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1.  This study was performed to investigate a mechanism of heat exchange in sea turtles and how temperature and different acclimation time affects their metabolic rates.  In another part of this thesis I aimed to test the possibility of a correlation between dive duration and both metabolic rate and state of buoyancy known to be regulated via the gas volume in the lungs of Chelonian sea turtles. 2.  All experiments were conducted on captive loggerhead (<i>Caretta caretta) </i>and green turtles (<i>Chelonia mydas)</i> housed in a individual tanks with circulating seawater from the adjacent Gulf of Naples (Western Mediterranean). The total range of body masses of turtles used encompassed 2 to 60 kg. 3.  It was demonstrated, using Doppler ultrasound, that sea turtles change blood flow in their appendages in response to external cooling and heating. Although this was efficient to accelerate whole body warming and delay the cooling of the body, turtles eventually equilibrated their body temperatures with that of the surrounding water. 4.  The Q₁₀ effect on metabolic rate of sea turtles subject to acute exposure to varying temperatures was 1.3. However, during long term exposure to seasonally decreasing water temperatures turtles showed a more pronounced reducted of metabolic rate (O₁₀ = 5.4). Contemporaneously food intake and general activity were greatly reduced as well and dive durations increased.  Body temperatures showed the same seasonal trend as the decreasing water temperatures. 5. Oxygen consumption rates of individual turtles, measured over 24-h-periods, peaked at different times of the day and no specific dynamic action after feeding could be detected.

The declining summer Arctic sea ice is impacting cyclone-forcing of dynamic and thermodynamic processes in Arctic sea at different spatial and temporal scales throughout the annual cycle. A catalogue of daily synoptic weather types is generated for the southern Beaufort Sea, covering the period 1979 to 2011 using NCEP/NCAR reanalysis mean sea level pressure data, principle components and k-means cluster analyses. Synoptic type statistics are used to assess changes in atmospheric circulation characteristics, sea ice vorticity, and lead formation. Significant (p < 0.05) seasonal synoptic type frequency anomalies are revealed between 1979 – 1998 and 1999 – 2011, and indicate a stronger Beaufort high, and increased easterly wind forcing in autumn and winter. High rates of young ice production in November and December 2007 were linked to strong easterly wind forcing. A case study of the atmospheric boundary layer during a lead formation event (03 – 18 February 2008) revealed sensible heat fluxes between 0 – 80.14 W • m2 (13 February 2008). First-ever observations of a physical forcing mechanism between Arctic cyclones, the Arctic Ocean, and Arctic sea ice within the southern Beaufort Sea were observed on 06 September 2009. Large swells intruded into the multi-year pack ice, causing instantaneous widespread fracturing, and reduced the large (>1 km) parent ice floes to small (100 – 150 m diameter) floes. This process increased the ice floe perimeter exposed to the ocean by a factor of 4.5. Analysis of Radarsat-2 imagery showed that open water fractional area in the multi-year ice cover initially decreased from 3.7% to 2.7%, then increased to ~20% due to wind-forced divergence. 11.54 MJ • m-2 of additional energy was estimated for lateral melting as a result of the fracture event using radiation budgets prior to and following the event. Earlier occurrences of flexural fracture could hypothetically provide up to three times more additional energy for lateral melt. Furthermore, this process may increase the likelihood of storm-driven upwelling of ocean heat, thereby enhancing bottom melt in the ice cover. This process is therefore presented as a potentially powerful positive feedback process that may accelerate the loss of Arctic sea ice.

During the summers of 2007 and 2008, we determined net, new and regenerated primary production and phytoplankton biomass in Arctic and Sub-Arctic marine waters around North America. Carbon and nitrogen uptake rates were measured using the 15N and 13C tracer technique in 24-hr on-deck incubations, and phytoplankton biomass was determined by in vitro fluorometry. Average net primary production was highest in the north Bering and south Chukchi Seas (998 mg C m-2 d-1) and defined as primarily new production (f-ratio of 0.57), potentially indicating high particulate export from surface waters. Phytoplankton biomass was also high (39 mg chl a m-2) in this region and comprised mostly (61%) of cells >5 μm, supporting the conclusion of a high export system. Average net primary production was lowest in the Canada Basin (50 mg C m-2 d-1) with an f-ratio of 0.17 and characterized by low phytoplankton biomass (8 mg chl a m-2), comprised of mostly (19%) cells <5 μm. In much of the study area, the presence of ice cover appeared influential in affecting Arctic primary production patterns. Water column stratification in the wake of retreating sea ice produced conditions favorable to initiating seasonal blooms, which most likely terminated due to nutrient exhaustion. Areas characterized by persistent sea ice cover were particularly unproductive, most likely due to light limitation, and nutrient exhaustion due to reduced wind-mixing. These results indicate that primary production in Arctic and Sub-Arctic waters is highly variable, and provide an important baseline for future studies of phytoplankton dynamics in this rapidly changing region. / Graduate

Atomic spectrometric techniques such as ICP-MS offer exceptional sensitivity and multi-element capability for trace metal analysis but the formation of polyatomic ions (particularly below m/z = 80) can cause serious interferences. Such interfering species may be introduced via precursor atoms in atmospheric gases, the sample matrix or impurities in the reagents and gases. There is an environmental need to establish rapid multi-element methods of analysis for trace metals in environmental waters and the subsequent speciation of these trace elements. Natural waters, particularly those with a high dissolved solids content such as sea water are difficult to analyse directly by ICP techniques due to the sample matrix forming polyatomic ion interferences when using ICP-MS and matrix modification of the background when undertaking ICP-AES studies. This thesis describes the development of analytical methodologies involving on-line sample preconcentration and matrix removal for the determination of trace elements in natural waters and brines using ICP-MS and ICPAES detection for the determination of a suite of trace elements including cadmium, cobalt, copper, lead manganese, nickel, selenium and zinc. Chapter one summarises the techniques used for such analyses and a review of solid phases used for sample preconcentration and matrix removal is given. Chapter two describes the development of an on-line Fl-atomic spectrometric matrix elimination method for the determination of trace metals in the samples discussed. The method involved the chelation of the analytes onto a Metpac CC-1® IDA resin with the simultaneous removal of matrix ions, e.g. Na and CI. The method was successfully validated for the analysis of open ocean sea water and riverine water, and the application of FI-FAAS to the determination of Mn in riverwater using extended preconcentration times to improve sensitivity is described. The influence of sample matrix on the atomic emission of these trace analytes is also discussed. Chapter three describes the application of the developed method to the quantification of trace elements in produced water samples from the north sea oil and gas production fields. Results using FI-ICP-MS and FI-ICP-AES are compared, and a sample is digested using U.V. radiation in order to determine the amount of trace analytes bound to organic material. The influence of matrix concentration on analyte retention and column capacity is investigated, and data obtained from a series of breakthrough curves is used to predict the maximum breakthrough volumes of sample required before analyte is lost as the operating capacity of the column is exceeded, for samples of differing salinities. Chapter four describes the development of an in-situ method of preconcentration of a suite of trace elements using the column system described previously. In-situ preconcentration offers a number of advantages over traditional sample collection and preservation techniques and minimises the potential for sample contamination. The in-situ method involves the use of a battery powered preconcentration unit containing columns, reagents and suitable reagent and sample pumping facilities, and subsequent analysis of these samples in the laboratory by the use of FI-ICP-AES. The method is successfully validated using a coastal sea water certified reference material, and the method is applied to the determination of trace elements in a sample taken from the Tamar Estuary, Devon. Chapter five describes the development of an on-line FI preconcentration-HG-ICP-AES method for the speciation of inorganic selenium in water. Sample was preconcentrated on a Benson BA-XIO® exchange resin. On-line separation of Se(IV) and Se(VI) was achieved, and sensitivity was improved by the adoption of hydride generation prior to analysis for the determination of Se(IV). Se(VI) was determined after off-line pre-reduction to Se(IV). The method was tested by the determination of inorganic selenium in an SRM, NIST 1643C, Trace elements in water and results compared with previous work.

Palaeoecological data can provide key information on depositional environments. This may be critical to the interpretation of marine sedimentary cycles and the recognition of ancient cycles and sequences. Although many recent studies have attempted to combine palaeoecology and sequence stratigraphy, the sequence stratigraphic model is commonly used to provide a temporally constrained framework for the evaluation of ecological and evolutionary events. This study shows how palaeoecology can be used as a powerful tool in the development of sequence stratigraphic models. A palaeoecological study of three Lower Cretaceous successions (at Ericeira, Cascais, Cabo Espichel) from the southern part of the Lusitanian Basin, Portugal, provides a basis for this study. This palaeoecological analysis allowed the construction of a detailed picture of the effects of relative sea-level, and other environmental factors, on sedimentary succession evolution. The results of this palaeoecological analysis have been represented on a series of depositional facies trend diagrams. The depositional facies diagrams have then been used to develop the sequence stratigraphy of the southern part of the Lusitanian Basin. The study successions record the temporal changes, and along-strike variation, in the evolution of three mixed carbonate-siliciclastic systems. The base of all the successions represents the development of narrow shelf with minor wave reworking. Siliciclastics were introduced by sand and gravel-load river dominated deltas with little reworking of the sediment at the channel mouths. This was characterised by the development of a clastic beach-barrier at Ericeira and a 'cool-water' carbonate ramp at Cascais. At Cabo Espichel a coral biostrome developed where coral ecology was controlled by terrigenous sedimentation and turbidity. The upper part of the successions represent a change in the morphology of the basin. A broad, shallow, low energy carbonate shelf developed that dissipated wave energy. In the nearshore environment siliciclastics were prevalent. The shelf carbonates are characteristic of the 'cool-water' type carbonates of the Cretaceous Tethyan realm. The more proximal Ericeira and Cabo Espichel successions record the alternation between marginal marine siliciclastic and shallow-water marine carbonate environments. The Cascais succession is characterised by carbonate platforms with abundant coral and rudist bivalve faunas. Palaeoecological analysis and development of the depositional facies trend diagrams have allowed the identification of one mega-sequence (2nd order), six sequences (3rd order) and higher resolution sequences and parasequences (4th order). 2nd and 3rd order sequences are correlatable across the southern part of the Lusitanian Basin. They also correlate with previously published sequence chronostratigraphy for the Tethyan realm. The palaeoecological analysis indicates that 2nd and 3rd order sequences are controlled by allocyclic processes and that 4th order cycles (sequences and parasequences) were dominated by autocyclic processes. As a result 4th order cycles cannot be correlated across the basin. This study has shown that detailed palaeoecological analysis can reveal a detailed, and more accurate, picture of the controls on the development of a basin fill than sedimentology alone. Along with the depositional trend diagrams, these data can provide a powerful method for the development of a sequence stratigraphic model and aid to interpretation of a basin fill.

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