Carbon 14 age dating of wood samples from the Alps

Glacially deformed pieces of wood, organic lake sediments and clasts of reworked peat have been collected in front of Alpine glaciers since AD 1990. The palaeoglaciological interpretation of these organic materials is related to earlier phases of glacier recession surpassing that of today's shrunken glaciers and to tree growth and peat accumulation in the valleys now occupied by the glaciers. Glacial transport of the material is indicated by wood anatomy, incorporated silt, sand and gravel particles, missing bark and deformed treerings. A total of 65 samples have been radiocarbon dated so far, and clusters of dates provide evidence of eight phases of glacier recession: 9910-9550, 9010-7980, 7250-6500, 6170-5950, 5290-3870, 3640-3360, 2740-2620 and 1530-1170 calibrated years BP. Allowing for the timelag between climatic fluctuations, glacier response and vegetation colonization, these recession phases may lag behind climatic changes by 100-200 years.

Sedimentology of cores from the Iberian margin

Bioturbation in marine sediments has basically two aspects of interest for palaeo-environmental studies. First, the traces left by the burrowing organisms reflect the prevailing environmental conditions at the seafloor and thus can be used to reconstruct the ecologic and palaeoceanographic situation. Traces have the advantage over other proxies of practically always being preserved in situ. Secondly, for high- resolution stratigraphy, bioturbation is a nuisance due to the stirring and mixing processes that destroy the stratigraphic record. In order to evaluate the applicability of biogenic traces as palaeoenvironmental indicators, a number of gravity cores from the Portuguese continental slope, covering the period from the last glacial to the present were investigated through X-ray radiographs. In addition, physical and chemical parameters were determined to define the environmental niche in each core interval. A number of traces could be recognized, the most important being: Thalassinoides, Planolites, Zoophycos, Chondrites, Scolicia, Palaeophycus, Phycosiphon and the generally pyritized traces Trichichnus and Mycellia. The shifts between the different ichnofabrics agree strikingly well with the variations in ocean circulation caused by the changing climate. On the upper and middle slope, variations in current intensity and oxygenation of the Mediterranean Outflow Water were responsible for shifts in the ichnofabric. Larger traces such as Planolites and Thalassinoides dominated in coarse, well oxygenated intervals, while small traces such as Chondrites and Trichichnus dominated in fine grained, poorly oxygenated intervals. In contrast, on the lower slope where calm steady sedimentation conditions prevail, changes in sedimentation rate and nutrient flux have controlled variations in the distribution of larger traces such as Planolites, Thalassinoides, and Palaeophycus. Additionally, distinct layers of abundant Chondrites correspond to Heinrich events 1, 2, and 4, and are interpreted as a response to incursions of nutrient rich, oxygen depleted Antarctic waters during phases of reduced thermohaline circulation. The results clearly show that not one single factor but a combination of several factors is necessary to explain the changes in ichnofabric. Furthermore, large variations in the extent and type of bioturbation and tiering between different settings clearly show that a more detailed knowledge of the factors governing bioturbation is necessary if we shall fully comprehend how proxy records are disturbed. A first attempt to automatize a part of the recognition and quantification of the ichnofabric was performed using the DIAna image analysis program on digitized X-ray radiographs. The results show that enhanced abundance of pyritized microburrows appears to be coupled to organic rich sediments deposited under dysoxic conditions. Coarse grained sediments inhibit the formation of pyritized burrows. However, the smallest changes in program settings controlling the grey scale threshold and the sensitivity resulted in large shifts in the number of detected burrows. Therefore, this method can only be considered to be semi-quantitative. Through AMS-^C dating of sample pairs from the Zoophycos spreiten and the surrounding host sediment, age reversals of up to 3,320 years could be demonstrated for the first time. The spreiten material is always several thousands of years younger than the surrounding host sediment. Together with detailed X-ray radiograph studies this shows that the trace maker collects the material on the seafloor, and then transports it downwards up to more than one meter in to the underlying sediment where it is deposited in distinct structures termed spreiten. This clearly shows that age reversals of several thousands of years can be expected whenever Zoophycos is unknowingly sampled. These results also render the hitherto proposed ethological models proposed for Zoophycos as largely implausible. Therefore, a combination of detritus feeding, short time caching, and hibernation possibly combined also with gardening, is suggested here as an explanation for this complicated burrow.

Carbon uptake rate calculated for melt pond water samples during POLARSTERN cruise ARK-XXVII/3 (IceArc) in 2012

Net Primary Production was measured using the 14**C uptake method with minor modifications. Melt pond samples were spiked with 0.1µCi ml**-1 of 14**C labelled sodium bicarbonate (Moravek Biochemicals, Brea, USA) and distributed in 10 clear bottles (20 ml each). Subsequently they were incubated for 12 h at -1.3°C under different scalar irradiances (0-420 µmol photons m**-2 s**-1) measured with a spherical sensor (Spherical Micro Quantum Sensor US-SQS/L, Heinz Walz, Effeltrich, Germany). At the end of the incubation, samples were filtered onto 0.2 µm nitrocellulose filters and the particulate radioactive carbon uptake was determined by liquid scintillation counting using Filter count scintillation cocktail (Perkin Elmer, Waltham, USA). The carbon uptake values in the dark were subtracted from the carbon uptake values measured in the light incubations. Dissolved inorganic carbon (DIC) was measured for each sample using the flow injection system (Hall and Aller, 1992). The DIC concentration was taken into account to calculate the amount of labeled bicarbonate incorporated into the cell. Carbon fixation rates were normalized volumetrically and by chlorophyll a. Photosynthesis-irradiance curves (PI curves) were fitted using MATLAB® according to the equation proposed by Platt et al. (1980) including a photoinhibition parameter (beta) and providing the main photosynthetic parameters: maximum Chla normalized carbon fixation rate if there were no photoinhibition (Pb) and the initial slope of the saturation curve (alpha). The derived parameters: light intensity at which photosynthesis is maximal (Im), the carbon fixation rate at that maximal irradiance (Pbm) and the adaptation parameter or photoacclimation index (Ik) were calculated according to Platt et al. (1982).

Experiment: Organic matter exudation by Emiliania huxleyi under simulated future ocean conditions

Emiliania huxleyi (strain B 92/11) was exposed to different nutrient supply, CO2 and temperature conditions in phosphorus controlled chemostats to investigate effects on organic carbon exudation and partitioning between the pools of particulate organic carbon (POC) and dissolved organic carbon (DOC). 14C incubation measurements for primary production (PP) and extracellular release (ER) were performed. Chemical analysis included the amount and composition of high molecular weight (>1 kDa) dissolved combined carbohydrates (HMW-dCCHO), particulate combined carbohydrates (pCCHO) and the carbon content of transparent exopolymer particles (TEP-C). Applied CO2 and temperature conditions were 300, 550 and 900 µatm pCO2 at 14 °C, and additionally 900 µatm pCO2 at 18 °C simulating a greenhouse ocean scenario. Enhanced nutrient stress by reducing the dilution rate (D) from D = 0.3 /d to D = 0.1 /d (D = µ) induced the strongest response in E. huxleyi. At µ = 0.3 /d, PP was significantly higher at elevated CO2 and temperature and DO14C production correlated to PO14C production in all treatments, resulting in similar percentages of extracellular release (PER; (DO14C production/PP) × 100) averaging 3.74 ± 0.94%. At µ = 0.1 /d, PO14C production decreased significantly, while exudation of DO14C increased. Thus, indicating a stronger partitioning from the particulate to the dissolved pool. Maximum PER of 16.3 ± 2.3% were observed at µ = 0.1 /d at elevated CO2 and temperature. While cell densities remained constant within each treatment and throughout the experiment, concentrations of HMW-dCCHO, pCCHO and TEP were generally higher under enhanced nutrient stress. At µ= 0.3 /d, pCCHO concentration increased significantly with elevated CO2 and temperature. At µ = 0.1 /d, the contribution (mol % C) of HMW-dCCHO to DOC was lower at elevated CO2 and temperature while pCCHO and TEP concentrations were higher. This was most pronounced under greenhouse conditions. Our findings suggest a stronger transformation of primary produced DOC into POC by coagulation of exudates under nutrient limitation. Our results further imply that elevated CO2 and temperature will increase exudation by E. huxleyi and may affect organic carbon partitioning in the ocean due to an enhanced transfer of HMW-dCCHO to TEP by aggregation processes.

Carbon uptake rate calculated for CTD water samples during POLARSTERN cruise ARK-XXVII/3 (IceArc) in 2012

Net Primary Production was measured using the 14**C uptake method with minor modifications. Seawater samples were spiked with 0.1µCi ml**-1 of 14**C labelled sodium bicarbonate (Moravek Biochemicals, Brea, USA) and distributed in 10 clear bottles (20 ml each). Subsequently they were incubated for 12 h at -1.3°C under different scalar irradiances (0-420 µmol photons m**-2 s**-1) measured with a spherical sensor (Spherical Micro Quantum Sensor US-SQS/L, Heinz Walz, Effeltrich, Germany). At the end of the incubation, samples were filtered onto 0.2 µm nitrocellulose filters and the particulate radioactive carbon uptake was determined by liquid scintillation counting using Filter count scintillation cocktail (Perkin Elmer, Waltham, USA). The carbon uptake values in the dark were subtracted from the carbon uptake values measured in the light incubations. Dissolved inorganic carbon (DIC) was measured for each sample using the flow injection system (Hall and Aller, 1992). The DIC concentration was taken into account to calculate the amount of labeled bicarbonate incorporated into the cell. Carbon fixation rates were normalized volumetrically and by chlorophyll a. Photosynthesis-irradiance curves (PI curves) were fitted using MATLAB® according to the equation proposed by Platt et al. (1980) including a photoinhibition parameter (beta) and providing the main photosynthetic parameters: maximum Chla normalized carbon fixation rate if there were no photoinhibition (Pb) and the initial slope of the saturation curve (alpha). The derived parameters: light intensity at which photosynthesis is maximal (Im), the carbon fixation rate at that maximal irradiance (Pbm) and the adaptation parameter or photoacclimation index (Ik) were calculated according to Platt et al. (1982).

Strong shift from HCO3- to CO2 uptake in Emiliania huxleyi with acidification: new approach unravels acclimation versus short-term pH effects

Effects of ocean acidification on Emiliania huxleyi strain RCC 1216 (calcifying, diploid life-cycle stage) and RCC 1217 (non-calcifying, haploid life-cycle stage) were investigated by measuring growth, elemental composition, and production rates under different pCO2 levels (380 and 950 µatm). In these differently acclimated cells, the photosynthetic carbon source was assessed by a (14)C disequilibrium assay, conducted over a range of ecologically relevant pH values (7.9-8.7). In agreement with previous studies, we observed decreased calcification and stimulated biomass production in diploid cells under high pCO2, but no CO2-dependent changes in biomass production for haploid cells. In both life-cycle stages, the relative contributions of CO2 and HCO3 (-) uptake depended strongly on the assay pH. At pH values =< 8.1, cells preferentially used CO2 (>= 90 % CO2), whereas at pH values >= 8.3, cells progressively increased the fraction of HCO3 (-) uptake (~45 % CO2 at pH 8.7 in diploid cells; ~55 % CO2 at pH 8.5 in haploid cells). In contrast to the short-term effect of the assay pH, the pCO2 acclimation history had no significant effect on the carbon uptake behavior. A numerical sensitivity study confirmed that the pH-modification in the (14)C disequilibrium method yields reliable results, provided that model parameters (e.g., pH, temperature) are kept within typical measurement uncertainties. Our results demonstrate a high plasticity of E. huxleyi to rapidly adjust carbon acquisition to the external carbon supply and/or pH, and provide an explanation for the paradoxical observation of high CO2 sensitivity despite the apparently high HCO3 (-) usage seen in previous studies.

Carbon uptake rate calculated for sea-ice core samples during POLARSTERN cruise ARK-XXVII/3 (IceArc) in 2012

Net Primary Production was measured using the 14**C uptake method with minor modifications. Melted sea ice samples were spiked with 0.1µCi ml**-1 of 14**C labelled sodium bicarbonate (Moravek Biochemicals, Brea, USA) and distributed in 10 clear bottles (20 ml each). Subsequently they were incubated for 12 h at -1.3°C under different scalar irradiances (0-420 µmol photons m**-2 s**-1) measured with a spherical sensor (Spherical Micro Quantum Sensor US-SQS/L, Heinz Walz, Effeltrich, Germany). At the end of the incubation, samples were filtered onto 0.2 µm nitrocellulose filters and the particulate radioactive carbon uptake was determined by liquid scintillation counting using Filter count scintillation cocktail (Perkin Elmer, Waltham, USA). The carbon uptake values in the dark were subtracted from the carbon uptake values measured in the light incubations. Dissolved inorganic carbon (DIC) was measured for each sample using the flow injection system (Hall and Aller, 1992). The DIC concentration was taken into account to calculate the amount of labeled bicarbonate incorporated into the cell. Carbon fixation rates were normalized volumetrically and by chlorophyll a. Photosynthesis-irradiance curves (PI curves) were fitted using MATLAB® according to the equation proposed by Platt et al. (1980) including a photoinhibition parameter (beta) and providing the main photosynthetic parameters: maximum Chla normalized carbon fixation rate if there were no photoinhibition (Pb) and the initial slope of the saturation curve (alpha). The derived parameters: light intensity at which photosynthesis is maximal (Im), the carbon fixation rate at that maximal irradiance (Pbm) and the adaptation parameter or photoacclimation index (Ik) were calculated according to Platt et al. (1982).

Detection of a variable intracellular acid-labile carbon pool in Thalassiosira weissflogii (Heterokontophyta) and Emiliania huxleyi (Haptophyta) in response to changes in the seawater carbon system

Accumulation of an intracellular pool of carbon (C(i) pool) is one strategy by which marine algae overcome the low abundance of dissolved CO2 (CO2 (aq) ) in modern seawater. To identify the environmental conditions under which algae accumulate an acid-labile C(i) pool, we applied a (14) C pulse-chase method, used originally in dinoflagellates, to two new classes of algae, coccolithophorids and diatoms. This method measures the carbon accumulation inside the cells without altering the medium carbon chemistry or culture cell density. We found that the diatom Thalassiosira weissflogii [(Grunow) G. Fryxell & Hasle] and a calcifying strain of the coccolithophorid Emiliania huxleyi [(Lohmann) W. W. Hay & H. P. Mohler] develop significant acid-labile C(i) pools. C(i) pools are measureable in cells cultured in media with 2-30 µmol/l CO2 (aq), corresponding to a medium pH of 8.6-7.9. The absolute C(i) pool was greater for the larger celled diatoms. For both algal classes, the C(i) pool became a negligible contributor to photosynthesis once CO2 (aq) exceeded 30 µmol/l. Combining the (14) C pulse-chase method and (14) C disequilibrium method enabled us to assess whether E. huxleyi and T. weissflogii exhibited thresholds for foregoing accumulation of DIC or reduced the reliance on bicarbonate uptake with increasing CO2 (aq) . We showed that the C(i) pool decreases with higher CO2 :HCO3 (-) uptake rates.

Planktic foraminiferal and sea surface temperature record during the last 1 Myr across the Subtropical Front, Southwest Pacific

Planktic foraminiferal faunas and modern analogue technique estimates of sea surface temperature (SST) for the last 1 million years (Myr) are compared between core sites to the north (ODP 1125, 178 faunas) and south (DSDP 594, 374 faunas) of the present location of the Subtropical Front (STF), east of New Zealand. Faunas beneath cool subtropical water (STW) north of the STF are dominated by dextral Neogloboquadrina pachyderma, Globorotalia inflata, and Globigerina bulloides, whereas faunas to the south are strongly dominated by sinistral N. pachyderma (80-95% in glacials), with increased G. bulloides (20-50%) and dextral N. pachyderma (15-50%) in interglacials (beneath Subantarctic Water, or SAW). Canonical correspondence analysis indicates that at both sites, SST and related factors were the most important environmental influences on faunal composition. Greater climate-related faunal fluctuations occur in the south. Significant faunal changes occur through time at both sites, particularly towards the end of the mid-Pleistocene climate transition, MIS18-15 (e.g., decline of Globorotalia crassula in STW, disappearance of Globorotalia puncticulata in SAW), and during MIS8-5. Interglacial SST estimates in the north are similar to the present day throughout the last 1 Myr. To the south, interglacial SSTs are more variable with peaks 4-7 °C cooler than present through much of the early and middle Pleistocene, but in MIS11, MIS5.5, and early MIS1, peaks are estimated to have been 2-4 °C warmer than present. These high temperatures are attributed to southward spread of the STF across the submarine Chatham Rise, along which the STF appears to have been dynamically positioned throughout most of the last 1 Myr. For much of the last 1 Myr, glacial SST estimates in the north were only 1-2 °C cooler than the present interglacial, except in MIS16, MIS8, MIS6, and MIS4-2 when estimates are 4-7 °C cooler. These cooler temperatures are attributed to jetting of SAW through the Mernoo Saddle (across the Chatham Rise) and/or waning of the STW current. To the south, glacial SST estimates were consistently 10-11 °C cooler than present, similar to temperatures and faunas currently found in the vicinity of the Polar Front. One interpretation is that these cold temperatures reflect thermocline changes and increased Circumpolar Surface Water spinning off the Subantarctic Front as an enhanced Bounty Gyre along the south side of the Chatham Rise. For most of the last 1 Myr, the temperature gradient across the STF has been considerably greater than the present 4 °C. During glacial episodes, the STF in this region did not migrate northwards, but instead there was an intensification of the temperature gradient across it (interglacials 4-11 °C; glacials 8-14 °C).

Rare earth element concentrations and geochemistry of carbonate minerals from the Logatchev Hydrothermal Field and the Gakkel Ridge

The ultramafic-hosted Logatchev Hydrothermal Field (LHF) at 15°N on the Mid-Atlantic Ridge and the Arctic Gakkel Ridge (GR) feature carbonate precipitates (aragonite, calcite, and dolomite) in voids and fractures within different types of host rocks. We present chemical and Sr isotopic compositions of these different carbonates to examine the conditions that led to their formation. Our data reveal that different processes have led to the precipitation of carbonates in the various settings. Seawater-like 87Sr/86Sr ratios for aragonite in serpentinites (0.70909 to 0.70917) from the LHF are similar to those of aragonite from the GR (0.70912 to 0.70917) and indicate aragonite precipitation from seawater at ambient conditions at both sites. Aragonite veins in sulfide breccias from LHF also have seawater-like Sr isotope compositions (0.70909 to 0.70915), however, their rare earth element (REE) patterns show a clear positive europium (Eu) anomaly indicative of a small (< 1%) hydrothermal contribution. In contrast to aragonite, dolomite from the LHF has precipitated at much higher temperatures (~100 °C), and yet its 87Sr/86Sr ratios (0.70896 to 0.70907) are only slightly lower than those of aragonite. Even higher temperatures are calculated for the precipitation of deformed calcite veins in serpentine-talc fault schists form north of the LHF. These calcites show unradiogenic 87Sr/86Sr ratios (0.70460 to 0.70499) indicative of precipitation from evolved hydrothermal fluids. A simple mixing model based on Sr mass balance and enthalpy conservation indicates strongly variable conditions of fluid mixing and heat transfers involved in carbonate formation. Dolomite precipitated from a mixture of 97% seawater and 3% hydrothermal fluid that should have had a temperature of approximately 14 °C assuming that no heat was transferred. The much higher apparent precipitation temperatures based on oxygen isotopes (~ 100 °C) may be indicative of conductive heating, probably of seawater prior to mixing. The hydrothermal calcite in the fault schist has precipitated from a mixture of 67% hydrothermal fluid and 33% seawater, which should have had an isenthalpic mixing temperature of ~ 250 °C. The significantly lower temperatures calculated from oxygen isotopes are likely due to conductive cooling of hydrothermal fluid discharging along faults. Rare earth element patterns corroborate the results of the mixing model, since the hydrothermal calcite, which formed from waters with the greatest hydrothermal contribution, has REE patterns that closely resemble those of vent fluids from the LHF. Our results demonstrate, for the first time, that (1) precipitation from pure seawater, (2) conductive heating of seawater, and (3) conductive cooling of hydrothermal fluids in the sub-seafloor all can lead to carbonate precipitation within a single ultramafic-hosted hydrothermal system.

Seawater carbonate chemistry and biological processes of Emiliania huxleyi (PML B92/11) during experiments, 2011

The present study investigates the combined effect of phosphorous limitation, elevated partial pressure of CO2 (pCO2) and temperature on a calcifying strain of Emiliania huxleyi (PML B92/11) by means of a fully controlled continuous culture facility. Two levels of phosphorous limitation were consecutively applied by renewal of culture media (N:P = 26) at dilution rates (D) of 0.3 d- and 0.1 d-1. CO2 and temperature conditions were 300, 550 and 900 µatm pCO2 at 14 °C and 900 µatm pCO2 at 18 °C. In general, the steady state cell density and particulate organic carbon (POC) production increased with pCO2, yielding significantly higher concentrations in cultures grown at 900 µatm pCO2 compared to 300 and 550 µatm pCO2. At 900 µatm pCO2, elevation of temperature as expected for a greenhouse ocean, further increased cell densities and POC concentrations. In contrast to POC concentration, C-quotas (pmol C cell-1) were similar at D = 0.3 d-1 in all cultures. At D = 0.1 d-1, a reduction of C-quotas by up to 15% was observed in the 900 µatm pCO2 at 18 °C culture. As a result of growth rate reduction, POC:PON:POP ratios deviated strongly from the Redfield ratio, primarily due to an increase in POC. Ratios of particulate inorganic and organic carbon (PIC:POC) ranged from 0.14 to 0.18 at D = 0.3 d-1, and from 0.11 to 0.17 at D = 0.1 d-1, with variations primarily induced by the changes in POC. At D = 0.1 d-1, cell volume was reduced by up to 22% in cultures grown at 900 µatm pCO2. Our results indicate that changes in pCO2, temperature and phosphorus supply affect cell density, POC concentration and size of E. huxleyi (PML B92/11) to varying degrees, and will likely impact bloom development as well as biogeochemical cycling in a greenhouse ocean.