High-resolution in situ oxygen microprofiles, porewater and solid phase geochemistry from the Crimean shelf (Black Sea) from Maria S. Merian cruise MSM15/1

The outer western Crimean shelf of the Black Sea is a natural laboratory to investigate effects of stable oxic versus varying hypoxic conditions on seafloor biogeochemical processes and benthic community structure. Bottom-water oxygen concentrations ranged from normoxic (175 µmol O2/L) and hypoxic (< 63 µmol O2/L) or even anoxic/sulfidic conditions within a few kilometers' distance. Variations in oxygen concentrations between 160 and 10 µmol/L even occurred within hours close to the chemocline at 134 m water depth. Total oxygen uptake, including diffusive as well as fauna-mediated oxygen consumption, decreased from 15 mmol/m**2/d on average in the oxic zone, to 7 mmol/m**2/d on average in the hypoxic zone, correlating with changes in macrobenthos composition. Benthic diffusive oxygen uptake rates, comprising respiration of microorganisms and small meiofauna, were similar in oxic and hypoxic zones (on average 4.5 mmol/m**2/d), but declined to 1.3 mmol/m**2/d in bottom waters with oxygen concentrations below 20 µmol/L. Measurements and modeling of porewater profiles indicated that reoxidation of reduced compounds played only a minor role in diffusive oxygen uptake under the different oxygen conditions, leaving the major fraction to aerobic degradation of organic carbon. Remineralization efficiency decreased from nearly 100 % in the oxic zone, to 50 % in the oxic-hypoxic zone, to 10 % in the hypoxic-anoxic zone. Overall, the faunal remineralization rate was more important, but also more influenced by fluctuating oxygen concentrations, than microbial and geochemical oxidation processes.

High resolution study of sediment core GeoB3606-1

Based on a high-resolution analysis of the diatom signal and biogenic bulk components at site GeoB3606-1 (25°S, off Namibia), we describe rapid palaeoceanographic changes in the Benguela Upwelling System (BUS) from early MIS 3 through to the early Holocene (55 000 to 7 000 14C yr BP). Coastal upwelling strongly varied at 25°S from MIS 3 through to MIS 2. The abrupt decrease in the accumulation rate of biogenic silica and diatoms from MIS 3 into MIS 2 records rapid oceanographic changes in the BUS off Namibia. During MIS 3, leakage of excess H4SiO4 acid from the Southern Ocean into low-latitude surface waters, as indicated by the occurrence of Antarctic diatoms, enhanced the production of spores of Chaetoceros at the expense of calcareous phytoplankton. Furthermore, shallower Antarctic Intermediate Water (AAIW) would have enriched the thermocline off Namibia with silicate transported from the Southern Ocean. The strong decrease of the siliceous signal throughout MIS 2 represents a decrease in the nutrient input to the BUS, even though the diatom assemblage is still dominated by spores of the upwelling-associated diatom genus Chaetoceros. Depletion of silicate in the thermocline from the onset of MIS 2 through to the early Holocene reflects the shutdown of AAIW injection from the Southern Ocean into the BUS, causing upwelled waters to become reduced in silicate, hence less favourable for diatom production. The deglaciation and early Holocene are characterised by the replacement of the upwelling-associated flora by a non-upwelling-related diatom community, reflecting weakened upwelling, retraction of the seaward extension of the chlorophyll filament off Lüderitz, and dominance of warmer waters.

High-resolution IP25 of three sediment cores in the western North Pacific and Bering Sea

Due to its strong influence on heat and moisture exchange between the ocean and the atmosphere, sea ice is an essential component of the global climate system. In the context of its alarming decrease in terms of concentration, thickness and duration, understanding the processes controlling sea-ice variability and reconstructing paleo-sea-ice extent in polar regions have become of great interest for the scientific community. In this study, for the first time, IP25, a recently developed biomarker sea-ice proxy, was used for a high-resolution reconstruction of the sea-ice extent and its variability in the western North Pacific and western Bering Sea during the past 18,000 years. To identify mechanisms controlling the sea-ice variability, IP25 data were associated with published sea-surface temperature as well as diatom and biogenic opal data. The results indicate that a seasonal sea-ice cover existed during cold periods (Heinrich Stadial 1 and Younger Dryas), whereas during warmer intervals (Bølling-Allerød and Holocene) reduced sea ice or ice-free conditions prevailed in the study area. The variability in sea-ice extent seems to be linked to climate anomalies and sea-level changes controlling the oceanographic circulation between the subarctic Pacific and the Bering Sea, especially the Alaskan Stream injection though the Aleutian passes.

Natural remanent magnetization (NRM) from ODP Site 1263 covering magnetochron C20r and C21n and high-resolution bulk carbon isotope (d13C) records from Sites 702 and 1263

To explore cause and consequences of past climate change, very accurate age models such as those provided by the astronomical timescale (ATS) are needed. Beyond 40 million years the accuracy of the ATS critically depends on the correctness of orbital models and radioisotopic dating techniques. Discrepancies in the age dating of sedimentary successions and the lack of suitable records spanning the middle Eocene have prevented development of a continuous astronomically calibrated geological timescale for the entire Cenozoic Era. We now solve this problem by constructing an independent astrochronological stratigraphy based on Earth's stable 405 kyr eccentricity cycle between 41 and 48 million years ago (Ma) with new data from deep-sea sedimentary sequences in the South Atlantic Ocean. This new link completes the Paleogene astronomical timescale and confirms the intercalibration of radioisotopic and astronomical dating methods back through the Paleocene-Eocene Thermal Maximum (PETM, 55.930 Ma) and the Cretaceous-Paleogene boundary (66.022 Ma). Coupling of the Paleogene 405 kyr cyclostratigraphic frameworks across the middle Eocene further paves the way for extending the ATS into the Mesozoic.

High resolution isotope and Mg/Ca record of sediment core GeoB12615-4

The importance of intermediate water masses in climate change and ocean circulation has been emphasized recently. In particular, Southern Ocean Intermediate Waters (SOIW), such as Antarctic Intermediate Water and Subantarctic Mode Water, are thought to have acted as active interhemispheric transmitter of climate anomalies. Here we reconstruct changes in SOIW signature and spatial and temporal evolution based on a 40 kyr time series of oxygen and carbon isotopes as well as planktic Mg/Ca based thermometry from Site GeoB12615-4 in the western Indian Ocean. Our data suggest that SOIW transmitted Antarctic temperature trends to the equatorial Indian Ocean via the "oceanic tunnel" mechanism. Moreover, our results reveal that deglacial SOIW carried a signature of aged Southern Ocean deep water. We find no evidence of increased formation of intermediate waters during the deglaciation.

High resolution benthic stable-isotope records from ODP Site 1263 and 1262

Recent studies have shown that the Early Eocene Climatic Optimum (EECO) was preceded by a series of short-lived global warming events, known as hyperthermals. Here we present high-resolution benthic stable carbon and oxygen isotope records from ODP Sites 1262 and 1263 (Walvis Ridge, SE Atlantic) between ~54 and ~52 million years ago, tightly constraining the character, timing, and magnitude of six prominent hyperthermal events. These events, which include Eocene Thermal Maximum (ETM) 2 and 3, are studied in relation to orbital forcing and long-term trends. Our findings reveal an almost linear relationship between d13C and d18O for all these hyperthermals, indicating that the eccentricity-paced co-variance between deep-sea temperature changes and extreme perturbations in the exogenic carbon pool persisted during these events towards the onset of the EECO, in accord with previous observations for the Paleocene Eocene Thermal Maximum (PETM) and ETM2. The covariance of d13C and d18O during H2 and I2, which are the second pulses of the "paired" hyperthermal events ETM2-H2 and I1-I2, deviates with respect to the other events. We hypothesize that this could relate to a relatively higher contribution of an isotopically heavier source of carbon, such as peat or permafrost, and/or to climate feedbacks/local changes in circulation. Finally, the d18O records of the two sites show a systematic offset with on average 0.2 per mil heavier values for the shallower Site 1263, which we link to a slightly heavier isotopic composition of the intermediate water mass reaching the northeastern flank of the Walvis Ridge compared to that of the deeper northwestern water mass at Site 1262.

Paleoenvironmental changes in the western Mediterranean since the last glacial maximum: High resolution multiproxy record from the Algero-Balearic basin

The present study uses a multiproxy approach in order to further understand the evolution of climate responses in the western Mediterranean as of the Last Glacial Maximum. Sediments from ODP Site 975 in the Algero-Balearic basin have been analysed at high resolution, both geochemically andmineralogicallly. The resulting data have been used as proxies to establish a sedimentary regime, primary marine productivity, the preservation of the proxies and oxygen conditions. Fluctuations in detrital element concentrations were mainly the consequence of wet/arid oscillations. Productivity has been established using Ba excess, according to which marine productivity appears to have been greatest during cold events Heinrich 1 and Younger Dryas. The S1 time interval was not as marked by increases in productivity as was the eastern Mediterranean. In contrast, the S1 interval was first characterized by a decreasing trend and then by a fall in productivity after the 8.2 ky BP dry-cold event. Since then productivity has remained low. Here we report that there was an important redox event in this basin, probably a consequence of the major oceanographic circulation change occurring in the western Mediterranean at 7.7 ky BP. This circulation change led to reventilation as well as to diagenetic remobilization of redox-sensitive elements and organic matter oxidation. Comparisons between our paleoceanographic reconstruction for this basin and those regarding other Mediterranean basins support the hypothesis that across the Mediterranean there were different types of responses to climate forcing mechanism. The Algero-Balearic basin is likely to be a key area for further understanding of the relationships between the North Atlantic and the eastern Mediterranean basins.

Measurement of 8-hydroxy-2′-deoxyguanosine in DNA by high-performance liquid chromatography-mass spectrometry: comparison with measurement by gas chromatography-mass spectrometry

Measurement of 8-hydroxy-2′-deoxyguanosine (8-OH-dGuo) in DNA by high-performance liquid chromatography/mass spectrometry (LC/MS) was studied. A methodology was developed for separation by LC of 8-OH-dGuo from intact and modified nucleosides in DNA hydrolyzed by a combination of four enzymes: DNase I, phosphodiesterases I and II and alkaline phosphatase. The atmospheric pressure ionization-electrospray process was used for mass spectral measurements. A stable isotope-labeled analog of 8-OH-dGuo was used as an internal standard for quantification by isotope-dilution MS (IDMS). Results showed that LC/IDMS with selected ion-monitoring (SIM) is well suited for identification and quantification of 8-OH-dGuo in DNA at background levels and in damaged DNA. The sensitivity level of LC/IDMS-SIM was found to be comparable to that reported previously using LC-tandem MS (LC/MS/MS). It was found that approximately five lesions per 106 DNA bases can be detected using amounts of DNA as low as 2 µg. The results also suggest that this lesion may be quantified in DNA at levels of one lesion per 106 DNA bases, or even lower, when more DNA is used. Up to 50 µg of DNA per injection were used without adversely affecting the measurements. Gas chromatography/isotope-dilution MS with selected-ion monitoring (GC/IDMS-SIM) was also used to measure this compound in DNA following its removal from DNA by acidic hydrolysis or by hydrolysis with Escherichia coli Fpg protein. The background levels obtained by LC/IDMS-SIM and GC/IDMS-SIM were almost identical. Calf thymus DNA and DNA isolated from cultured HeLa cells were used for this purpose. This indicates that these two techniques can provide similar results in terms of the measurement of 8-OH-dGuo in DNA. In addition, DNA in buffered aqueous solution was damaged by ionizing radiation at different radiation doses and analyzed by LC/IDMS-SIM and GC/IDMS-SIM. Again, similar results were obtained by the two techniques. The sensitivity of GC/MS-SIM for 7,8-dihydro-8-oxoguanine was also examined and found to be much greater than that of LC/MS-SIM and the reported sensitivity of LC/MS/MS for 8-OH-dGuo. Taken together, the results unequivocally show that LC/IDMS-SIM is well suited for sensitive and accurate measurement of 8-OH-dGuo in DNA and that both LC/IDMS-SIM and GC/IDMS-SIM can provide similar results.

Direct measurement of oligonucleotide binding stoichiometry of gene V protein by mass spectrometry.

The binding stoichiometry of gene V protein from bacteriophage f1 to several oligonucleotides was studied using electrospray ionization-mass spectrometry (ESI-MS). Using mild mass spectrometer interface conditions that preserve noncovalent associations in solution, gene V protein was observed as dimer ions from a 10 mM NH4OAc solution. Addition of oligonucleotides resulted in formation of protein-oligonucleotide complexes with stoichiometry of approximately four nucleotides (nt) per protein monomer. A 16-mer oligonucleotide gave predominantly a 4:1 (protein monomer: oligonucleotide) complex while oligonucleotides shorter than 15 nt showed stoichiometries of 2:1. Stoichiometries and relative binding constants for a mixture of oligonucleotides were readily measured using mass spectrometry. The binding stoichiometry of the protein with the 16-mer oligonucleotide was measured independently using size-exclusion chromatography and the results were consistent with the mass spectrometric data. These results demonstrate, for the first time, the observation and stoichiometric measurement of protein-oligonucleotide complexes using ESI-MS. The sensitivity and high resolution of ESI-MS should make it a useful too] in the study of protein-DNA interactions.

Development of a novel pyrolysis-gas chromatography/mass spectrometry method for the analysis of poly(lactic acid) thermal degradation products

Thermal degradation of PLA is a complex process since it comprises many simultaneous reactions. The use of analytical techniques, such as differential scanning calorimetry (DSC) and thermogravimetry (TGA), yields useful information but a more sensitive analytical technique would be necessary to identify and quantify the PLA degradation products. In this work the thermal degradation of PLA at high temperatures was studied by using a pyrolyzer coupled to a gas chromatograph with mass spectrometry detection (Py-GC/MS). Pyrolysis conditions (temperature and time) were optimized in order to obtain an adequate chromatographic separation of the compounds formed during heating. The best resolution of chromatographic peaks was obtained by pyrolyzing the material from room temperature to 600 °C during 0.5 s. These conditions allowed identifying and quantifying the major compounds produced during the PLA thermal degradation in inert atmosphere. The strategy followed to select these operation parameters was by using sequential pyrolysis based on the adaptation of mathematical models. By application of this strategy it was demonstrated that PLA is degraded at high temperatures by following a non-linear behaviour. The application of logistic and Boltzmann models leads to good fittings to the experimental results, despite the Boltzmann model provided the best approach to calculate the time at which 50% of PLA was degraded. In conclusion, the Boltzmann method can be applied as a tool for simulating the PLA thermal degradation.