Environmental factors modulating the abundance and distribution of Callinectes danae (Decapoda: Portunidae) from two areas of the southeastern coast of Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Azobenzol- und Perylendiimid-funktionalisierte Polyphenylen-Dendrimere

Die Dissertation 'Azobenzol- und Perylendiimid-funktionalisierte Polyphenylen-Dendrimere - Synthese, Charakterisierung und Eigenschaften' gliedert sich in vier Themengebiete. Der erste Abschnitt beschäftigt sich mit der Synthese unterschiedlich dichter Dendrimere um einen Azobenzol-Kern. Einkristallstrukturen und Molekülvisualisierungen verdeutlichen die dreidimensionale Gestalt der Dendrimere. Die Dendrimere zeigen erstmalig eine Abhängigkeit des Isomerisationsverhaltens von der das Chromophor umgebenden Struktur. Der zweite Abschnitt hat Interaktionen von Chromophoren, deren Distanz und Orientierung zueinander gezielt durch einen äußeren Impuls geändert werden können, zum Thema. Die Verbindung von Azobenzol und PMI führt durch deren gegenseitige Beeinflussung zu einem Verlust der charakteristischen Eigenschaften der Chromophore. Eine Oligo-L-Lysinkette, deren Enden mit NMI und PMI funktionalisiert sind, stellt ein FRET-System dar. Distanz und Orientierung der Chromophore zueinander werden durch den mittels TFE induzierten Übergang des Peptids vom Knäuel zur Helix verändert. Der dritte Abschnitt führt die Synthese von PDI-gekernten Dendrimeren durch Substitution in der bay-Region des Chromophors ein. Die Eignenschaften der Verbindungen wurden mittels optischer Methoden und cyclovoltammetrischen Studien untersucht. Weiter wurde die Oberflächenfunktionalisierung mit Aminosäuren und Oligopeptiden zu wasserlöslichen Dendrimeren mit hoher Oberflächenladung verfolgt. Das letzte Kapitel stellt Untersuchungen zur Organisation von Polyphenylen-Dendrimeren auf HOPG vor. Es lassen sich einerseits Nanofasern formieren, andererseits können auch geordnete Mono- und Multilagen erzeugt werden.

Organic matter C and N composition and N. pachyderma stable isotope ratios of ODP Hole 188-1166A sediments

We report the results of downhole stable isotopic (d13Corg [organic carbon] and d15N) and elemental measurements (total organic carbon [TOC], total nitrogen [TN], and carbon/nitrogen [C/N]) of sedimentary organic matter (SOM) along with stable isotopic measurements (d18O and d13C) of left-coiling Neogloboquadrina pachyderma planktonic foraminifers from Ocean Drilling Program Site 1166. TOC and TN measurements indicate a large change from organic-rich preglacial sediments with primary organic matter to organic-poor early glacial and glacial sediments, with mainly recycled organic matter. Results of the stable isotopic measurements of SOM show a range of values that are typical of both marine and terrestrial organic matter, probably reflecting a mixture of the two. However, C/N values are mostly high (>15), suggesting greater input and/or preservation of terrestrial organic matter. Foraminifers are only present in glacial/glaciomarine sediments of latest Pliocene to Pleistocene age at Site 1166 (lithostratigraphic Unit I). The majority of this unit has d13Corg and TOC values that are similar to those of glacial sediments recovered at Site 1167 (lithostratigraphic Unit II) on the slope and may have the same source(s). Although the low resolution of the N. pachyderma (s.) d18O and d13C data set precludes any specific paleoclimatic interpretation, downcore variations in foraminifer d18O and d13C values of 0.5 per mil to 1 per mil amplitude may indicate glacial-interglacial changes in ice volume/temperature in the Prydz Bay region.

Debris flow magnitudes: a global catalog

The episodic occurrence of debris flow events in response to stochastic precipitation and wildfire events makes hazard prediction challenging. Previous work has shown that frequency-magnitude distributions of non-fire-related debris flows follow a power law, but less is known about the distribution of post-fire debris flows. As a first step in parameterizing hazard models, we use frequency-magnitude distributions and cumulative distribution functions to compare volumes of post-fire debris flows to non-fire-related debris flows. Due to the large number of events required to parameterize frequency-magnitude distributions, and the relatively small number of post-fire event magnitudes recorded in the literature, we collected data on 73 recent post-fire events in the field. The resulting catalog of 988 debris flow events is presented as an appendix to this article. We found that the empirical cumulative distribution function of post-fire debris flow volumes is composed of smaller events than that of non-fire-related debris flows. In addition, the slope of the frequency-magnitude distribution of post-fire debris flows is steeper than that of non-fire-related debris flows, evidence that differences in the post-fire environment tend to produce a higher proportion of small events. We propose two possible explanations: 1) post-fire events occur on shorter return intervals than debris flows in similar basins that do not experience fire, causing their distribution to shift toward smaller events due to limitations in sediment supply, or 2) fire causes changes in resisting and driving forces on a package of sediment, such that a smaller perturbation of the system is required in order for a debris flow to occur, resulting in smaller event volumes.

Mineralogical-sedimentological and chemical investigation of sediments from Cross Bank off Florida

The sediments of a core of.1.55 m length taken on the windward side of the Cross Bank, Florida Bay, are clearly subdivided into two portions, as shown by grain size analysis: silt-sized particles predominate in the relatively homogeneous lower two thirds of the core. This is succeeded abruptly by a thin layer of sand, containing fragments of Halimeda. They indicate a catastrophic event in the Florida Bay region, because Halimeda does not grow within Florida Bay. Above this layer, the amount of sand decreases at first and then continuously increases right to the present sediment-water-interface. The median and skewness increase simultaneously with the increase in the sand and granule portion. We assume that the changing grain size distribution was determined chiefly by the density of the marine flora: during the deposition of the lower two thirds of the core a dense grass cover acted as a sediment catcher for the fine-grained detritus washed out of the shallow basins of the Florida Bay, and simultaneously prohibited renewed reworking. Similar processes go on today on the surface of most mud banks of Florida Bay. The catastrophic event indicated by the sand layer probably changed the morphology of the bank to such an extent that the sampling point was shifted more to the windward side of the bank. This side is characterized by less dense plant growth. Therefore, less detritus could be caught and the material deposited could be reworked. The pronounced increase in skewness in the upper third of the core certainly indicates a strong washing out of the smaller-sized particles. The sediments are predominantly made up of carbonates, averagely 88.14 percent. The average CaCO3-content is 83.87 percent and the average MgCO3-content amounts to 4.27 percent. The chief carbonate mineral is aragonite making up 60.1 percent of the carbonate portion in the average, followed by high-magnesian calcite (33.8 percent) and calcite (6.1 percent). With increasing grain size the aragonite clearly increases at the cost of high-magnesian calcite in the upper third of the core. Chemically, this is shown by an increase of the CaCO3 : MgCO3-ratio. This increase is mainly caused by the more common occurrence of aragonitic fragments of mollusks in the coarse grain fractions. The bulk of the carbonates is made up of mollusks, foraminifera, ostracods, and - to a much lesser extent - of corals, worm-tubes, coccolithophorids, and calcareous algae, as shown by microscopic investigations. The total amount of the carbonate in the sediments is biogenic detritus with the possible exception of a very small amount of aragonite needles in the clay and fine silt fraction. The individual carbonate components of the gravel and sand fraction can be relatively easy identified as members of a particular animal or plant group. This becomes very difficult in the silt and clay fraction. Brownish aggregates are very common in the coarse and medium silt fraction. It was not always possible to clarify their origin (biogenic detritus, faecal pellets or carbonate particles cemented by carbonates or organic slime, etc.). Organic matter (plant fragments, rootlets), quartz, opal (siliceous sponge needles), and feldspar also occur in the sediments, besides carbonates. The lowermost part of the core has an age of 1365 +/- 90 years, as shown by 14C analysis.

Ice-rafted debris in ODP Holes 177-1090D and 188-1165B

Constraining the nature of Antarctic Ice Sheet (AIS) response to major past climate changes may provide a window onto future ice response and rates of sea level rise. One approach to tracking AIS dynamics, and differentiating whole system versus potentially heterogeneous ice sheet sector changes, is to integrate multiple climate proxies for a specific time slice across widely distributed locations. This study presents new iceberg-rafted debris (IRD) data across the interval that includes Marine Isotope Stage 31 (MIS 31: 1.081-1.062 Ma, a span of ~19 kyr; Lisiecki and Raymo, 2005), which lies on the cusp of the mid-Brunhes climate transition (as glacial cycles shifted from ~41,000 yr to ~100,000 yr duration). Two sites are studied - distal Ocean Drilling Program (ODP) Leg 177 Site 1090 (Site 1090) in the eastern subantarctic sector of the South Atlantic Ocean, and proximal ODP Leg 188 Site 1165 (Site 1165), near Prydz Bay, in the Indian Ocean sector of the Antarctic margin. At each of these sites, MIS 31 is marked by the presence of the Jaramillo Subchron (0.988-1.072 Ma; Lourens et al., 2004) which provides a time-marker to correlate these two sites with relative precision. At both sites, records of multiple climate proxies are available to aid in interpretation. The presence of IRD in sediments from our study areas, which include garnets indicating a likely East Antarctic Ice Sheet (EAIS) origin, supports the conclusion that although the EAIS apparently withdrew significantly over MIS 31 in the Prydz Bay region and other sectors, some sectors of the EAIS must still have maintained marine margins capable of launching icebergs even through the warmest intervals. Thus, the EAIS did not respond in complete synchrony even to major climate changes such as MIS 31. Further, the record at Site 1090 (supported by records from other subantarctic locations) indicates that the glacial MIS 32 should be reduced to no more than a stadial, and the warm interval of Antarctic ice retreat that includes MIS 31 should be expanded to MIS 33-31. This revised warm interval lasted about 52 kyr, in line with several other interglacials in the benthic d18O records stack of Lisiecki and Raymo (2005), including the super-interglacials MIS 11 (duration of 50 kyr) and MIS 5 (duration of 59 kyr). The record from Antarctica-proximal Site 1165, when interpreted in accord with the record from ANDRILL-1B, indicates that in these southern high latitude sectors, ice sheet retreat and the effects of warming lasted longer than at Site 1090, perhaps until MIS 27. In the current interpretations of the age models of the proximal sites, ice sheet retreat began relatively slowly, and was not really evident until the start of MIS 31. In another somewhat more speculative interpretation, ice sheet retreat began noticeably with MIS 33, and accelerated during MIS 31. Ice sheet inertia (the lag-times in the large-scale responses of major ice sheets to a forcing) likely plays an important part in the timing and scale of these events in vulnerable sectors of the AIS.

Archive of the PASATA (PASsive Acoustic Tracking of Antarctic marine mammals) field documentation

Recordings from the PerenniAL Acoustic Observatory in the Antarctic ocean (PALAOA) show seasonal acoustic presence of 4 Antarctic ice-breeding seal species (Ross seal, Ommatophoca rossii, Weddell seal, Leptonychotes weddellii, crabeater, Lobodon carcinophaga, and leopard seal, Hydrurga leptonyx). Apart from Weddell seals, inhabiting the fast-ice in Atka Bay, the other three (pack-ice) species however have to date never (Ross and leopard seal) or only very rarely (crabeater seals) been sighted in the Atka Bay region. The aim of the PASATA project is twofold: the large passive acoustic hydrophone array (hereafter referred to as large array) aims to localize calling pack-ice pinniped species to obtain information on their location and hence the ice habitat they occupy. This large array consists of four autonomous passive acoustic recorders with a hydrophone sensor deployed through a drilled hole in the sea ice. The PASATA recordings are time-stamped and can therefore be coupled to the PALAOA recordings so that the hydrophone array spans the bay almost entirely from east to west. The second, smaller hydrophone array (hereafter referred to as small array), also consists of four autonomous passive acoustic recorders with hydrophone sensors deployed through drilled holes in the sea ice. The smaller array was deployed within a Weddell seal breeding colony, located further south in the bay, just off the ice shelf. Male Weddell seals are thought to defend underwater territories around or near tide cracks and breathing holes used by females. Vocal activity increases strongly during the breeding season and vocalizations are thought to be used underwater by males for the purpose of territorial defense and advertisement. With the smaller hydrophone array we aim to investigate underwater behaviour of vocalizing male and female Weddell seals to provide further information on underwater movement patterns in relation to the location of tide cracks and breathing holes. As a pilot project, one on-ice and three underwater camera systems have been deployed near breathing holes to obtain additional visual information on Weddell seal behavioural activity. Upon each visit in the breeding colony, a census of colony composition on the ice (number of animals, sex, presence of dependent pups, presence and severity of injuries-indicative of competition intensity) as well as GPS readings of breathing holes and positions of hauled out Weddell seals are taken.

The [(G/C)3NN]n motif: a common DNA repeat that excludes nucleosomes.

Nucleosomes, the basic structural elements of chromosomes, consist of 146 bp of DNA coiled around an octamer of histone proteins, and their presence can strongly influence gene expression. Considerations of the anisotropic flexibility of nucleotide triplets containing 3 cytosines or guanines suggested that a [5'(G/C)3 NN3']n motif might resist wrapping around a histone octamer. To test this, DNAs were constructed containing a 5'-CCGNN-3' pentanucleotide repeat with the Ns varied. Using in vitro nucleosome reconstitution and electron microscopy, a plasmid with 48 contiguous CCGNN repeats strongly excluded nucleosomes in the repeat region. Competitive reconstitution gel retardation experiments using DNA fragments containing 12, 24, or 48 CCGNN repeats showed that the propensity to exclude nucleosomes increased with the length of the repeat. Analysis showed that a 268-bp DNA containing a (CCGNN)48 block is 4.9 +/- 0.6-fold less efficient in nucleosome assembly than a similar length pUC19 fragment and approximately 78-fold less efficient than a similar length (CTG)n sequence, based on results from previous studies. Computer searches against the GenBank database for matches with a [(G/C)3NN]48 sequence revealed numerous examples that frequently were present in the control regions of "TATA-less" genes, including the human ETS-2 and human dihydrofolate reductase genes. In both cases the (G/C)3NN repeat, present in the promoter region, co-maps with loci previously shown to be nuclease hypersensitive sites.

Nieuwe en Accurate Caart vann de Omleggende Lande van Belgrado: als mede des selfs Belegeringh, ende Marse der Keyserlycke Armee, Ao. 1717

by Joachim Ottens.

Sedimentological, mineralogical, biogeochemical and micropaleontological parameters on sediment core PS69/849-2, Burton Basin, MacRobertson Shelf, East Antarctica

A multi-proxy study including sedimentological, mineralogical, biogeochemical and micropaleontological methods was conducted on sediment core PS69/849-2 retrieved from Burton Basin, MacRobertson Shelf, East Antarctica. The goal of this study was to depict the deglacial and Holocene environmental history of the MacRobertson Land-Prydz Bay region. A special focus was put on the timing of ice-sheet retreat and the variability of bottom-water formation due to sea ice formation through the Holocene. Results from site PS69/849-2 provide the first paleo-environmental record of Holocene variations in bottom-water production probably associated to the Cape Darnley polynya, which is the second largest polynya in the Antarctic. Methods included end-member modeling of laser-derived high-resolution grain size data to reconstruct the depositional regimes and bottom-water activity. The provenance of current-derived and ice-transported material was reconstructed using clay-mineral and heavy-mineral analysis. Conclusions on biogenic production were drawn by determination of biogenic opal and total organic carbon. It was found that the ice shelf front started to retreat from the site around 12.8 ka BP. This coincides with results from other records in Prydz Bay and suggests warming during the early Holocene optimum next to global sea level rise as the main trigger. Ice-rafted debris was then supplied to the site until 5.5 cal. ka BP, when Holocene global sea level rise stabilized and glacial isostatic rebound on MacRobertson Land commenced. Throughout the Holocene, three episodes of enhanced bottom-water activity probably due to elevated brine rejection in Cape Darnley polynya occured between 11.5 and 9 cal. ka BP, 5.6 and 4.5 cal. ka BP and since 1.5 cal. ka BP. These periods are related to shifts from warmer to cooler conditions at the end of Holocene warm periods, in particular the early Holocene optimum, the mid-Holocene warm period and at the beginning of the neoglacial. In contrast, between 7.7 and 6.7 cal. ka BP, brine rejection shut down, maybe owed to warm conditions and pronounced open-water intervals.

Effects of Land Use on Sources and Ages of Inorganic and Organic Carbon in Temperate Headwater Streams

The amounts, sources and relative ages of inorganic and organic carbon pools were assessed in eight headwater streams draining watersheds dominated by either forest, pasture, cropland or urban development in the lower Chesapeake Bay region (Virginia, USA). Streams were sampled at baseflow conditions six different times over 1 year. The sources and ages of the carbon pools were characterized by isotopic (δ13C and ∆14C) analyses and excitation emission matrix fluorescence with parallel factor analysis (EEM–PARAFAC). The findings from this study showed that human land use may alter aquatic carbon cycling in three primary ways. First, human land use affects the sources and ages of DIC by controlling different rates of weathering and erosion. Relative to dissolved inorganic carbon (DIC) in forested streams which originated primarily from respiration of young, 14C-enriched organic matter (OM; δ13C = −22.2 ± 3 ‰; ∆14C = 69 ± 14 ‰), DIC in urbanized streams was influenced more by sedimentary carbonate weathering (δ13C = −12.4 ± 1 ‰; ∆14C = −270 ± 37 ‰) and one of pasture streams showed a greater influence from young soil carbonates (δ13C = −5.7 ± 2.5 ‰; ∆14C = 69 ‰). Second, human land use alters the proportions of terrestrial versus autochthonous/microbial sources of stream water OM. Fluorescence properties of dissolved OM (DOM) and the C:N of particulate OM (POM) suggested that streams draining human-altered watersheds contained greater relative contributions of DOM and POM from autochthonous/microbial sources than forested streams. Third, human land uses can mobilize geologically aged inorganic carbon and enable its participation in contemporary carbon cycling. Aged DOM (∆14C = −248 to −202 ‰, equivalent14C ages of 1,811–2,284 years BP) and POM (∆14C = −90 to −88 ‰, 14C ages of 669–887 years BP) were observed exclusively in urbanized streams, presumably a result of autotrophic fixation of aged DIC (−297 to −244 ‰, 14C age = 2,251–2,833 years BP) from sedimentary shell dissolution and perhaps also watershed export of fossil fuel carbon. This study demonstrates that human land use may have significant impacts on the amounts, sources, ages and cycling of carbon in headwater streams and their associated watersheds.

Synthesis and Properties of a Series of 1,1,n,n-Tetramethyl[n](2,11)teropyrenophanes

The work described in this thesis revolves around the 1,1,n,ntetramethyl[n](2,11)teropyrenophanes, which are a series of [n]cyclophanes with a severely bent, board-shaped polynuclear aromatic hydrocarbons (PAH). The thesis is divided into seven Chapters. The first Chapter conatins an overview of the seminal work on [n]cyclophanes of the first two members of the “capped rylene” series of PAHs: benzene and pyrene. Three different general strategies for the synthesis of [n]cyclophanes are discussed and this leads in to a discussion of some slected syntheses of [n]paracyclopahnes and [n](2,7)pyrenophanes. The chemical, structural, spectroscopic and photophysical properties of these benzene and pyrene-derived cyclophanes are discussed with emphasis on the changes that occur with changes in the structure of the aromatic system. Chapter 1 concludes with a brief introduction to [n]cyclophanes of the fourth member of the capped rylene series of PAHs: teropyrene. The focus of the work described in Chapter 2 is the synthesis of of 1,1,n,ntetramethyl[n](2,11)teropyrenophane (n = 6 and 7) using a double-McMurry strategy. While the synthesis 1,1,7,7-tetramethyl[7](2,11)teropyrenophane was successful, the synthesis of the lower homologue 1,1,6,6-tetramethyl[6](2,11)teropyrenophane was not. The conformational behaviour of [n.2]pyrenophanes was also studied by 1H NMR spectroscopy and this provided a conformation-based rationale for the failure of the synthesis of 1,1,6,6-tetramethyl[6](2,11)teropyrenophane. Chapter 3 contains details of the synthesis of 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n = 7-9) using a Wurtz / McMurry strategy, which proved to be more general than the double McMurry strategy. The three teropyrenophanes were obtained in ca. 10 milligram quantities. Trends in the spectroscopic properties that accompany changes in the structure of the teropyrene system are discussed. A violation of Kasha’s rule was observed when the teropyrenophanes were irradiated at 260 nm. The work described in the fourth Chapter concentrates on the development of gram-scale syntheses of 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n = 7–10) using the Wurtz / McMurry strategy. Several major modifications to the orginal synthetic pathway had to be made to enable the first several steps to be performed comfortably on tens of grams of material. Solubility problems severely limited the amount of material that could be produced at a late stage of the synthetic pathways leading to the evennumbered members of the series (n = 8, 10). Ultimately, only 1,1,9,9- tetramethyl[9](2,11)teropyrenophane was synthesized on a multi-gram scale. In the final step in the synthesis, a valence isomerization / dehydrogenation (VID) reaction, the teropyrenophane was observed to become unstable under the conditions of its formation at n = 8. The synthesis of 1,1,10,10-tetramethyl[10](2,11)teropyrenophane was achieved for the first time, but only on a few hundred milligram scale. In Chapter 5, the results of an investigation of the electrophilic aromatic bromination of the 1,1,n,n-tetramethyl[n](2,11)teropyrenophanes (n = 7–10) are presented. Being the most abundant cyclophane, most of the work was performed on 1,1,9,9-tetramethyl[9](2,11)teropyrenophane. Reaction of this compound with varying amounts of of bromine revealed that bromination occurs most rapidly at the symmetryrelated 4, 9, 13 and 18 positions (teropyrene numbering) and that the 4,9,13,18- tetrabromide could be formed exclusively. Subsequent bromination occurs selectively on the symmetry-related 6, 7, 15 and 16 positions (teropyrene numbering), but considerably more slowly. Only mixtures of penta-, hexa-, hepta and octabromides could be formed. Bromination reactions of the higher and lower homologues (n = 7, 8 and 10) revealed that the reactivity of the teropyrene system increased with the degree of bend. Crystal structures of some tetra-, hexa-, hepta- and octa-brominated products were obtained. The goal of the work described in Chapter 6 is to use 1,1,9,9- tetramethyl[9](2,11)teropyrenophane as a starting material for the synthesis of warped nanographenophanes. A bromination, Suzuki-Miyaura, cyclodehydrogenation sequence was unsuccessful, as was a C–H arylation / cyclodehydrogenation approach. Itami’s recently-developed K-region-selective annulative -extension (APEX) reaction proved to be successful, affording a giant [n]cyclophane with a C84 PAH. Attempted bay-region Diels-Alder reactions and some cursory host-guest chemistry of teropyrenophanes are also discussed. In Chapter 7 a synthetic approach toward a planar model compound, 2,11-di-tbutylteropyrene, is described. The synthesis could not be completed owing to solubility problems at the end of the synthetic pathway.

(Table, Appendix C) Metal content of nodules at Sea Scope stations based upon XRF analyses at the Ore Microscopy Laboratory, Washington State Unicersity, USA

New information on possible resource value of sea floor manganese nodule deposits in the eastern north Pacific has been obtained by a study of records and collections of the 1972 Sea Scope Expedition. Nodule abundance (percent of sea floor covered) varies greatly, according to photographs from eight stations and data from other sources. All estimates considered reliable are plotted on a map of the region. Similar maps show the average content of Ni, Cu, Mn and Co at 89 stations from which three or more nodules were analyzed. Variations in nodule metal content at each station are shown graphically in an appendix, where data on nodule sizes are also given. Results of new analyses of 420 nodules from 93 stations for mn, fe, ni, cu, CO, and zn are listed in another appendix. Relatively high Ni + Cu content is restricted chiefly to four groups of stations in the equatorial region, where group averages are 1.86, 1.99, 2.47, and 2.55 weight-percent. Prepared for United States Department of the Interior, Bureau of Mines. Grant no. GO284008-02-MAS. - NTIS PB82-142571.