High-Resolution In Situ Oxygen-Argon Studies of Surface Biological and Physical Processes in the Polar Oceans

The Arctic Ocean and Western Antarctic Peninsula (WAP) are the fastest warming regions on the planet and are undergoing rapid climate and ecosystem changes. Until we can fully resolve the coupling between biological and physical processes we cannot predict how warming will influence carbon cycling and ecosystem function and structure in these sensitive and climactically important regions. My dissertation centers on the use of high-resolution measurements of surface dissolved gases, primarily O2 and Ar, as tracers or physical and biological functioning that we measure underway using an optode and Equilibrator Inlet Mass Spectrometry (EIMS). Total O2 measurements are common throughout the historical and autonomous record but are influenced by biological (net metabolic balance) and physical (temperature, salinity, pressure changes, ice melt/freeze, mixing, bubbles and diffusive gas exchange) processes. We use Ar, an inert gas with similar solubility properties to O2, to devolve distinct records of biological (O2/Ar) and physical (Ar) oxygen. These high-resolution measurements that expose intersystem coupling and submesoscale variability were central to studies in the Arctic Ocean, WAP and open Southern Ocean that make up this dissertation.

Key findings of this work include the documentation of under ice and ice-edge blooms and basin scale net sea ice freeze/melt processes in the Arctic Ocean. In the WAP O2 and pCO2 are both biologically driven and net community production (NCP) variability is controlled by Fe and light availability tied to glacial and sea ice meltwater input. Further, we present a feasibility study that shows the ability to use modeled Ar to derive NCP from total O2 records. This approach has the potential to unlock critical carbon flux estimates from historical and autonomous O2 measurements in the global oceans.

Studies in asymmetric and heterocyclic synthesis: I. chiral ketones II. Quinolones III. Trifluoromethylated pyrones

This thesis is split into three sections based on three different areas of research. In the first section, investigations into the α-alkylation of ketones using a novel chiral auxiliary is reported. This chiral auxiliary was synthesised containing a pyrrolidine ring in the chiral arm and was applied in the preparation of α-alkylated ketones which were obtained in up to 92% ee and up to 63% yield over two steps. Both 3-pentanone and propiophenone based ketones were used in the investigation with a variety of both alkyl and benzyl based electrophiles. The novel chiral auxiliary was also successful when applied to Michael and aldol reactions. A diamine precursor en route to the chiral auxiliary was also applied as an organocatalyst in a Michael reaction, with the product obtained in excellent enantioselectivity. In the second section, investigations into potential anti-quorum sensing molecules are reported. The bacteria Pseudomonas aeruginosa is an antibiotic-resistant pathogen that demonstrates cooperative behaviours and communicates using small chemical molecules in a process termed quorum sensing. A variety of C-3 analogues of the quorum sensing molecules used by P. aeruginosa were synthesised. Expanding upon previous research within the group, investigations were carried out into alternative protecting group strategies of 2-heptyl-4-(1H)- quinolone with the aim of improving the yields of products of cross-coupling reactions. In the third section, investigations into fluorination and trifluoromethylation of 2-pyrones, pyridones and quinolones is reported. The incorporation of a fluorine atom or a trifluoromethyl group into a molecule is important in pharmaceutical drug discovery programmes as it can lead to increased lipophilicity and bioavailability, however late-stage incorporation is rarely reported. Both direct fluorination and trifluoromethylation were attempted. Eight trifluoromethylated 2-pyrones, five trifluoromethylated 2-pyridones and a trifluoromethylated 2-quinolone were obtained in a late-stage synthesis from their respective iodinated precursors using methyl fluorosulfonyldifluoroacetate as a trifluoromethylating reagent.

Annotated record and chemical composition of Mn deposits from R/V Mahi Cruise Abyssal Hills 69 stations

A University of Hawaii oceanographic cruise, Abyssal Hills 69, with the R/V Mahi, was carried out to study the association of manganese nodules with an abyssal hill. Manganese nodules from three dredge hauls on an abyssal hill located at 36°W and 157°W exhibited differences in morphology and composition between stations only three miles apart. The morphology of the nodules suggests that nodules from a single site have similar morphologies because they began growth at the same time, probably because of a volcanic event. Differences in morphology between stations indicate a local supply of elements. Atomic absorption analysis for manganese, iron, cobalt, nickel, and copper revealed that nodules nearest to a probable fault line and source of volcanism have a, lower manganese to iron ratio than nodules farther removed. This finding supports the theory that volcanism contributes to the formation of some nodules. Additional evidence showing association with volcanism consists of volcanic nuclei in nodules, crusts formed on layers of volcanic ash, and basalt encrusted to various degrees. The variation in cobalt, nickel, and copper contents Gt the nodules from a single dredge is two-to threefold, but iron content is more uniiorm. Four of the six cores from the area increased in manganese concentration with depth, suggesting that diffusion is concentrating manganese in the upper zone of the sediments or in nodules. The author concludes that volcanism is contributing to the formation of nodules by supplying nuclei and transition elements, but is not necessary for the formation of manganese nodules.

(Table 4) Chemical composition of a hydrothermal body from the Red Sea rift zone

The main features of geological structures of ocean rift zones based on results of studies of the P.P. Shirshov Institute of Oceanology with use of manned submersibles "Pisces" are under consideration in the book. Multiyear experience of geological exploration in rift zones with the use of these submersibles is summarized. Methodology of underwater operations is described. The main structural features of the Red Sea and Gulf of Aden rifts as well as the rift zone of the Reykjanes Ridge are considered.

(Table 2, page 72) Chemical compositin of the two nodule types used in this investigation

Two Pacific Ocean manganese nodules, one from the ocean basin and one from a sea-mount, were examined in transmission electron microscopes at 100 and 650 kV. Of the many specimens examined, ten electron diffraction crystal spot patterns were identified. Sodium birnessite was observed six times and todorokite, Giavanoli's synthetic birnessite, hydrohausmanite and -Fe2O3 one time each. Ferric hydroxide was synthesized in the laboratory and shown to be the same as the primary iron mineral observed in the manganese nodules. The ferric hydroxide had a particle size range from 30 to 450 ?. Manganese oxide particles were frequently embedded in a mass of smaller ferric hydroxide particles.

Chemical composition of a manganese nodule from the Blake Plateau, Atlantic Ocean

The area surveyed during project AMC-11-67 was the portion of the Blake Plateau between latitude 30°00'N and 33°00'N and between the 100 to 1000 fathom curves. The survey was conducted from 3 October until 18 October 1967. Survey operations included dredgings, camera and multi-sensor lowerings. A collection of manganese and phosphate concretions as well as coral and sediment samples were examined by the ESSA(NOAA) Atlantic Oceanographic Laboratories. Chemical analyses were conducted at the NASA Manned Spacecraft Center, Houston by Richard A. Laidley for X-Ray Fluorescence Analysis and H. Costello for Atomic Absorption Analysis. Later the whole collection of samples was transferred to the Smithsonian National Museum of Natural History were it is available for study (see, http://mineralsciences.si.edu/collections.htm).

Madrepora oculata and Lophelia pertusa mass and 210Pb-226Ra chronology, Røst Reef, Norway, 2011

Here we show the use of the 210Pb-226Ra excess method to determine the growth rate of corals from one of the world's largest known cold-water coral reef, the Røst Reef off Norway. Two large branching framework-forming cold-water coral specimens, one Lophelia pertusa and one Madrepora oculata were collected alive at 350 m water depth from the Røst Reef at ~67° N and ~9° E. Pb and Ra isotopes were measured along the major growth axis of both specimens using low level alpha and gamma spectrometry and the corals trace element compositions were studied using ICP-QMS. Due to the different chemical behaviors of Pb and Ra in the marine environment, 210Pb and 226Ra were not incorporated the same way into the aragonite skeleton of those two cold-water corals. Thus to assess of the growth rates of both specimens we have here taken in consideration the exponential decrease of initially incorporated 210Pb as well as the ingrowth of 210Pb from the decay of 226Ra. Moreover a~post-depositional 210Pb incorporation is found in relation to the Mn-Fe coatings that could not be entirely removed from the oldest parts of the skeletons. The 226Ra activities in both corals were fairly constant, then assuming constant uptake of 210Pb through time the 210Pb-226Ra chronology can be applied to calculate linear growth rate. The 45.5 cm long branch of M. oculata reveals an age of 31 yr and a~linear growth rate of 14.4 ± 1.1 mm yr-1, i.e. 2.6 polyps per year. However, a correction regarding a remaining post-depositional Mn-Fe oxide coating is needed for the base of the specimen. The corrected age tend to confirm the radiocarbon derived basal age of 40 yr (using 14C bomb peak) with a mean growth rate of 2 polyps yr-1. This rate is similar to the one obtained in Aquaria experiments under optimal growth conditions. For the 80 cm-long specimen of L. pertusa a remaining contamination of metal-oxides is observed for the middle and basal part of the coral skeleton, inhibiting similar accurate age and growth rate estimates. However, the youngest branch was free of Mn enrichment and this 15 cm section reveals a growth rate of 8 mm yr-1 (~1 polyp every two to three years). However, the 210Pb growth rate estimate is within the lowermost ranges of previous growth rate estimates and may thus reflect that the coral was not developing at optimal growth conditions. Overall, 210Pb-226Ra dating can be successfully applied to determine the age and growth rate of framework-forming cold-water corals, however, removal of post-depositional Mn-Fe oxide deposits is a prerequisite. If successful, large branching M. oculata and L. pertusa coral skeletons provide unique oceanographic archive for studies of intermediate water environmentals with an up to annual time resolution and spanning over many decades.

Chemical composition and phytoplankton characteristics of water samples obtained during POLARSTERN cruise ANT-XXIV/3

The fixation of dissolved inorganic carbon (DIC) by marine phytoplankton provides an important feedback mechanism on concentrations of CO2 in the atmosphere. As a consequence it is important to determine whether oceanic primary productivity is susceptible to changing atmospheric CO2 levels Among numerous other factors, the acquisition of DIC by microalgae particularly in the polar seas is projected to have a significant effect on future phytoplanktonic production and hence atmospheric CO2 concentrations. Using the isotopic disequilibrium technique the contribution of different carbon species (CO2 and bicarbonate) to the overall DIC uptake and the extent to which external Carbonic Anhydrase (eCA) plays a role in facilitating DIC uptake was estimated. Simultaneous uptake of CO2 and HCO3- was observed in all cases, but the proportions in which different DIC species contributed to carbon assimilation varied considerably between stations. Bicarbonate as well as CO2 could be the major DIC source for local phytoplankton assemblages. There was a positive correlation between the contribution of CO2 to total DIC uptake and ambient concentration of CO2 in seawater suggesting that Southern Ocean microalgae could increase the proportion of CO2 uptake under future high atmospheric CO2 levels. Results will be discussed in view of metabolic costs related to DIC acquisition of Southern Ocean phytoplankton.

Physical oceanography and processed 2 minutes-averaged continuous VM-ADCP profiles during POLARSTERN cruise ANT-XXVIII/3

The physical and biological carbon pumps in the different hydrographic and biogeochemical regimes of the Atlantic Sector of the Southern Ocean are controlled by a series of coupled physical, chemical and biological processes and a project named Eddy-Pump was designed to study them. The Eddy Pump field campaign was carried out during RV Polarstern Cruise ANT-XXVIII/3 between January and March 2012. Particular emphasis was laid on the differences which occur along the axis of the Antarctic Circumpolar Current (ACC) with its associated mesoscale eddy field. The study sites were selected in order to represent (1) the central ACC with its regular separation in different frontal jets, investigated by a meridional transect along 10°E; (2) a large-scale bloom west of the Mid-Atlantic Ridge which lasted several months with conspicuous chlorophyll-poor waters to its immediate east studied by a three-dimensional mesoscale survey centred at 12°40'W; and (3) the Georgia Basin north of the island of South Georgia, which regularly features an extended and dense phytoplankton bloom, was investigated by a mesoscale survey centred at 38°12'W. While Eddy-Pump represents an interdisciplinary project by design, we here focus on describing the variable physical environment within which the different biogeochemical regimes developed. For describing the physical environment we use measurements of temperature, salinity and density, of mixed-layer turbulence parameters, of dynamic heights and horizontal current vectors, and of flow trajectories obtained from surface drifters and submerged floats. This serves as background information for the analyses of biological and chemical processes and of biogeochemical fluxes addressed by other papers in this issue. The section along 10°E between 44°S and 53°S showed a classical ACC structure with well-known hydrographic fronts, the Subantarctic Front (SAF) at 46.5°S, the Antarctic Polar Front (APF) split in two, at 49.25°S and 50.5°S, and the Southern Polar Front (SPF) at 52.5°S. Each front was associated with strong eastward flows. The West Mid-Atlantic Ridge Survey showed a weak and poorly resolved meander structure between the APF and the SPF. During the first eight days of the survey the oceanographic conditions at the Central Station at 12°40'W remained reasonably constant. However after that, conditions became more variable in the thermocline with conspicuous temperature inversions and interleavings and also a decrease in temperature in the surface layer. At the very end of the period of observation the conditions in the thermocline returned to being similar to those observed during the early part of the period with however the mixed layer temperature raised. The period of enhanced thermohaline variability was accompanied by increased currents. The Georgia Basin Survey showed a very strong zonal jet at its northern edge which connects to a large cyclonic meander that itself joins an anticyclonic eddy in the southeastern quadrant. The water mass contrasts in this survey were stronger than in the West Mid-Atlantic Ridge Survey, but similar to those met along 10°E with the exception that the warm and saline surface water typical of the northern side of the SAF was not covered by the Georgia Basin Survey. Mixed layers found during Eddy-Pump were typically deep, but varied between the three survey areas; the mean depths and standard variations of the mixed layer along the 10°E were 77.2±24.7 m, at the West Mid-Atlantic Ridge 66.7±17.7 m, and in the Georgia Basin 36.8±10.7 m.

Chemical composition of ferromanganese nodules from the Western Sicily Jurassic limestone beds

The stratigraphic study focuses on the description of lithofacies and geological sections of secondary, tertiary and quaternary formations in different parts of western Sicily. The tectonic analysis derived from field studies is used to trace the history and effects of the Alpine orogeny on the geology of Western Sicily. During his field study the author conducted several chemical element analysis on fossil manganese nodules extracted from Jurassic limestone beds.