Osmium, and stable carbon and oxygen isotope record accross the PETM

In the latest Paleocene an abrupt shift to more negative d13C values has been documented at numerous marine and terrestrial sites (Bralower et al., 1997, doi:10.1130/0091-7613(1997)025<0963:HRROTL>2.3.CO;2; Cramer et al., 1999; Kaiho et al., 1996, doi:10.1029/96PA01021; Kennett and Stott, 1991, doi:10.1038/353225a0; Koch et al., 1992, doi:10.1038/358319a0; Stott et al., 1996; Thomas and Shackleton, 1996, doi:10.1144/GSL.SP.1996.101.01.20; Zachos et al., 1993). This carbon isotope event (CIE) is coincident with oxygen isotope data that indicate warming of surface waters at high latitudes of nearly 4°-6°C (Kennett and Stott, 1991, doi:10.1038/353225a0) and more moderate warming in the subtropics (Thomas et al., 1999, doi:10.1029/1999PA900031). Here we report 187Os/188Os isotope records from the North Atlantic and Indian Oceans which demonstrate a >10% increase in the 187Os/188Os ratio of seawater coincident with the late Paleocene CIE. This excursion to higher 187Os/188Os ratios is consistent with a global increase in weathering rates. The inference of increased chemical weathering during this interval of unusual warmth is significant because it provides empirical evidence supporting the operation of a feedback between chemical weathering rates and warm global climate, which acts to stabilize Earth's climate (Walker et al., 1981). Estimates of the duration of late Paleocene CIE (Bains et al., 1999, doi:10.1126/science.285.5428.724; Bralower et al., 1997, doi:10.1130/0091-7613(1997)025<0963:HRROTL>2.3.CO;2; Norris and Röhl, 1999, doi:10.1038/44545; Röhl et al., 2000, doi:10.1130/0091-7613(2000)28<927:NCFTLP>2.0.CO;2) in conjunction with the Os isotope data imply that intensified chemical weathering in response to warm, humid climates can occur on timescales of 104-105 years. This interpretation requires that the late Paleocene thermal maximum Os isotope excursion be produced mainly by increased Os flux to the ocean rather than a transient excursion to higher 187Os/188Os ratios in river runoff. Although we argue that the former is more likely than the latter, we cannot rule out significant changes in the 187Os/188Os ratio of rivers.

Dissolved organic matter in the Lena Delta in 2009

Large Arctic rivers discharge significant amounts of dissolved organic matter (DOM) into the Arctic Ocean. We sampled natural waters of the Lena River, the Buor-Khaya Bay (Laptev Sea), permafrost melt water creeks, ice complex melt water creeks and a lake. The goal of this study was to characterize the molecular DOM composition with respect to different water bodies within the Lena Delta. We aimed at an identification of source-specific DOM molecular markers and their relative contribution to DOM of different origin. The molecular characterization was performed for solid-phase extracted DOM by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Average dissolved organic carbon concentrations in the original samples were 490±75 µmol C/L for riverine and bay samples and 399±115 µmol C/L for permafrost melt water creeks. Average TDN concentrations were elevated in the permafrost melt waters (19.7±7.1 µmol N/L) in comparison to the river and the bay (both 13.2±2.6 µmol N/L). FT-ICR MS and statistical tools demonstrated that the origin of DOM in the Lena Delta was systematically reflected in its molecular composition. Magnitude weighted parameters calculated from MS data (O/Cwa, H/Cwa, C/Nwa) highlighted preliminary sample discrimination. The highest H/Cwa of 1.315 was found for DOM in melt water creeks in comparison to 1.281 for river and 1.230 for the bay samples. In the bay samples we observed a higher fraction of oxygen-rich components which was reflected in an O/Cwa ratio of 0.445 in comparison to 0.425 and 0.427 in the river and creeks, respectively. From the southernmost location to the bay a relative depletion of nitrogenous molecular markers and an enrichment of oxidized DOM components occurred. The highest contribution of nitrogenous components was indicative for creeks reflected in a C/Nwa of 104 in comparison to 143 and 176 in the river and bay, respectively. These observations were studied on a molecular formula level using principal component and indicator value analyses. The results showed systematic differences with respect to water origin and constitute an important basis for a better mechanistic understanding of DOM transformations in the changing Arctic rivers.

The effects of elevated CO2 on the growth and toxicity of field populations and cultures of the saxitoxin-producing dinoflagellate, Alexandrium fundyense

The effects of coastal acidification on the growth and toxicity of the saxitoxin-producing dinoflagellate Alexandrium fundyense were examined in culture and ecosystem studies. In culture experiments, Alexandrium strains isolated from Northport Bay, New York, and the Bay of Fundy, Canada, grew significantly faster (16-190%; p < 0.05) when exposed to elevated levels of PCO2 ( 90-190 Pa=900-1900 µatm) compared to lower levels ( 40 Pa=400 µatm). Exposure to higher levels of PCO2 also resulted in significant increases (71-81%) in total cellular toxicity (fg saxitoxin equivalents/cell) in the Northport Bay strain, while no changes in toxicity were detected in the Bay of Fundy strain. The positive relationship between PCO2 enrichment and elevated growth was reproducible in natural populations from New York waters. Alexandrium densities were significantly and consistently enhanced when natural populations were incubated at 150 Pa PCO2 compared to 39 Pa. During natural Alexandrium blooms in Northport Bay, PCO2 concentrations increased over the course of a bloom to more than 170 Pa and were highest in regions with the greatest Alexandrium abundances, suggesting Alexandrium may further exacerbate acidification and/or be especially adapted to these acidi-fied conditions. The co-occurrence of Alexandrium blooms and elevated PCO2 represents a previously unrecognized, compounding environmental threat to coastal ecosystems. The ability of elevated PCO2 to enhance the growth and toxicity of Alexandrium indicates that acidification promoted by eutrophication or climate change can intensify these, and perhaps other, harmful algal blooms.

Morphology of Orbulina universa and Globorotalia scitula across local extinctions during Sapropel S5 (Eastern Mediterranean Sea, c.126-121 ka)

Extinction is a remarkably difficult phenomenon to study under natural conditions. This is because the outcome of stress exposure and associated fitness reduction is not known until the extinction occurs and it remains unclear whether there is any phenotypic reaction of the exposed population that can be used to predict its fate. Here we take advantage of the fossil record, where the ecological outcome of stress exposure is known. Specifically, we analyze shell morphology of planktonic Foraminifera in sediment samples from the Mediterranean, during an interval preceding local extinctions. In two species representing different plankton habitats, we observe shifts in trait state and decrease in variance in association with non-terminal stress, indicating stabilizing selection. At terminal stress levels, immediately before extinction, we observe increased growth asymmetry and trait variance, indicating disruptive selection and bet-hedging. The pre-extinction populations of both species show a combination of trait states and trait variance distinct from all populations exposed to non-terminal levels of stress. This finding indicates that the phenotypic history of a population may allow the detection of threshold levels of stress, likely to lead to extinction. It is thus an alternative to population dynamics in studying and monitoring natural population ecology.

Organic matter and sediment properties of samples from site GeoB15105 from the Black Sea

Dissolved organic matter (DOM) in marine sediments is a complex mixture of thousands of individual constituents that participate in biogeochemical reactions and serve as substrates for benthic microbes. Knowledge of the molecular composition of DOM is a prerequisite for a comprehensive understanding of the biogeochemical processes in sediments. In this study, interstitial water DOM was extracted with Rhizon samplers from a sediment core from the Black Sea and compared to the corresponding water-extractable organic matter fraction (<0.4 µm) obtained by Soxhlet extraction, which mobilizes labile particulate organic matter and DOM. After solid phase extraction (SPE) of DOM, samples were analyzed for the molecular composition by Fourier Transform Ion-Cyclotron Resonance Mass Spectrometry (FT-ICR MS) with electrospray ionization in negative ion mode. The average SPE extraction yield of the dissolved organic carbon (DOC) in interstitial water was 63%, whereas less than 30% of the DOC in Soxhlet-extracted organic matter was recovered. Nevertheless, Soxhlet extraction yielded up to 4.35% of the total sedimentary organic carbon, which is more than 30-times the organic carbon content of the interstitial water. While interstitial water DOM consisted primarily of carbon-, hydrogen- and oxygen-bearing compounds, Soxhlet extracts yielded more complex FT-ICR mass spectra with more peaks and higher abundances of nitrogen- and sulfur-bearing compounds. The molecular composition of both sample types was affected by the geochemical conditions in the sediment; elevated concentrations of HS- promoted the early diagenetic sulfurization of organic matter. The Soxhlet extracts from shallow sediment contained specific three- and four-nitrogen-bearing molecular formulas that were also detected in bacterial cell extracts and presumably represent proteinaceous molecules. These compounds decreased with increasing sediment depth while one- and two-nitrogen-bearing molecules increased, resulting in a higher similarity of both sample types in the deep sediment. In summary, Soxhlet extraction of sediments accessed a larger and more complex pool of organic matter than present in interstitial water DOM.

Quantification and molecular characterization of dissolved organic sulfur in water samples obtained during POLARSTERN cruise ANT-XXV (PS73) to the East Atlantic and the Southern Ocean

Although sulfur is an essential element for marine primary production and critical for climate processes, little is known about the oceanic pool of non-volatile dissolved organic sulfur (DOS). We present a basin-scale distribution of solid phase extractable DOS in the East Atlantic Ocean and the Atlantic sector of the Southern Ocean. While molar DOS versus dissolved organic nitrogen (DON) ratios of 0.11 ± 0.024 in Atlantic surface water resembled phytoplankton stoichiometry (S/N ~ 0.08), increasing dissolved organic carbon (DOC) versus DOS ratios and decreasing methionine-S yield demonstrated selective DOS removal and active involvement in marine biogeochemical cycles. Based on stoichiometric estimates, the minimum global inventory of marine DOS is 6.7 Pg S, exceeding all other marine organic sulfur reservoirs by an order of magnitude.