SCFA and acetate with the estimated FC-DF 4 and FC-NSP 4 when considering all of the study participants (n = 122). Similar correlations were observed with the data for valid participants (n = 78). It was also observed that FC-DF and FC-NSP had positive correlations with 24 h urinary acetate and SCFA compared with DF and NSP alone. Hence, it could be hypothesised that using the developed index to estimate FC in the diet form dietary records, might predict SCFA production in the colon in vivo in humans. The next study in this thesis aimed to validate the FC equations developed using in vitro models of small intestinal digestion and human colon fermentation. The main findings in these in vitro studies were that there were several strong agreements between the amounts of SCFA produced after actual in vitro fermentation of single fibre and different mixtures of NDCs, and those predicted by the estimated FC from our developed equation FC-DF 4. These results which demonstrated a strong relationship between SCFA production in vitro from a range of fermentations of single fibres and mixtures of NDCs and that from the predicted FC equation, support the use of the FC equation for estimation of FC from dietary records. Therefore, we can conclude that the newly developed predicted equations have been deemed a valid and practical tool to assess SCFA productions for in vitro fermentation.

Endoluminal calprotectin measurement in assessment of pouchitis and a new index of disease activity: a pilot study

Pouchitis is the most common complication following proctocolectomy with ileal pouch-anal anastomosis for ulcerative colitis (UC). To provide a standardized definition of pouchitis clinical, endoscopic and histological markers were grouped and weighted in the pouch disease activity index (PDAI). However, the delay in the assessment of the final score due to the time requested for histological analysis remains the main obstacle to the index implementation in clinical practice so that the use of modified-PDAI (mPDAI) with exclusion of histologic subscore has been proposed. We tested the ability of calprotectin measurement in the pouch endoluminal content to mimic the histologic score as defined in the PDAI, the index that we adopted as gold standard for pouchitis diagnosis. Calprotectin was measured by ELISA in the pouch endoluminal content collected during endoscopy in 40 consecutive patients with J-pouch. In each patient PDAI and mPDAI were calculated and 15% of patients were erroneously classified by mPDAI. ROC analysis of calprotectin values vs. acute histological subscore ≥ 3 identified different calprotectin cut-off values with corresponding sensitivity and specificity allowing the definition and scoring of different range of calprotectin subscores. We incorporated the calprotectin score in the mPDAI obtaining a new score that shows the same specificity as PDAI for diagnosis of pouchitis and higher sensitivity when compared with mPDAI. The use of the proposed new score, once validated in a larger series of patients, might be useful in the early management of patients with symptoms of pouchitis.