Sensitivity and Fragmentation Calibration of the ROSINA Reflectron-type Time-Of-Flight Mass Spectrometer

The goal of this work was to increase the performance and to calibrate one of the ROSINA sensors, the Reflectron-type Time-Of-Flight mass spectrometer, currently flying aboard the ESA Rosetta spacecraft. Different optimization techniques were applied to both the lab and space models, and a static calibration was performed using different gas species expected to be detected in the vicinity of comet 67P/Churyumov-Gerasimenko. The database thus created was successfully applied to space data, giving consistent results with the other ROSINA sensors.

Sensitivity and fragmentation calibration of the ROSINA double focusing mass spectrometer

The goal of this work has been to calibrate sensitivities and fragmentation pattern of various molecules as well as further characterize the lab model of the ROSINA Double Focusing Mass Spectrometer (DFMS) on board ESA’s Rosetta spacecraft bound to comet 67P/Churyumov-Gerasimenko. The detailed calibration and characterization of the instrument is key to understand and interpret the results in the coma of the comet. A static calibration was performed for the following species: Ne, Ar, Kr, Xe, H2O, N2, CO2, CH4, C2H6, C3H8, C4H10, and C2H4. The purpose of the calibration was to obtain sensitivities for all detectors and emissions, the fragmentation behavior of the ion source and to show the capabilities to measure isotopic ratios at the comet. The calibration included the recording of different correction factors to evaluate the data, including a detailed investigation of the detector gain. The quality of the calibration that could be tested for different gas mixtures including the calibration of the density inside the ion source when calibration gas from the gas calibration unit is introduced. In conclusion the calibration shows that DFMS meets the design requirements and that DFMS will be able to measure the D/H at the comet and help shed more light on the puzzle about the origin of water on Earth.

Chemical Composition of Micrometer-Sized Filaments in an Aragonite Host by a Miniature Laser Ablation/Ionization Mass Spectrometer

Detection of extraterrestrial life is an ongoing goal in space exploration, and there is a need for advanced instruments and methods for the detection of signatures of life based on chemical and isotopic composition. Here, we present the first investigation of chemical composition of putative microfossils in natural samples using a miniature laser ablation/ionization time-of-flight mass spectrometer (LMS). The studies were conducted with high lateral (similar to 15 mu m) and vertical (similar to 20-200 nm) resolution. The primary aim of the study was to investigate the instrument performance on micrometer-sized samples both in terms of isotope abundance and element composition. The following objectives had to be achieved: (1) Consider the detection and calculation of single stable isotope ratios in natural rock samples with techniques compatible with their employment of space instrumentation for biomarker detection in future planetary missions. (2) Achieve a highly accurate chemical compositional map of rock samples with embedded structures at the micrometer scale in which the rock matrix is easily distinguished from the micrometer structures. Our results indicate that chemical mapping of strongly heterogeneous rock samples can be obtained with a high accuracy, whereas the requirements for isotope ratios need to be improved to reach sufficiently large signal-to-noise ratio (SNR). Key Words: Biogenicity-Biomarkers-Biosignatures-Filaments-Fossilization. Astrobiology 15, 669-682.

A growth factor-induced, spatially organizing cytoskeletal module enables rapid and persistent fibroblast migration

Directional migration requires robust front/back polarity. We find that fibroblasts treated with platelet-derived growth factor (PDGF) and prepolarized by plating on a fibronectin line substrate exhibit persistent migration for hours. This does not occur in the absence of PDGF or on uniformly coated fibronectin substrates. Persistent migration arises from establishment of two functional modules at cell front and back. At the front, formation of a zone containing podosome-like structures (PLS) dynamically correlates with low RhoA and myosin activity and absence of a contractile lamella. At the back, myosin contractility specifically controls tail retraction with minimal crosstalk to the front module. The PLS zone is maintained in a dynamic steady state that preserves size and position relative to the cell front, allowing for long-term coordination of front and back modules. We propose that front/back uncoupling achieved by the PLS zone is crucial for persistent migration in the absence of directional cues.

Validation of a Spatially Continuous EDEN Water-Surface Model for the Everglades, Florida

The Everglades Depth Estimation Network (EDEN) is an integrated network of realtime water-level monitoring, ground-elevation modeling, and water-surface modeling that provides scientists and managers with current (2000-present), online water-stage and water-depth information for the entire freshwater portion of the Greater Everglades. Continuous daily spatial interpolations of the EDEN network stage data are presented on grid with 400-square-meter spacing. EDEN offers a consistent and documented dataset that can be used by scientists and managers to: (1) guide large-scale field operations, (2) integrate hydrologic and ecological responses, and (3) support biological and ecological assessments that measure ecosystem responses to the implementation of the Comprehensive Everglades Restoration Plan (CERP) (U.S. Army Corps of Engineers, 1999). The target users are biologists and ecologists examining trophic level responses to hydrodynamic changes in the Everglades. The first objective of this report is to validate the spatially continuous EDEN water-surface model for the Everglades, Florida developed by Pearlstine et al. (2007) by using an independent field-measured data-set. The second objective is to demonstrate two applications of the EDEN water-surface model: to estimate site-specific ground elevation by using the validated EDEN water-surface model and observed water depth data; and to create water-depth hydrographs for tree islands. We found that there are no statistically significant differences between model-predicted and field-observed water-stage data in both southern Water Conservation Area (WCA) 3A and WCA 3B. Tree island elevations were derived by subtracting field water-depth measurements from the predicted EDEN water-surface. Water-depth hydrographs were then computed by subtracting tree island elevations from the EDEN water stage. Overall, the model is reliable by a root mean square error (RMSE) of 3.31 cm. By region, the RMSE is 2.49 cm and 7.77 cm in WCA 3A and 3B, respectively. This new landscape-scale hydrological model has wide applications for ongoing research and management efforts that are vital to restoration of the Florida Everglades. The accurate, high-resolution hydrological data, generated over broad spatial and temporal scales by the EDEN model, provides a previously missing key to understanding the habitat requirements and linkages among native and invasive populations, including fish, wildlife, wading birds, and plants. The EDEN model is a powerful tool that could be adapted for other ecosystem-scale restoration and management programs worldwide.

Growth rates and stable carbon and oxygen isotope record of corals from the Red Sea

Monthly delta18O records of 2 coral colonies (Porites cf. lutea and P. cf. nodifera) from different localities (Aqaba and Eilat) from the northern Gulf of Aqaba, Red Sea, were calibrated with recorded sea surface temperatures (SST) between 1988 and 2000. The results show high correlation coefficients between SST and delta18O. Seasonal variations of coral delta18O in both locations could explain 91% of the recorded SST. Different delta18O/SST relations from both colonies and from the same colonies were obtained, indicating that delta18O from coral skeletons were subject to an extension rate effect. Significant delta18O depletions are associated with high extension rates and higher values with low extension rates. The relation between coral skeletal delta18O and extension rate is not linear and can be described by a simple exponential model. An inverse relationship extends over extension rates from 1 to 5 mm/yr, while for more rapidly growing corals and portions of colonies the relation is constant and the extension rate does not appear to have a significant effect. We recommend that delta18O values be obtained from fast-growing corals or from portions in which the isotopic disequilibrium is fairly constant (extension rate >5 mm/yr). The results show that interspecific differences in corals may produce a significant delta18O profile offset between 2 colonies that is independent of environmental and extension-rate effects. We conclude that the rate of skeletal extension and the species of coral involved have an important influence on coral delta18O and must be considered when using delta18O records for paleoclimatic reconstructions.

Alpine permafrost index map

The objective of this study is the production of an Alpine Permafrost Index Map (APIM) covering the entire European Alps. A unified statistical model that is based on Alpine-wide permafrost observations is used for debris and bedrock surfaces across the entire Alps. The explanatory variables of the model are mean annual air temperatures, potential incoming solar radiation and precipitation. Offset terms were applied to make model predictions for topographic and geomorphic conditions that differ from the terrain features used for model fitting. These offsets are based on literature review and involve some degree of subjective choice during model building. The assessment of the APIM is challenging because limited independent test data are available for comparison and these observations represent point information in a spatially highly variable topography. The APIM provides an index that describes the spatial distribution of permafrost and comes together with an interpretation key that helps to assess map uncertainties and to relate map contents to their actual expression in terrain. The map can be used as a first resource to estimate permafrost conditions at any given location in the European Alps in a variety of contexts such as research and spatial planning. Results show that Switzerland likely is the country with the largest permafrost area in the Alps, followed by Italy, Austria, France and Germany. Slovenia and Liechtenstein may have marginal permafrost areas. In all countries the permafrost area is expected to be larger than the glacier-covered area.

Planktonic foraminifera fluxes and stable isotope ratios in the Irminger Sea

Past water column stratification can be assessed through comparison of the d18O of different planktonic foraminiferal species. The underlying assumption is that different species form their shells simultaneously, but at different depths in the water column. We evaluate this assumption using a sediment trap time-series of Neogloboquadrina pachyderma (s) and Globigerina bulloides from the NW North Atlantic. We determined fluxes, d18O and d13C of shells from two size fractions to assess size-related effects on shell chemistry and to better constrain the underlying causes of isotopic differences between foraminifera in deep-sea sediments. Our data indicate that in the subpolar North Atlantic differences in the seasonality of the shell flux, and not in depth habitat or test size, determine the interspecies Delta d18O. N. pachyderma (s) preferentially forms from early spring to late summer, whereas the flux ofG. bulloides peaks later in the season and is sustained until autumn. Likewise, seasonality influences large and small specimens differently, with large shells settling earlier in the season. The similarity of the seasonal d18O patterns between the two species indicates that they calcify in an overlapping depth zone close to the surface. However, their d13C patterns are markedly different (>1 per mil). Both species have a seasonally variable offset from d13CDIC that appears to be governed primarily by temperature, with larger offsets associated with higher temperatures. The variable offset from d13CDIC implies that seasonality of the flux affects the fossil d13C signal, which has implications for reconstruction of the past oceanic carbon cycle.

U/Th systematics of authigenic carbonates and d18O records from Hydrate Ridge, off the coast of Oregon, USA

Uranium (U) concentrations and activity ratios (d234U) of authigenic carbonates are sensitive recorders of different fluid compositions at submarine seeps of hydrocarbon-rich fluids ("cold seeps") at Hydrate Ridge, off the coast of Oregon, USA. The low U concentrations (mean: 1.3 ± 0.4 µg/g) and high 234U values (165-317 per mil) of gas hydrate carbonates reflect the influence of sedimentary pore water indicating that these carbonates were formed under reducing conditions below or at the seafloor. Their 230Th/234U ages span a time interval from 0.8 to 6.4 ka and cluster around 1.2 and 4.7 ka. In contrast, chemoherm carbonates precipitate from marine bottom water marked by relatively high U concentrations (mean: 5.2 ± 0.8 µg/g) and a mean d234U ratio of 166 ± 3 per mil. Their U isotopes reflect the d234U ratios of the bottom water being enriched in 234U relative to normal seawater. Simple mass balance calculations based on U concentrations and their corresponding d234U ratios reveal a contribution of about 11% of sedimentary pore water to the bottom water. From the U pore water flux and the reconstructed U pore water concentration a mean flow rate of about 147 ± 68 cm/a can be estimated. 230Th/234U ages of chemoherm carbonates range from 7.3 to 267.6 ka. 230Th/234U ages of two chemoherms (Alvin and SE-Knoll chemoherm) correspond to time intervals of low sealevel stands in marine isotope stages (MIS) 2, 4, 5, 6, 7 and 8. This observation indicates that fluid flow at cold seep sites sensitively reflects pressure changes of the hydraulic head in the sediments. The d18OPDB ratios of the chemoherm carbonates support the hypothesis of precipitation during glacial times. Deviations of the chemoherm d18O values from the marine d18O record can be interpreted as to reflect temporally and spatially varying bottom water and/or vent fluid temperatures during carbonate precipitation between 2.6 and 8.6°C.

(Table 1) Summary of accelerator mass spectrometer (AMS) radiocarbon ages in ODP Sites 169-1033 and 169-1034

Continuous coring in Saanich Inlet (Ocean Drilling Program, ODP Leg 169S), British Columbia, Canada, yielded a detailed record of Late Quaternary climate, oceanography, marine productivity, and terrestrial vegetation. Two sites (1033 and 1034) were drilled to maximum depths of 105 and 118 m, recovering sediments ranging in age from 13,300 to less than 300 14C yr. Earliest sediments consist of dense, largely massive, gray glaciomarine muds with dropstones and sand and silt laminae deposited during the waning stages of glaciation. Deposition of organic-rich olive gray sediments began in the fjord about 12,000 14C yr ago, under well-oxygenated conditions as reflected by the presence of bioturbation and a diverse infaunal bivalve community. At about 10,500 14C yr, a massive, gray unit, 40-50 cm thick, was emplaced in a very short span of time. The unit is marked by a sharp lower contact, a gradational upper contact and an abundance of reworked Tertiary microfossils. It has been interpreted as resulting from massive flood events caused by the collapse of glacial dams in the Fraser Valley of mainland British Columbia. Progressively greater anoxia in bottom waters of Saanich Inlet began about 7000 14C yr ago. This is reflected in the preservation of varved sediments consisting of diatomaceous spring-summer laminae and terrigenous winter laminae. Correlation of the sediments was based on: marked lithologic changes, the presence of massive intervals (reflecting localized sediment gravity flow events), the Mazama Ash, occasional thin gray laminae (indicative of abnormal flood events in nearby watersheds), varve counts between marker horizons, and 71 accelerator mass spectrometry (AMS) radiocarbon dates.

Sea surface reconstruction for sediments of the California continental margin

Organic matter in sediment samples from three ODP sites (Ocean Drilling Program Leg 167) that form a south-north transect was investigated to reconstruct the paleoclimatic and oceanographic conditions on the California continental margin during the last 160 kyr. Alkenone-derived paleosea surface temperatures (SST) are 3 to 6°C colder in glacial stages and reveal a clear relationship with global climate changes; the differences are greater in the north. Latitudinal SST comparison exhibits water mixing of the colder California Current with warmer waters from the south, particularly in the southern central California borderland area. Organic matter accumulation on the California continental margin indicates an interplay between climatic and atmospheric glacial-interglacial variations and spatially and temporally changing nutrient availability along the California coastline. Climatic and atmospheric dependent circulations apparently caused variations in the intensity of coastal upwelling along the southern central California margin and this suggests, due to the close connection of the California Current to the local wind patterns, that the California Current was weaker during glacial and stronger during interglacial periods.

Geochemistry on Holocene sediments from the Mediterranean

The enhanced accumulation of organic matter in Eastern Mediterranean sapropels and their unusually low d15N values have been attributed to either enhanced nutrient availability which led to elevated primary production and carbon sequestration or to enhanced organic matter preservation under anoxic conditions. In order to evaluate these two hypothesis we have determined Ba/Al ratios, amino acid composition, N and organic C concentrations and d15N in sinking particles, surface sediments, eight spatially distributed core records of the youngest sapropel S1 (10-6 ka) and older sapropels (S5, S6) from two locations. These data suggest that (i) temporal and spatial variations in d15N of sedimentary N are driven by different degrees of diagenesis at different sites rather than by changes in N-sources or primary productivity and (ii) present day TOC export production would suffice to create a sapropel like S1 under conditions of deep-water anoxia. This implies that both enhanced TOC accumulation and d15N depletion in sapropels were due to the absence of oxygen in deep waters. Thus preservation plays a major role for the accumulation of organic-rich sediments casting doubt on the need of enhanced primary production for sapropel formation.

Western Arabian Sea SST estimation

Millennial-scale records of planktonic foraminiferal Mg/Ca, bulk sediment UK37', and planktonic foraminiferal d18O are presented across the last two deglaciations in sediment core NIOP929 from the Arabian Sea. Mg/Ca-derived temperature variability during the penultimate and last deglacial periods falls within the range of modern day Arabian Sea temperatures, which are influenced by monsoon-driven upwelling. The UK37'-derived temperatures in MIS 5e are similar to modern intermonsoon values and are on average 3.5°C higher than the Mg/Ca temperatures in the same period. MIS 5e UK37' and Mg/Ca temperatures are 1.5°C warmer than during the Holocene, while the UK37'-Mg/Ca temperature difference was about twice as large during MIS 5e. This is surprising as, nowadays, both proxy carriers have a very similar seasonal and depth distribution. Partial explanations for the MIS 5e UK37'-Mg/Ca temperature offset include carbonate dissolution, the change in dominant alkenone-producing species, and possibly lateral advection of alkenone-bearing material and a change in seasonal or depth distribution of proxy carriers. Our findings suggest that (1) Mg/Ca of G. ruber documents seawater temperature in the same way during both studied deglaciations as in the present, with respect to, e.g., season and depth, and (2) UK37'-based temperatures from MIS 5 (or older) represent neither upwelling SST nor annual average SST (as it does in the present and the Holocene) but a higher temperature, despite alkenone production mainly occurring in the upwelling season. Further we report that at the onset of the deglacial warming, the Mg/Ca record leads the UK37' record by 4 ka, of which a maximum of 2 ka may be explained by postdepositional processes. Deglacial warming in both temperature records leads the deglacial decrease in the d18O profile, and Mg/Ca-based temperature returns to lower values before d18O has reached minimum interglacial values. This indicates a substantial lead in Arabian Sea warming relative to global ice melting.

Late Neogene carbonate sedimentation and stable isotope record of ODP Site 121-758

The evolution of oceanic and climatic conditions the northeast Indian Ocean during the last 7 m.y. is revealed in the sediments from Site 758. We present detailed and continuous records of d18O and d13C from planktonic foraminifers, weight percent calcium carbonate, weight percent coarse fraction, magnetic susceptibility, and geomagnetic reversals. Sample spacing of the records ranges from 3 to 10 cm and is equivalent to an average time interval of 2000 to 6000 yr. Despite the fact that core recovery ranged between 100% and 105%, recovery gaps as large as 2.7 m occurred at nearly every break between advanced hydraulic piston cores. Approximately 12% of the late Neogene sequence was not recovered in each of the two holes drilled at Site 758. To circumvent the discontinuity introduced by the gaps, a composite depth section was constructed from multiple cores taken from offset holes at Site 758. The resulting composite depth section extends continuously from 0 to 116 mbsf, from the Holocene to the upper Miocene. A detailed chronostratigraphy is based on geomagnetic reversals which extend from the Brunhes Chron to Chron 6, and on d18O stages 1 through 105, which span from 0 to 2.5 Ma. The d18O record is dominated by a ~40-k.y. cycle in the late Pliocene and early Pleistocene, and is followed by a change to a ~100-k.y. cycle in the late Pleistocene. The mid-Pleistocene transition between these two modes of variability occurs between d18O stages 25 and 22 (between 860 and 800 Ka). Thirteen major volcanic ash horizons from the Indonesian arc are observed throughout the sedimentary section and are dated by their relative position within the geomagnetic reversals and the d18O chronostratigraphy. Since 5 Ma, there has been a long-term decline in weight percent CaCO3 and CaCO3 mass accumulation rates, and an associated rise in non-CaCO3 mass accumulation rates. We attribute these changes to a decrease in CaCO3 productivity and an increase in terrigenous sedimentation through enhanced riverine input. Such input may be linked to rapid tectonic uplift of the Himalayas and the Tibetan Plateau via mechanisms such as the intensification of the monsoonal rains, increased fluvial erosion, and regional glaciation. The long-term increase in percent coarse fraction since 5 Ma suggests a gradual increase in CaCO3 preservation. Higher frequency fluctuations in CaCO3 preservation are superimposed on the long-term trend and are related to climate fluctuations. The abrupt drop (-50%) in CaCO3 accumulation at 3.4 Ma signals a dramatic decrease in CaCO3 production that occurred over much of the Indian Ocean.