Alkenones and SST of surface sediments (Appendix)

We have analysed alkenones in 149 surface sediments from the eastern South Atlantic in order to establish a sediment-based calibration of the U37K' paleotemperature index. Our study covers the major tropical to subpolar production systems and sea-surface temperatures (SST's) between 0° and 27°C. In order to define the most suitable calibration for this region, the U37K' values were correlated to seasonal, annual, and production-weighted annual mean atlas temperatures and compared to previously published culture and core-top calibrations. The best linear correlation between U37K' and SST was obtained using annual mean SST from 0 to 10 m water depth (U37K' = 0.033 T + 0.069, r**2 = 0.981). Data scattering increased significantly using temperatures of waters deeper than 20 m, suggesting that U37K' reflects mixed-layer SST and that alkenone production at thermocline depths was not high enough to significantly bias the mixed-layer signal. Regressions based on both production-weighted and on actual annual mean atlas SST were virtually identical, indicating that regional variations in the seasonality of primary production have no discernible effect on the U37K' vs. SST relationship. Comparison with published core-top calibrations from other oceanic regions revealed a high degree of accordance. We, therefore, established a global core-top calibration using U37K' data from 370 sites between 60°S and 60°N in the Atlantic, Indian, and Pacific Oceans and annual mean atlas SST (0-29°C) from 0 m water depth. The resulting relationship (U37K' = 0.033 T + 0.044, r**2 = 958) is identical within error limits to the widely used E. huxleyi calibrations of and attesting their general applicability. The observation that core-top calibrations extending over various biogeographical coccolithophorid zones are strongly linear and in better accordance than culture calibrations suggests that U37K' is less species-dependent than is indicated by culture experiments. The results also suggest that variations in growth rate of algae and nutrient availability do not significantly affect the sedimentary record of U37K' in open ocean environments.

Alkenone data of sediment traps off Cape Blanc, NW Africa

We analysed long-chain alkenones in sinking particles and surface sediments from the filamentous upwelling region off Cape Blanc, NW Africa, to evaluate the transfer of surface water signals into the geological record. Our study is based on time-series sediment trap records from 730 m (1990-1991) to 2195-3562 m depth (1988-1991). Alkenone fluxes showed considerable interannual variations and no consistent seasonality. The average flux of C37 and C38 alkenones to the deep traps was 1.9 µg/m**2/d from March 1988 to October 1990 and sevenfold higher in the subsequent year. Alkenone fluxes to the shallower traps were on average twice as high and showed similar temporal variations. The alkenone unsaturation indices UK'37, UK38Me and UK38Et closely mirrored the seasonal variations in sea-surface temperature (weekly Reynolds SST). Time lags of 10-48 days between the SST and unsaturation maxima suggest particle sinking rates of about 80 and 280 m/d for the periods of low and high alkenone fluxes, respectively. The average flux-weighted UK'37 temperature for the 4-year time series of the deeper traps was 22.1°C, in perfect agreement with the mean weekly SST for the same period. This and the comparison with seasonal temperature variations in the upper 100 m of the water column suggests that UK'37 records principally the yearly average of the mixed-layer temperature in this region. A comparison between the average annual alkenone fluxes to the lower traps (2400 µg/m**2/yr) and into the underlying sediments (4 µg/m**2/yr) suggests that only about 0.2% of the alkenones reaching the deep ocean became preserved in the sediments. The flux-weighted alkenone concentrations also decreased considerably, from 2466 µg/gC in the water column to 62 µg/gC in the surface sediments. Such a low degree of alkenone preservation is typical for slowly accumulating oxygenated sediments. Despite these dramatic diagenetic alkenone losses, the UK'37 ratio was not affected. The average UK'37 value of the sediments (0.796±0.010 or 22.3±0.3°C) was identical within error limits to the 4-year average of the lower traps. The unsaturation indices for C38 alkenones and the ratio between C37 and C38 alkenones also revealed a high degree of stability. Our results do not support the hypothesis that UK'37 is biased towards higher values during oxic diagenesis.

Magnesium/Calcium ratios in benthic foraminifera from surface sediments

We used modern epibenthic foraminifer tests of Cibicidoides mundulus and Planulina wuellerstorfi from South Atlantic core top sediments in order to establish Mg/Ca-temperature relationships for the temperature range from 0 to 15°C. We obtained the following calibrations: Mg/Ca (mmol/mol) = 0.830*exp(0.145*BWT (°C)) for P. wuellerstorfi, and Mg/Ca (mmol/mol) = 0.627*exp(0.143*BWT (°C)) for C. mundulus. However, a number of tests, especially those bathed in North Atlantic Deep Water, revealed higher Mg/Ca ratios than predicted from the calibration. Our data suggest that d[CO3 2-] of bottom water exerts a significant control on dMg/Ca (temperature-corrected) of C. mundulus (dMg/Ca = 0.017*d[CO3 2-] -0.14), while dMg/Ca of P. wuellerstorfi is more likely to be governed by TCO2 (dMg/Ca = -0.007*TCO2 + 15). Since both d[CO3 2-] and TCO2 are closely linked to [CO3 2-], it is inferred that carbonate ion acts as secondary control, after temperature, on benthic shell Mg/Ca below -4°C. A drop in [CO3 2-] by 25 ?mol/kg at 4 km water depth, as suggested for the Last Glacial Maximum, would decrease Mg/Ca by up to 0.4 mmol/mol, which leads to an underestimation of bottom water temperature by -3.5°C. Therefore our results indicate that the Mg/Ca thermometer should be used cautiously for benthic foraminifers where changes in the carbonate chemistry are present in the paleoceanographic record.

Summary of boron isotope and Mg/Ca data

Biological productivity and carbon export in the equatorial Atlantic are thought to have been dramatically higher during the last glacial period than during the Holocene. Here we reconstruct the pH and CO2 content of surface waters from the eastern equatorial Atlantic Ocean over the past ~30 k.y. using the boron isotope composition of Globigerinoides ruber (a mixed-layer-dwelling planktic foraminifera). Our new record, combined with previously published data, indicates that during the last glacial, in contrast to today, a strong west to east gradient existed in the extent of air:sea equilibrium with respect to pCO2 (DeltapCO2), with the eastern equatorial Atlantic acting as a significant source of CO2 (+100 µatm) while the western Atlantic remained close to equilibrium (+25 µatm). This pattern suggests that a fivefold increase in the upwelling rate of deeper waters drove increased Atlantic productivity and large-scale regional cooling during the last glacial, but the higher than modern DeltapCO2 in the east indicates that export production did not keep up with enhanced upwelling of nutrients. However, the downstream decline of DeltapCO2 provides evidence that the unused nutrients from the east were eventually used for biologic carbon export, thereby effectively negating the impact of changes in upwelling on atmospheric CO2 levels. Our findings indicate that the equatorial Atlantic exerted a minimal role in contributing to lower glacial-age atmospheric CO2.

Shell preservation of Limacina inflata in surface sediments of the Central and South Atlantic

Over 300 surface sediment samples from the Central and South Atlantic Ocean and the Caribbean Sea were investigated for the preservation state of the aragonitic test of Limacina inflata. Results are displayed in spatial distribution maps and are plotted against cross-sections of vertical water mass configurations, illustrating the relationship between preservation state, saturation state of the overlying waters, and overall water mass distribution. The microscopic investigation of L. inflata (adults) yielded the Limacina dissolution index (LDX), and revealed three regional dissolution patterns. In the western Atlantic Ocean, sedimentary preservation states correspond to saturation states in the overlying waters. Poor preservation is found within intermediate water masses of southern origin (i.e. Antarctic intermediate water (AAIW), upper circumpolar water (UCDW)), which are distinctly aragonite-corrosive, whereas good preservation is observed within the surface waters above and within the upper North Atlantic deep water (UNADW) beneath the AAIW. In the eastern Atlantic Ocean, in particular along the African continental margin, the LDX fails in most cases (i.e. less than 10 tests of L. inflata per sample were found). This is most probably due to extensive "metabolic" aragonite dissolution at the sediment-water interface combined with a reduced abundance of L. inflata in the surface waters. In the Caribbean Sea, a more complex preservation pattern is observed because of the interaction between different water masses, which invade the Caribbean basins through several channels, and varying input of bank-derived fine aragonite and magnesian calcite material. The solubility of aragonite increases with increasing pressure, but aragonite dissolution in the sediments does not simply increase with water depth. Worse preservation is found in intermediate water depths following an S-shaped curve. As a result, two aragonite lysoclines are observed, one above the other. In four depth transects, we show that the western Atlantic and Caribbean LDX records resemble surficial calcium carbonate data and delta13C and carbonate ion concentration profiles in the water column. Moreover, preservation of L. inflata within AAIW and UCDW improves significantly to the north, whereas carbonate corrosiveness diminishes due to increased mixing of AAIW and UNADW. The close relationship between LDX values and aragonite contents in the sediments shows much promise for the quantification of the aragonite loss under the influence of different water masses. LDX failure and uncertainties may be attributed to (1) aragonite dissolution due to bottom water corrosiveness, (2) aragonite dissolution due to additional CO2 release into the bottom water by the degradation of organic matter based on an enhanced supply of organic matter into the sediment, (3) variations in the distribution of L. inflata and hence a lack of supply into the sediment, (4) dilution of the sediments and hence a lack of tests of L. inflata, or (5) redeposition of sediment particles.

Calcareous dinoflagellates in the eastern equatorial Atlantic

Sediments of the Equatorial Atlantic (core GeoB 1105-4) have been investigated for both calcareous dinoflagellates and organic-walled dinoflagellate cysts. In order to determine the ecological affinity of calcareous dinoflagellates the statistical methods of Detrended Correspondence Analysis (DCA) and Redundancy Analysis (RDA) were used. Utilising DCA, distribution patterns of calcareous dinoflagellates have been compared with those of the ecologically much better known organic-walled dinoflagellate cysts. This method was also used to determine which environmental gradients have a major influence on the species composition. By using existing environmental information based on benthic and planktic foraminifera, such as Sea Surface Temperature (SST) and stable oxygen and carbon isotopes, as well as information on the amount of Calcium Carbonate and Total Organic Carbon (TOC) in bottom sediments, these gradients could be interpreted in terms of productivity and glacial-interglacial trends. Using RDA, the direct relationships between the distribution patterns of calcareous dinoflagellates with the above mentioned external variables could be determined. For the studied region and time interval (141-6.7 ka) the calcareous dinoflagellates show enhanced abundances in periods with reduced productivity most probably related to decreased divergence and relatively stratified, oligotrophic oceanic conditions.

Geochemistry of surface sediment samples from the South Atlantic Ocean

The aim of the present study is an evaluation of the applicability of biogenic barium as a proxy for productivity. For this purpose, 190 surface sediment samples from the South Atlantic Ocean were analysed for their barium and aluminium concentrations. Biogenic barium is estimated by subtracting the calculated terrigenous barium (obtained from the terrigenous Ba/Al ratio and the amount of Al in the sample) from the total Ba content in the sample. Based on the accumulation rates of biogenic barium, export production is estimated using three different algorithms proposed by [Paleoceanography 7 (1992) 163, doi:10.1029/92PA00181; Global Biogeochem. Cycles 9 (1995) 289, doi:10.1029/95GB00021; Geomar. Report 38 (1995) 105]. Primary productivity was calculated from these different export productions and compared with measurements of recent primary productivity in the overlying surface waters. Only the primary productions calculated on the basis of the algorithm of [Paleoceanography 7 (1992) 163, doi:10.1029/92PA00181] yield productivity values comparable to those existing in ocean surface waters. This study further reveals that it is not sufficient to use a constant, generally applicable organic carbon/biogenic barium ratio, as is postulated by [Global Biogeochem. Cycles 9 (1995) 289, doi:10.1029/95GB00021]. This ratio has to be assessed regionally. For the sediments of the Cape Basin in the eastern South Atlantic Ocean, a new algorithm is developed which gives plausible primary productivities for the overlying surface waters.

Sea-surface temperature reconstructions for the Quaternary western Atlantic

Paleotemperature estimates calculated by the SIMMAX Modern Analog Technique are presented for two gravity cores from the Rio Grande Rise, one from the Brazil Slope, and one from the Ceara Rise. The estimates are based on comparisons between modern and fossil planktonic foraminiferal assemblages and were carried out on samples from Quaternary sediments. Estimated warm-season temperatures from the Rio Grande Rise (at approx. 30° S) range from around 19°C to 24°C, with some coincidence of warm peaks with interglacial stages. The temperature estimates (also warm-season) from the more tropical Brazil Slope (at approx. 8° S) and Ceara Rise (at approx. 4° N) cores are more stable, remaining between 26°C and 28°C throughout most of their lengths. This fairly stable situation in the tropical western Atlantic is interrupted in oxygen isotope stage 6 by a significant drop of 2-3°C in both of these cores. Temperature estimates from the uppermost samples in all cores compare very well to the modern-day measured values. Affinities of some foraminiferal species for warmer or cooler surface temperatures are identified within the temperature range of the examined samples based on their abundance values. Especially notable among the warmer species are, Globorotalia menardii, Globigerinita glutinata, Globigerinoides ruber, and Globigerinoides sacculifer. Species indicative of cooler surface temperatures include Globorotalia inflata, Globigerina bulloides, Neogloboquadrina pachyderma, and Globigerina falconensis. A cluster analysis was carried out to assist in understanding the degree of variation which occurs in the foraminiferal assemblages, and how temperature differences influence the faunal compositions of the samples. It is demonstrated that fairly similar samples may have unexpectedly different estimated temperatures due to small differences in key species and, conversely, quite different assemblages can result in similar or identical temperature estimates which confirms that other parameters than just temperature affect faunal content.

Controlling Long-Range Ordered Self-assembly of Solid-Binding Peptide Monolayers on Atomically Flat Layered Materials

Thesis (Master's)--University of Washington, 2016-06

Exploring the biological basis for Salmonella persistence in food manufacturing environments

The persistence of Salmonella spp. in low moisture foods is a challenge for the food industry as despite control strategies already in place, notable outbreaks still occur. The aim of this study was to characterise isolates of Salmonella, known to be persistent in the food manufacturing environment, by comparing their microbiological characteristics with a panel of matched clinical and veterinary isolates. The gross morphology of the challenge panel was phenotypically characterised in terms of cellular size, shape and motility. In all the parameters measured, the factory isolates were indistinguishable from the human, clinical and veterinary strains. Further detailed metabolic profiling was undertaken using the biolog Microbial ID system. Multivariate analysis of the metabolic microarray revealed differences in metabolism of the factory isolate of S.Montevideo, based on its upregulated ability to utilise glucose and the sugar alcohol groups. The remainder of the serotype-matched isolates were metabolically indistinguishable. Temperature and humidity are known to influence bacterial survival and through environmental monitoring experimental parameters were defined. The results revealed Salmonella survival on stainless steel was affected by environmental temperatures that may be experienced in a food processing environment; with higher survival rates (D25=35.4) at temperatures at 25°C and lower humidity levels of 15% RH, however a rapid decline in cell count (D10=3.4) with lower temperatures of 10°C and higher humidity of 70% RH. Several resident factories strains survived in higher numbers on stainless steel (D25=29.69) compared to serotype matched clinical and veterinary isolates (D25=22.98). Factory isolates of Salmonella did not show an enhanced growth rate in comparison to serotype matched solates grown in Luria broth, Nutrient broth and M9 minimal media indicating that as an independent factor, growth was unlikely to be a major factor driving Salmonella persistence. Using a live / dead stain coupled with fluorescence microscopy revealed that when no longer culturable, isolates of S.Schwarzengrund entered into a viable nonculturable state. The biofilm forming capacity of the panel was characterised and revealed that all were able to form biofilms. None of the factory isolates showed an enhanced capability to form biofilms in comparison to serotype-matched isolates. In disinfection studies, planktonic cells were more susceptible to disinfectants than cells in biofilm and all the disinfectants tested were successful in reducing bacterial load. Contact time was one of the most important factors for reducing bacterial populations in a biofilm. The genomes of eight strains were sequenced. At the nucleotide and amino acid level the food factory isolates were similar to those of isolates from other environments; no major genomic rearrangements were observed, supporting the conclusions of the phenotypic and metabolic analysis. In conclusion, having investigated a variety of morphological, biochemical and genomic factors, it is unlikely that the persistence of Salmonella in the food manufacturing environment is attributable to a single phenotypic, metabolic or genomic factor. Whilst a combination of microbiological factors may be involved it is also possible that strain persistence in the factory environment is a consequence of failure to apply established hygiene management principles.

Influence of hydrobiogeochemistry on transport of chromium through manganese -containing sediments: Experimental and modeling approaches

Chromium (Cr) is a metal of particular environmental concern, owing to its toxicity and widespread occurrence in groundwater, soil, and soil solution. A combination of hydrological, geochemical, and microbiological processes governs the subsurface migration of Cr. Little effort has been devoted to examining how these biogeochemical reactions combine with hydrologic processes influence Cr migration. This study has focused on the complex problem of predicting the Cr transport in laboratory column experiments. A 1-D reactive transport model was developed and evaluated against data obtained from laboratory column experiments. ^ A series of dynamic laboratory column experiments were conducted under abiotic and biotic conditions. Cr(III) was injected into columns packed with β-MnO 2-coated sand at different initial concentrations, variable flow rates, and at two different pore water pH (3.0 and 4.0). In biotic anaerobic column experiments Cr(VI) along with lactate was injected into columns packed with quartz sand or β-MnO2-coated sand and bacteria, Shewanella alga Simidu (BrY-MT). A mathematical model was developed which included advection-dispersion equations for the movement of Cr(III), Cr(VI), dissolved oxygen, lactate, and biomass. The model included first-order rate laws governing the adsorption of each Cr species and lactate. The equations for transport and adsorption were coupled with nonlinear equations for rate-limited oxidation-reduction reactions along with dual-monod kinetic equations. Kinetic batch experiments were conducted to determine the reduction of Cr(VI) by BrY-MT in three different substrates. Results of the column experiments with Cr(III)-containing influent solutions demonstrate that β-MnO2 effectively catalyzes the oxidation of Cr(III) to Cr(VI). For a given influent concentration and pore water velocity, oxidation rates are higher, and hence effluent concentrations of Cr(VI) are greater, at pH 4 relative to pH 3. Reduction of Cr(VI) by BrY-MT was rapid (within one hour) in columns packed with quartz sand, whereas Cr(VI) reduction by BrY-MT was delayed (57 hours) in presence of β-MnO 2-coated sand. BrY-MT grown in BHIB (brain heart infusion broth) reduced maximum amount of Cr(VI) to Cr(III) followed by TSB (tryptic soy broth) and M9 (minimum media). The comparisons of data and model results from the column experiments show that the depths associated with Cr(III) oxidation and transport within sediments of shallow aquatic systems can strongly influence trends in surface water quality. The results of this study suggests that carefully performed, laboratory column experiments is a useful tool in determining the biotransformation of redox-sensitive metals even in the presence of strong oxidant, like β-MnO2. ^

Compilation of downward flux observations from sediment trap deployments in the Atlantic Ocean - Contribution to EURO-BASIN's Data integration

We provide a compilation of downward fluxes (total mass, POC, PON, BSiO2, CaCO3, PIC and lithogenic/terrigenous fluxes) from over 6000 sediment trap measurements distributed in the Atlantic Ocean, from 30 degree North to 49 degree South, and covering the period 1982-2011. Data from the Mediterranean Sea are also included. Data were compiled from different sources: data repositories (BCO-DMO, PANGAEA), time series sites (BATS, CARIACO), published scientific papers and/or personal communications from PI's. All sources are specifed in the data set. Data from the World Ocean Atlas 2009 were extracted to provide each flux observation with contextual environmental data, such as temperature, salinity, oxygen (concentration, AOU and percentage saturation), nitrate, phosphate and silicate.