Stable oxygen isotope record and age determination of sediments from the North Atlantic Ocean

Sea surface temperature and salinity estimates reconstructed using planktonic foraminiferal abundance and delta18O records from core SU90-03 (40°N, 32°W, 2475 m water depth) reveal large climatic fluctuations linked to major instabilities in Northern Hemisphere ice sheets over the last 150 000 years. Episodes of enhanced ice rafted detritus (IRD) input were accompanied by discrete temperature minima, representing coolings of between 4 and 8°C, and reductions in surface salinity of up to 2.5-3.5 per mil. Several additional cooling episodes of a similar magnitude were documented during intervals of low IRD input that appear to be synchronous, within the limits of dating, with ice rafting events spatially confined to higher latitudes. Accelerator mass spectrometer 14C dates for Heinrich events (H1 - 14.2 ka, H2 - 21.4 ka, H3 - 26.7 ka, H4 - 34.8 ka, H5 - 47.2 ka) obtained from core SU90-03 agree well with other published age estimates and suggest a contemporaneous pattern of climate change throughout the North Atlantic during the last glacial period. This interpretation is supported by a comparison of IRD and palaeotemperature records from DSDP site 609 and core SU90-03, which clearly shows that the major climatic fluctuations identified at high latitudes were transmitted toward the subtropics. However, 14C dates suggest that ice rafting episodes may be diachronous to some extent. The northward migration of the polar front after the H1 event at 40°N in the mid-Atlantic occurred at 14 ka, approximately 500 years earlier than along the Portuguese margin, where the southerly advection of polar waters persisted within eastern boundary current system.

(Appendix 1-4) Geochemistry, desorption methods, TOC, TC, and mineral content of different settings

Sorption of volatile hydrocarbon gases (VHCs) to marine sediments is a recognized phenomenon that has been investigated in the context of petroleum exploration. However, little is known about the biogeochemistry of sorbed methane and higher VHCs in environments that are not influenced by thermogenic processes. This study evaluated two different extraction protocols for sorbed VHCs, used high pressure equipment to investigate the sorption of methane to pure clay mineral phases, and conducted a geochemical and mineralogical survey of sediment samples from different oceanographic settings and geochemical regimes that are not significantly influenced by thermogenic gas. Extraction of sediments under alkaline conditions yielded higher concentrations of sorbed methane than the established protocol for acidic extraction. Application of alkaline extraction in the environmental survey revealed the presence of substantial amounts of sorbed methane in 374 out of 411 samples (91%). Particularly high amounts, up to 2.1 mmol kg**-1 dry sediment, were recovered from methanogenic sediments. Carbon isotopic compositions of sorbed methane suggested substantial contributions from biogenic sources, both in sulfate-depleted and sulfate-reducing sediments. Carbon isotopic relationships between sorbed and dissolved methane indicate a coupling of the two pools. While our sorption experiments and extraction conditions point to an important role for clay minerals as sorbents, mineralogical analyses of marine sediments suggest that variations in mineral composition are not controlling variations in quantities of sorbed methane. We conclude that the distribution of sorbed methane in sediments is strongly influenced by in situ production.

Seasonal changes in the D/H ratio of fatty acids of pelagic microorganisms

Culture studies of microorganisms have shown that the hydrogen isotopic composition of fatty acids depends on their metabolism, but there are only few environmental studies available to confirm this observation. Here we studied the seasonal variability of the deuterium/hydrogen (D/H) ratio of fatty acids in the coastal Dutch North Sea and compared this with the diversity of the phyto- and bacterioplankton. Over the year, the stable hydrogen isotopic fractionation factor epsilon between fatty acids and water ranged between -172 per mil and -237 per mil, the algal-derived polyunsaturated fatty acid nC20:5 being the most D-depleted and nC18:0 the least D-depleted fatty acid. The D-depleted nC20:5 is in agreement with culture studies, which indicates that photoautotrophic microorganisms produce fatty acids which are significantly depleted in D relative to water. The epsilon-lipid/water of all fatty acids showed a transient shift towards increased fractionation during the spring phytoplankton bloom, indicated by increasing chlorophyll a concentrations and relative abundance of the nC20:5 PUFA, suggesting increased contributions of photoautotrophy. Time periods with decreased fractionation (less negative epsilon-lipid/water values) can be explained by an increased contribution by heterotrophy to the fatty acid pool. Our results show that the hydrogen isotopic composition of fatty acids is a useful tool to assess the community metabolism of coastal plankton.

Seawater carbonate chemistry and swimming behaviors of the raphidophyte Heterosigma akashiwo in a laboratory experiment

We investigated the effects of pH on movement behaviors of the harmful algal bloom causing raphidophyte Heterosigma akashiwo. Motility parameters from >8000 swimming tracks of individual cells were quantified using 3D digital video analysis over a 6-h period in 3 pH treatments reflecting marine carbonate chemistry during the pre-industrial era, currently, and the year 2100. Movement behaviors were investigated in two different acclimation-to-target-pH conditions: instantaneous exposure and acclimation of cells for at least 11 generations. There was no negative impairment of cell motility when exposed to elevated PCO2 (i.e., low pH) conditions but there were significant behavioral responses. Irrespective of acclimation condition, lower pH significantly increased downward velocity and frequency of downward swimming cells (p < 0.001). Rapid exposure to lower pH resulted in 9% faster downward vertical velocity and up to 19% more cells swimming downwards (p < 0.001). Compared to pH-shock experiments, pre-acclimation of cells to target pH resulted in ~30% faster swimming speed and up to 46% faster downward velocities (all p < 0.001). The effect of year 2100 PCO2 levels on population diffusivity in pre-acclimated cultures was >2-fold greater than in pH-shock treatments (2.2 × 105 µm**2/s vs. 8.4 × 104 µm**2/s). Predictions from an advection-diffusion model, suggest that as PCO2 increased the fraction of the population aggregated at the surface declined, and moved deeper in the water column. Enhanced downward swimming of H. akashiwo at low pH suggests that these behavioral responses to elevated PCO2 could reduce the likelihood of dense surface slick formation of H. akashiwo through reductions in light exposure or growth independent surface aggregations. We hypothesize that the HAB alga's response to higher PCO2 may exploit the signaling function of high PCO2 as indicative of net heterotrophy in the system, thus indicative of high predation rates or depletion of nutrients.

Age determination of sediment core MD07-3088

The Southern Ocean plays a prominent role in the Earth's climate and carbon cycle. Changes in the Southern Ocean circulation may have regulated the release of CO2 to the atmosphere from a deep-ocean reservoir during the last deglaciation. However, the path and exact timing of this deglacial CO2 release are still under debate. Here we present measurements of deglacial surface reservoir 14C age changes in the eastern Pacific sector of the Southern Ocean, obtained by 14C dating of tephra deposited over the marine and terrestrial regions. These results, along with records of foraminifera benthic-planktic 14C age and d13C difference, provide evidence for three periods of enhanced upwelling in the Southern Ocean during the last deglaciation, supporting the hypothesis that Southern Ocean upwelling contributed to the deglacial rise in atmospheric CO2. These independently dated marine records suggest synchronous changes in the Southern Ocean circulation and Antarctic climate during the last deglaciation.

Geochemical data derived from an absolutely dated shell-based chronology for the Irish Sea

The identification in various proxy records of periods of rapid (decadal scale) climate change over recent millennia, together with the possibility that feedback mechanisms may amplify climate system responses to increasing atmospheric CO2, highlights the importance of a detailed understanding, at high spatial and temporal resolutions, of forcings and feedbacks within the system. Such an understanding has hitherto been limited because the temperate marine environment has lacked an absolute timescale of the kind provided by tree-rings for the terrestrial environment and by corals for the tropical marine environment. Here we present the first annually resolved, multi-centennial (489-year), absolutely dated, shell-based marine master chronology. The chronology has been constructed by detrending and averaging annual growth increment widths in the shells of multiple specimens of the very long-lived bivalve mollusc Arctica islandica, collected from sites to the south and west of the Isle of Man in the Irish Sea. The strength of the common environmental signal expressed in the chronology is fully comparable with equivalent statistics for tree-ring chronologies. Analysis of the 14C signal in the shells shows no trend in the marine radiocarbon reservoir correction (DR), although it may be more variable before ~1750. The d13C signal shows a very significant (R**2 = 0.456, p < 0.0001) trend due to the 13C Suess effect.