(Table 2, page 1376) Chemical analyses of manganese nodules and crusts from the South-western Pacific

Phosphate deposits which apparently formed during the Miocene climatic optimum are widespread on the Chatham Rise and Camp bell Plateau, and on seamounts in the north Tasman Sea. They formed under oxidising conditions by the phosphatisation of older or contemporaneous foraminiferal oozes (Campbell Plateau and Chatham Rise) and coral limestones (Tasman Sea). The phosphorites of the rise and plateau were formed where current activity was sufficiently strong to prevent normal sedimentation, and now form lag deposits. After the Miocene, phosphorite formation ceased and was followed by manganese oxide deposition where conditions were highly oxidising on the eastern Campbell Plateau and north Tasman seamounts, and by glauconite formation in the much less oxidising environments of the western Campbell Plateau and the Chat ham Rise. The manganese deposits are not volcanogenic, as was formerly thought, but formed by slow precipitation from well oxygenated sea water.

Middle Miocene evolution and stable isotope ratios of Globorotalia (Fohsella) in the western equatorial Pacific

Evolution of the planktic foraminiferal lineage Globorotalia (Fohsella) occurred during the Miocene between 23.7 and 11.8 Ma and forms the basis for stratigraphic subdivision of the early middle Miocene (Zones N 10 through N 12). Important morphologic changes within the G. (Fohsella) lineage included a marked increase in test size, a transition from a rounded to an acute periphery, and the development of a keel in later forms. We found that the most rapid changes in morphology of G. (Fohsella) occurred between 13 and 12.7 Ma and coincided with an abrupt increase in the delta18O ratios of shell calcite. Comparison of isotopic results of G. (Fohsella) with other planktic foraminifers indicate that delta18O values of the lineage diverge from surface-dwelling species and approach deep-dwelling species after 13.0 Ma, indicating a change in depth habitat from the surface mixed layer to intermediate depth near the thermocline. Isotopic and faunal evidence suggests that this change in depth stratification was associated with an expansion of the thermocline in the western equatorial Pacific. After adapting to a deeper water habitat at 13.0 Ma, the G. (Fohsella) lineage became extinct abruptly at 11.8 Ma during a period when isotopic and faunal evidence suggest a shoaling of the thermocline. Following the extinction of G. (Fohsella), the ecologic niche of the lineage was filled by the Globorotalia (Menardella) group, which began as a deep-water form and later evolved to an intermediate-water habitat. We suggest that the evolution of G. (Fohsella) and G. (Menardella) were tightly linked to changes in the structure of the thermocline in the western equatorial Pacific.

Strength of the Iberian intraplate lithosphere: Cenozoic deformations and seismicity

Previous studies about the strength of the lithosphere in the Iberia centre fail to resolve the depth of earthquakes because of the rheological uncertainties. Therefore, new contributions are considered (the crustal structure from a density model) and several parameters (tectonic regime, mantle rheology, strain rate) are checked in this paper to properly examine the role of lithospheric strength in the intraplate seismicity and the Cenozoic evolution. The strength distribution with depth, the integrated strength, the effective elastic thickness and the seismogenic thickness have been calculated by a finite element modelling of the lithosphere across the Central System mountain range and the bordering Duero and Madrid sedimentary basins. Only a dry mantle under strike-slip/extension and a strain rate of 10-15 s-1, or under extension and 10-16 s-1, causes a strong lithosphere. The integrated strength and the elastic thickness are lower in the mountain chain than in the basins. These anisotropies have been maintained since the Cenozoic and determine the mountain uplift and the biharmonic folding of the Iberian lithosphere during the Alpine deformations. The seismogenic thickness bounds the seismic activity in the upper–middle crust, and the decreasing crustal strength from the Duero Basin towards the Madrid Basin is related to a parallel increase in Plio–Quaternary deformations and seismicity. However, elasto–plastic modelling shows that current African–Eurasian convergence is resolved elastically or ductilely, which accounts for the low seismicity recorded in this region.

Anatomy and variability of "Cuvierichelys parisiensis", a geoemydid turtle that crosses the Eocene-Oligocene boundary in Belgium

Abundant material of turtles from the early Oligocene site of Boutersem-TGV (Boutersem, Belgium), is presented here. No information on the turtles found there was so far available. All the turtle specimens presented here are attributable to a single freshwater taxon that is identified as a member of Geoemydidae, Cuvierichelys. It is the first representative of the ‘Palaeochelys s. l.–Mauremys’ group recognized in the Belgian Paleogene record. This material, which allows to know all the elements of both the carapace and the plastron of the taxon, cannot be attributed to the only species of the genus Cuvierichelys so far identified in the Oligocene, the Spanish form Cuvierichelys iberica. The taxon from Boutersem is recognized as Cuvierichelys parisiensis. Thus, both the paleobiogeographic and the biostratigraphic distributions of Cuvierichelys parisiensis are extended, its presence being confirmed for the first time outside the French Eocene record. The validity of some European forms is refuted, and several characters previously proposed as different between Cuvierichelys iberica and Cuvierichelys parisiensis are recognized as subjected to intraspecific variability.

Temporal differences across a bio-geographical boundary reveal slow response of sub-littoral benthos to climate change

The English Channel is located at the biogeographical boundary between the northern Boreal and southern Lusitanian biozones and therefore represents an important area to study the effects of global warming on marine organisms. While the consequences of climatic change in the western English Channel have been relatively well documented for fish, plankton and inter-tidal benthic communities, data highlighting the same effects on the distribution of sub-littoral benthic organisms does, to date, not exist. The present study resurveyed a subset of sites originally surveyed from 1958 to 1959 along the UK coast of the English Channel. The main aims of this resurvey were to describe the present status of benthic communities and to investigate potential temporal changes, in particular distributional changes in western stenothermal ‘cold’ water and southern Lusitanian ‘warm’ water species. The increase in water temperature observed since the historic survey was predicted to have caused a contraction in the distribution of cold water species and an extension in the distribution of warm water species. The temporal comparison did not show any clear broad-scale distributional changes in benthic communities consistent with these predictions. Nevertheless, 2 warm water species, the sting winkle Ocenebra erinacea and the introduced American slipper limpet Crepidula fornicata, did show range extensions and increased occurrence, possibly related to climatic warming. Similarly, warm water species previously not recorded by the historic survey were found. The absence of broad-scale temporal differences in sub-tidal communities in response to climatic warming has been reported for other areas and may indicate that these communities respond far more slowly to environmental changes compared to plankton, fish and inter-tidal organisms.

Temporal differences across a bio-geographical boundary reveal slow response of sub-littoral benthos to climate change

The English Channel is located at the biogeographical boundary between the northern Boreal and southern Lusitanian biozones and therefore represents an important area to study the effects of global warming on marine organisms. While the consequences of climatic change in the western English Channel have been relatively well documented for fish, plankton and inter-tidal benthic communities, data highlighting the same effects on the distribution of sub-littoral benthic organisms does, to date, not exist. The present study resurveyed a subset of sites originally surveyed from 1958 to 1959 along the UK coast of the English Channel. The main aims of this resurvey were to describe the present status of benthic communities and to investigate potential temporal changes, in particular distributional changes in western stenothermal ‘cold’ water and southern Lusitanian ‘warm’ water species. The increase in water temperature observed since the historic survey was predicted to have caused a contraction in the distribution of cold water species and an extension in the distribution of warm water species. The temporal comparison did not show any clear broad-scale distributional changes in benthic communities consistent with these predictions. Nevertheless, 2 warm water species, the sting winkle Ocenebra erinacea and the introduced American slipper limpet Crepidula fornicata, did show range extensions and increased occurrence, possibly related to climatic warming. Similarly, warm water species previously not recorded by the historic survey were found. The absence of broad-scale temporal differences in sub-tidal communities in response to climatic warming has been reported for other areas and may indicate that these communities respond far more slowly to environmental changes compared to plankton, fish and inter-tidal organisms.

GIS technologies and spatial organization patterns among hunter-gatherers: an archaeological case study from Southern Patagonia (southern South America)

This paper discusses some aspects of hunter-gatherer spatial organization in southern South Patagonia, in later times to 10,000 cal yr BP. Various methods of spatial analysis, elaborated with a Geographic Information System (GIS) were applied to the distributional pattern of archaeological sites with radiocarbon dates. The shift in the distributional pattern of chronological information was assessed in conjunction with other lines of evidence within a biogeographic framework. Accordingly, the varying degrees of occupation and integration of coastal and interior spaces in human spatial organization are explained in association with the adaptive strategies hunter-gatherers have used over time. Both are part of the same human response to changes in risk and uncertainty variability in the region in terms of resource availability and environmental dynamics.

A cross-sectional evaluation of community pharmacists’ perceptions of intermediate care and medicines management across the healthcare interface

Background Despite the importance placed on the concept of the multidisciplinary team in relation to intermediate care (IC), little is known about community pharmacists’ (CPs) involvement. 
Objective To determine CPs’ awareness of and involvement with IC services, perceptions of the transfer of patients’ medication information between healthcare settings and views of the development of a CP–IC service. 
Setting Community pharmacies in Northern Ireland. 
Methods A postal questionnaire, informed by previous qualitative work was developed and piloted. 
Main outcome measure CPs’ awareness of and involvement with IC. Results The response rate was 35.3 % (190/539). Under half (47.4 %) of CPs ‘agreed/strongly agreed’ that they understood the term ‘intermediate care’. Three quarters of respondents were either not involved or unsure if they were involved with providing services to IC. A small minority (1.2 %) of CPs reported that they received communication regarding medication changes made in hospital or IC settings ‘all of the time’. Only 9.5 and 0.5 % of respondents ‘strongly agreed’ that communication from hospital and IC, respectively, was sufficiently detailed. In total, 155 (81.6 %) CPs indicated that they would like to have greater involvement with IC services. ‘Current workload’ was ranked as the most important barrier to service development.
Conclusion It was revealed that CPs had little awareness of, or involvement with, IC. Communication of information relating to patients’ medicines between settings was perceived as insufficient, especially between IC and community pharmacy settings. CPs demonstrated willingness to be involved with IC and services aimed at bridging the communication gap between healthcare settings.

Generations and intention to leave current job : Belgian nurses in the workplace

This master thesis aims to identify work-related factors making Belgian nurses consider leaving their job voluntary and to compare the work-related factors across different generations. The purpose of this master thesis has a descriptive nature of research. The research approach chosen is a deductive approach and the research design chosen is a quantitative research design. Cluster sampling in combination with simple random sampling was used as sampling technique. 128 nurses were surveyed from April to May 2016. Nurses who reported to leave the organization due to retirement reasons, temporary employment contract or maternity leave were excluded from the study as this study investigates the voluntary turnover intention. A total of 68 nurses were included in the study which indicates an overall response rate of 53 %. Numerous of the findings in this master thesis are consistent with previous studies on turnover intention of different generations in other western-countries than Belgium. The work-related factor workload was most often reported by Belgian nurses with no intention to leave their job. Belgian nurses with an intention to leave their job indicated most often the work-related factor (non-)financial benefits. The generation-specific findings indicated both similarities and differences between the work-related factors selected. It was observed that Baby Boomers with an intention to leave their job selected most often variables related to the work-related factors (non-)financial benefits, supportive organization and workload. The variable lack of recognition appeared among Baby Boomers with an intention and no intention to leave their job. Surprisingly was the often selected variables lack of direct and/clear feedback on performances and unsupportive supervisor among Baby Boomers with professional turnover intention. Further, it was observed that Generation Xers with an intention to leave their job selected most often variables related to the work-related factors supportive organization, communication, (non-)financial benefits, work content and workload. The variables inadequate opportunity for advancement/professional growth and imbalance work-life appeared among Generation Xers with an intention and no intention to leave their job. Generation Yers with an intention to leave their job selected most frequently variables related to the work-related factors (non-)financial benefits, workload and commitment. The variables inadequate salary and opportunities elsewhere appeared among nurses with an intention and no intention to leave their job. Surprisingly was the often selected variable inadequate salary among Generation Yers with professional turnover intention.

Herd management and livestock productivity in the Altai region of Western Mongolia

This thesis analyses the influence of qualitative and quantitative herbage production on seasonal rangelands, and of herd and pasture use strategies on feed intake, body mass development and reproductive performance of sheep and goats in the Altai mountain region of Bulgan county (soum) in Khovd province (aimag). This westernmost county of Mongolia is characterized by a very poor road network and thus very difficult access to regional and national markets. The thesis explores in this localized context the current rural development, the economic settings and political measures that affect the traditional extensive livestock husbandry system and its importance for rural livelihoods. Livestock management practices still follow the traditional transhumant mode, fully relying on natural pasture. This renders animal feeding very vulnerable to the highly variable climatic conditions which is one of many reasons for gradually declining quantity and quality of pasture vegetation. Small ruminants, and especially goats, are the main important species securing economic viability of their owners’ livelihood, and they are well adapted to the harsh continental climate and the present low input management practices. It is likely that small ruminants will keep their vital role for the rural community in the future, since the weak local infrastructure and slow market developments currently do not allow many income diversification options. Since the profitability of a single animal is low, animal numbers tend to increase, whereas herd management does not change. Possibilities to improve the current livestock management and thus herders’ livelihoods in an environmentally, economically and socially sustainable manner are simulated through bio-economic modelling and the implications are discussed at the regional and national scale. To increase the welfare of the local population, a substantial infrastructural and market development is needed, which needs to be accompanied by suitable pasture management schemes and policies

Investigation of the Nucleation and Growth of Colloidal Indium Phosphide: from Molecular Precursors to Semiconductor Nanocrystals through In37P20(O2CR)51 as a Magic-Size Intermediate

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

Muscle Dysmorphia: Current Insights

Since 1997, there has been increasing research focused on Muscle Dysmorphia, a condition underpinned by people’s beliefs they have insufficient muscularity, in both the Western and non-western medical and scientific communities. Much of this empirical interest has surveyed nonclinical samples, and there is limited understanding of people with the condition beyond knowledge about their characteristics. Much existing knowledge about people with the condition is unsurprising and inherent in the definition of the disorder, such as dissatisfaction with muscularity and adherence to muscle-building activities. Only recently have investigators started to explore questions beyond these limited tautological findings that may give rise to substantial knowledge advances, such as the examination of masculine and feminine norms. There is limited understanding of additional topics such as etiology, prevalence, nosology, prognosis, and treatment. Further, the evidence is largely based on a small number of unstandardized case reports and descriptive studies (involving small samples), largely confined to Western (North American, British, and Australian) males. Although much research has been undertaken since the term Muscle Dysmorphia entered the psychiatric lexicon in 1997, there remains tremendous scope for knowledge advancement. A primary task in the short term is for investigators to examine the extent that the condition exists among well-defined populations to help determine the justification for research funding relative to other public health issues. A greater variety of research questions and designs may contribute to a broader and more robust knowledge base than currently exists. Future work will help clinicians assist a group of people whose quality of life and health is placed at risk by their muscular preoccupation.

Functional alkali tantalate 2D structures for microelectronics and related applications

Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.

Electrolytes for ceramic oxide fuel cells

The main objective of this dissertation is the development and processing of novel ionic conducting ceramic materials for use as electrolytes in proton or oxide-ion conducting solid oxide fuel cells. The research aims to develop new processing routes and/or materials offering superior electrochemical behavior, based on nanometric ceramic oxide powders prepared by mechanochemical processes. Protonic ceramic fuel cells (PCFCs) require electrolyte materials with high proton conductivity at intermediate temperatures, 500-700ºC, such as reported for perovskite zirconate oxides containing alkaline earth metal cations. In the current work, BaZrO3 containing 15 mol% of Y (BZY) was chosen as the base material for further study. Despite offering high bulk proton conductivity the widespread application of this material is limited by its poor sinterability and grain growth. Thus, minor additions of oxides of zinc, phosphorous and boron were studied as possible sintering additives. The introduction of ZnO can produce substantially enhanced densification, compared to the un-doped material, lowering the sintering temperature from 1600ºC to 1300ºC. Thus, the current work discusses the best solid solution mechanism to accommodate this sintering additive. Maximum proton conductivity was shown to be obtained in materials where the Zn additive is intentionally adopted into the base perovskite composition. P2O5 additions were shown to be less effective as a sintering additive. The presence of P2O5 was shown to impair grain growth, despite improving densification of BZY for intermediate concentrations in the range 4 – 8 mol%. Interreaction of BZY with P was also shown to have a highly detrimental effect on its electrical transport properties, decreasing both bulk and grain boundary conductivities. The densification behavior of H3BO3 added BaZrO3 (BZO) shows boron to be a very effective sintering aid. Nonetheless, in the yttrium containing analogue, BaZr0.85Y0.15O3- (BZY) the densification behavior with boron additives was shown to be less successful, yielding impaired levels of densification compared to the plain BZY. This phenomenon was shown to be related to the undesirable formation of barium borate compositions of high melting temperatures. In the last section of the work, the emerging oxide-ion conducting materials, (Ba,Sr)GeO3 doped with K, were studied. Work assessed if these materials could be formed by mechanochemical process and the role of the ionic radius of the alkaline earth metal cation on the crystallographic structure, compositional homogeneity and ionic transport. An abrupt jump in oxide-ion conductivity was shown on increasing operation temperature in both the Sr and Ba analogues.

AN EXAMINATION OF HYDROXYL RADICAL: OUR CURRENT UNDERSTANDING OF THE OXIDATIVE CAPACITY OF THE TROPOSPHERE THROUGH EMPIRICAL, BOX, AND GLOBAL MODELING APPROACHES

Hydroxyl radical (OH) is the primary oxidant in the troposphere, initiating the removal of numerous atmospheric species including greenhouse gases, pollutants that are detrimental to human health, and ozone-depleting substances. Because of the complexity of OH chemistry, models vary widely in their OH chemistry schemes and resulting methane (CH4) lifetimes. The current state of knowledge concerning global OH abundances is often contradictory. This body of work encompasses three projects that investigate tropospheric OH from a modeling perspective, with the goal of improving the tropospheric community’s knowledge of the atmospheric lifetime of CH4. First, measurements taken during the airborne CONvective TRansport of Active Species in the Tropics (CONTRAST) field campaign are used to evaluate OH in global models. A box model constrained to measured variables is utilized to infer concentrations of OH along the flight track. Results are used to evaluate global model performance, suggest against the existence of a proposed “OH Hole” in the tropical Western Pacific, and investigate implications of high O3/low H2O filaments on chemical transport to the stratosphere. While methyl chloroform-based estimates of global mean OH suggest that models are overestimating OH, we report evidence that these models are actually underestimating OH in the tropical Western Pacific. The second project examines OH within global models to diagnose differences in CH4 lifetime. I developed an approach to quantify the roles of OH precursor field differences (O3, H2O, CO, NOx, etc.) using a neural network method. This technique enables us to approximate the change in CH4 lifetime resulting from variations in individual precursor fields. The dominant factors driving CH4 lifetime differences between models are O3, CO, and J(O3-O1D). My third project evaluates the effect of climate change on global fields of OH using an empirical model. Observations of H2O and O3 from satellite instruments are combined with a simulation of tropical expansion to derive changes in global mean OH over the past 25 years. We find that increasing H2O and increasing width of the tropics tend to increase global mean OH, countering the increasing CH4 sink and resulting in well-buffered global tropospheric OH concentrations.