Discriminant Sets of Families of Hyperbolic Polynomials of Degree 4 and 5

∗ Research partially supported by INTAS grant 97-1644

Global compilation of benthic data sets I

Approaches to quantify the organic carbon accumulation on a global scale generally do not consider the small-scale variability of sedimentary and oceanographic boundary conditions along continental margins. In this study, we present a new approach to regionalize the total organic carbon (TOC) content in surface sediments (<5 cm sediment depth). It is based on a compilation of more than 5500 single measurements from various sources. Global TOC distribution was determined by the application of a combined qualitative and quantitative-geostatistical method. Overall, 33 benthic TOC-based provinces were defined and used to process the global distribution pattern of the TOC content in surface sediments in a 1°x1° grid resolution. Regional dependencies of data points within each single province are expressed by modeled semi-variograms. Measured and estimated TOC values show good correlation, emphasizing the reasonable applicability of the method. The accumulation of organic carbon in marine surface sediments is a key parameter in the control of mineralization processes and the material exchange between the sediment and the ocean water. Our approach will help to improve global budgets of nutrient and carbon cycles.

Glacial North Atlantic: Sea surface conditions reconstructed by GLAMAP 2000

The response of the tropical ocean to global climate change and the extent of sea ice in the glacial nordic seas belong to the great controversies in paleoclimatology. Our new reconstruction of peak glacial sea surface temperatures (SSTs) in the Atlantic is based on census counts of planktic foraminifera, using the Maximum Similarity Technique Version 28 (SIMMAX-28) modern analog technique with 947 modern analog samples and 119 well-dated sediment cores. Our study compares two slightly different scenarios of the Last Glacial Maximum (LGM), the Environmental Processes of the Ice Age: Land, Oceans, Glaciers (EPILOG), and Glacial Atlantic Ocean Mapping (GLAMAP 2000) time slices. The comparison shows that the maximum LGM cooling in the Southern Hemisphere slightly preceeded that in the north. In both time slices sea ice was restricted to the north western margin of the nordic seas during glacial northern summer, while the central and eastern parts were ice-free. During northern glacial winter, sea ice advanced to the south of Iceland and Faeroe. In the central northern North Atlantic an anticyclonic gyre formed between 45° and 60°N, with a cool water mass centered west of Ireland, where glacial cooling reached a maximum of >12°C. In the subtropical ocean gyres the new reconstruction supports the glacial-to-interglacial stability of SST as shown by CLIMAP Project Members (CLIMAP) [1981]. The zonal belt of minimum SST seasonality between 2° and 6°N suggests that the LGM caloric equator occupied the same latitude as today. In contrast to the CLIMAP reconstruction, the glacial cooling of the tropical east Atlantic upwelling belt reached up to 6°-8°C during Northern Hemisphere summer. Differences between these SIMMAX-based and published U37[k]- and Mg/Ca-based equatorial SST records are ascribed to strong SST seasonalities and SST signals that were produced by different planktic species groups during different seasons.

Distribution of planktic foraminifera in surface sediments of the Atlantic Ocean

We present a data set of 738 planktonic foraminiferal species counts from sediment surface samples of the eastern North Atlantic and the South Atlantic between 87°N and 40°S, 35°E and 60°W including published Climate: Long-Range Investigation, Mapping, and Prediction (CLIMAP) data. These species counts are linked to Levitus's [1982] modern water temperature data for the four caloric seasons, four depth ranges (0, 30, 50, and 75 m), and the combined means of those depth ranges. The relation between planktonic foraminiferal assemblages and sea surface temperature (SST) data is estimated using the newly developed SIMMAX technique, which is an acronym for a modern analog technique (MAT) with a similarity index, based on (1) the scalar product of the normalized faunal percentages and (2) a weighting procedure of the modern analog's SSTs according to the inverse geographical distances of the most similar samples. Compared to the classical CLIMAP transfer technique and conventional MAT techniques, SIMMAX provides a more confident reconstruction of paleo-SSTs (correlation coefficient is 0.994 for the caloric winter and 0.993 for caloric summer). The standard deviation of the residuals is 0.90°C for caloric winter and 0.96°C for caloric summer at 0-m water depth. The SST estimates reach optimum stability (standard deviation of the residuals is 0.88°C) at the average 0- to 75-m water depth. Our extensive database provides SST estimates over a range of -1.4 to 27.2°C for caloric winter and 0.4 to 28.6°C for caloric summer, allowing SST estimates which are especially valuable for the high-latitude Atlantic during glacial times.

Investigation of N. pachyderma from the North Atlantic

The shells of the planktonic foraminifer Neogloboquadrina pachyderma have become a classical tool for reconstructing glacial-interglacial climate conditions in the North Atlantic Ocean. Palaeoceanographers utilize its left- and right-coiling variants, which exhibit a distinctive reciprocal temperature and water mass related shift in faunal abundance both at present and in late Quaternary sediments. Recently discovered cryptic genetic diversity in planktonic foraminifers now poses significant questions for these studies. Here we report genetic evidence demonstrating that the apparent 'single species' shell-based records of right-coiling N. pachyderma used in palaeoceanographic reconstructions contain an alternation in species as environmental factors change. This is reflected in a species-dependent incremental shift in right-coiling N. pachyderma shell calcite d18O between the Last Glacial Maximum and full Holocene conditions. Guided by the percentage dextral coiling ratio, our findings enhance the use of d18O records of right-coiling N. pachyderma for future study. They also highlight the need to genetically investigate other important morphospecies to refine their accuracy and reliability as palaeoceanographic proxies.

Compilation of 220 sediment core d13C data from the glacial Atlantic Ocean

We compare a compilation of 220 sediment core d13C data from the glacial Atlantic Ocean with three-dimensional ocean circulation simulations including a marine carbon cycle model. The carbon cycle model employs circulation fields which were derived from previous climate simulations. All sediment data have been thoroughly quality controlled, focusing on epibenthic foraminiferal species (such as Cibicidoides wuellerstorfi or Planulina ariminensis) to improve the comparability of model and sediment core carbon isotopes. The model captures the general d13C pattern indicated by present-day water column data and Late Holocene sediment cores but underestimates intermediate and deep water values in the South Atlantic. The best agreement with glacial reconstructions is obtained for a model scenario with an altered freshwater balance in the Southern Ocean that mimics enhanced northward sea ice export and melting away from the zone of sea ice production. This results in a shoaled and weakened North Atlantic Deep Water flow and intensified Antarctic Bottom Water export, hence confirming previous reconstructions from paleoproxy records. Moreover, the modeled abyssal ocean is very cold and very saline, which is in line with other proxy data evidence.

Epibenthic foraminiferal d13C in the Recent deep Arctic Ocean

Low planktic and benthic d18O and d13C values in sediments from the Nordic seas of cold stadials of the last glaciation have been attributed to brines, formed similar to modern ones in the Arctic Ocean. To expand on the carbon isotopes of this hypothesis I investigated benthic d13C from the modern Arctic Ocean. I show that mean d13C values of live epibenthic foraminifera from the deep Arctic basins are higher than mean d13C values of upper slope epibenthic foraminifera. This agrees with mean high d13C values of dissolved inorganic carbon (DIC) in Arctic Bottom Water (ABW), which are higher than mean d13CDIC values from shallower water masses of mainly Atlantic origin. However, adjustments for oceanic 13C-Suess depletion raise subsurface and intermediate water d13CDIC values over ABW d13CDIC ones. Accordingly, during preindustrial Holocene times, the d13CDIC of ABW was as high or higher than today, but lower than the d13CDIC of younger subsurface and intermediate water. If brine-enriched water significantly ventilated ABW, brines should have had high d13CDIC values. Analogously, high-d13CDIC brines may have been formed in the Nordic seas during warm interstadials. During cold stadials, when most of the Arctic Ocean was perennially sea-ice covered, a cessation of high-d13CDIC brine rejection may have lowered d13CDIC values of ABW, and ultimately the d13CDIC in Nordic seas intermediate and deep water. So, in contrast to the idea of enhanced brine formation during cold stadials, the results of this investigation imply that a cessation of brine rejection would be more likely.

Organic carbon accumulation in the South Atlantic Ocean

A compilation of 1118 surface sediment samples from the South Atlantic was used to map modern seafloor distribution of organic carbon content in this ocean basin. Using new data on Holocene sedimentation rates, we estimated the annual organic carbon accumulation in the pelagic realm (>3000 m water depth) to be approximately 1.8*10**12 g C/year. In the sediments underlying the divergence zone in the Eastern Equatorial Atlantic (EEA), only small amounts of organic carbon accumulate in spite of the high surface water productivity observed in that area. This implies that in the Eastern Equatorial Atlantic, organic carbon accumulation is strongly reduced by efficient degradation of organic matter prior to its burial. During the Last Glacial Maximum (LGM), accumulation of organic carbon was higher than during the mid-Holocene along the continental margins of Africa and South America (Brazil) as well as in the equatorial region. In the Eastern Equatorial Atlantic in particular, large relative differences between LGM and mid-Holocene accumulation rates are found. This is probably to a great extent due to better preservation of organic matter related to changes in bottom water circulation and not just a result of strongly enhanced export productivity during the glacial period. On average, a two- to three-fold increase in organic carbon accumulation during the LGM compared to mid-Holocene conditions can be deduced from our cores. However, for the deep-sea sediments this cannot be solely attributed to a glacial productivity increase, as changes in South Atlantic deep-water circulation seem to result in better organic carbon preservation during the LGM.

Star formation in a stellar mass-selected sample of galaxies to z=3 from the GOODS-NICMOS Survey

We present a study of the star-forming properties of a stellar mass-selected sample of galaxies in the GOODS (Great Observatories Origins Deep Survey) NICMOS Survey (GNS), based on deep Hubble Space Telescope (HST) imaging of the GOODS North and South fields. Using a stellar mass-selected sample, combined with HST/ACS and Spitzer data to measure both ultraviolet (UV) and infrared-derived star formation rates (SFRs), we investigate the star forming properties of a complete sample of ∼1300 galaxies down to log M_*= 9.5 at redshifts 1.5 < z < 3. Eight per cent of the sample is made up of massive galaxies with M_*≥ 10^11 M_⊙. We derive optical colours, dust extinctions and UV and infrared SFR to determine how the SFR changes as a function of both stellar mass and time. Our results show that SFR increases at higher stellar mass such that massive galaxies nearly double their stellar mass from star formation alone over the redshift range studied, but the average value of SFR for a given stellar mass remains constant over this ∼2 Gyr period. Furthermore, we find no strong evolution in the SFR for our sample as a function of mass over our redshift range of interest; in particular we do not find a decline in the SFR among massive galaxies, as is seen at z < 1. The most massive galaxies in our sample (log M_*≥ 11) have high average SFRs with values SFR_UV, corr= 103 ± 75 M_⊙ yr^−1, and yet exhibit red rest-frame (U−B) colours at all redshifts. We conclude that the majority of these red high-redshift massive galaxies are red due to dust extinction. We find that A_2800 increases with stellar mass, and show that between 45 and 85 per cent of massive galaxies harbour dusty star formation. These results show that even just a few Gyr after the first galaxies appear, there are strong relations between the global physical properties of galaxies, driven by stellar mass or another underlying feature of galaxies strongly related to the stellar mass.

Enantioselective chemoenzymatic synthesis of 3-hydroxytetrahydrofurans

The research described in this thesis is concerned with the synthesis and stereoselective transformations of 4,5-dihydro-3(2H)-furanones and their 3-hydroxy derivatives. In Chapter 1, a review of synthetic routes to 3-hydroxytetrahydrofurans is presented. This incorporates the wide range of applications for these types of compounds. Preparative routes to and stereoselective transformations of the furanones investigated in this study are discussed in Chapter 2. The bulk of the work centers on stereoselective carbonyl group reductions to generate the 3-hydroxytetrahydrofuran derivatives in racemic form followed by kinetic resolution via lipase mediated esterification, resulting in enantioenriched 3-acetoxy and 3-hydroxytetrahydrofuran derivatives. In many cases, these processes proceed in a highly enantioselective manner. The influence of the lipase species and concentration of enzyme employed on the yield and stereochemical outcome of the reactions is examined in detail. Access to the complementary series of furanone and hydroxytetrahydrofuran derivatives by oxidation or reduction of the enantioenriched compounds was achieved through conventional synthetic methods. Chapter 2 also contains details of a novel synthetic route to a range of 2,3,5-trisubstituted furans from α-hydroxyenones and 4,5-dihydro-3(2H)-furanones. The mechanistic rationale for these transformations and the migratory aptitude of alkyl groups towards the formation of these furans is discussed in detail. Finally, Chapter 2 outlines the synthesis of a series of diarylcyclopentenones that were synthesised as part of our investigations. Chapter 3 contains a description of the synthetic procedures and biotransformations carried out together with key analytical and spectroscopic properties of the compounds studied and where appropriate, their analysis using chiral HPLC analysis.