Nitrogen isotopes of bulk sediments for OAE2 samples

Sediment records of the stable isotopic composition of N (d15N) show light d15N values at several sites in the proto-North Atlantic during Oceanic Anoxic Event 2 (OAE 2) at the Cenomanian-Turonian transition (~94 Ma). The low d15N during the event is generally attributed to an increase in N2-fixation and incomplete uptake of ammonium for phytoplankton growth. A compilation of all reliable data for the proto North-Atlantic during OAE 2 demonstrates that the most pronounced negative shift in d15N from pre-OAE 2 to OAE 2 occurs in the open ocean, but with d15N never lower than -3 ppm. Using a box model of N cycling for the proto-North Atlantic during OAE 2, we show that N2-fixation is a major contributor to the d15N signal, especially in the open ocean. Incomplete uptake of ammonium for phytoplankton growth is important in regions dominated by downwelling, with lateral transport of ammonium acting as a major source. In the southern proto-North Atlantic, where bottom waters were euxinic, the light d15N signature is largely explained by upwelling of ammonium . Our study provides an overview of regional differences in d15N in the proto-North Atlantic and highlights the role of lateral exchange of water and nutrients, in addition to local biogeochemical processes, in determining d15N values of OAE 2 sediments.

Calcium isotopes in planktonic foraminifera - core tops and sediment trap samples

For paleoceanographic studies, it is important to understand the processes that influence the calcium (Ca) isotopic composition of foraminiferal calcite tests preserved in the sediment record. Seven species of planktonic foraminifera from coretop sediments collectively exhibited a Ca temperature dependent fractionation of 0.013 per mil per °C. This is in agreement with previously published estimates for most species of planktonic foraminifera as well as biogenic and inorganic calcite and aragonite. Four species of planktonic foraminifera collected from a sediment trap showed a considerable amount of scatter and no consistent temperature dependent fractionation. Analyzed size fractions of coretop samples show no significant relationship with d44/40Ca. However, preliminary results suggest that the symbiotic and spinose foraminifera G. sacculifer might exhibit a relationship between test size and d44/40Ca. A one-box model in which Ca isotopes are allowed to fractionate by Rayleigh distillation from a biomineralization reservoir (internal pool) was used to constrain the isotopic composition of the original biomineralization Ca reservoir, assuming around 85% of the Ca reservoir is precipitated and the fractionation factor during precipitation is 0.9985 + 0.00002(T ºC). To explain the foraminiferal Ca isotope data, this model indicates that the Ca isotopic composition of the biomineralization reservoir is offset from seawater (approximately -0.8per mil).

Porewater and particulate geochemistry during Maria S. Merian cruise MSM17/4

We present sedimentary geochemical data and in situ benthic flux measurements of dissolved inorganic nitrogen (DIN: NO3-, NO2-, NH4+) and oxygen (O2) from 7 sites with variable sand content along 18°N offshore Mauritania (NW Africa). Bottom water O2 concentrations at the shallowest station were hypoxic (42 µM) and increased to 125 µM at the deepest site (1113 m). Total oxygen uptake rates were highest on the shelf (-10.3 mmol O2 /m2 d) and decreased quasi-exponentially with water depth to -3.2 mmol O2 /m2 d. Average denitrification rates estimated from a flux balance decreased with water depth from 2.2 to 0.2 mmol N /m2 d. Overall, the sediments acted as net sink for DIN. Observed increases in delta 15NNO3 and delta 18ONO3 in the benthic chamber deployed on the shelf, characterized by muddy sand, were used to calculate apparent benthic nitrate fractionation factors of 8.0 pro mille (15epsilon app) and 14.1 pro mille (18epsilon app). Measurements of delta 15NNO2 further demonstrated that the sediments acted as a source of 15N depleted NO2-. These observations were analyzed using an isotope box model that considered denitrification and nitrification of NH4+ and NO2-. The principal findings were that (i) net benthic 14N/15N fractionation (epsilon DEN) was 12.9 ± 1.7pro mille, (ii) inverse fractionation during nitrite oxidation leads to an efflux of isotopically light NO2- (-22 ± 1.9 pro mille), and (iii) direct coupling between nitrification and denitrification in the sediment is negligible. Previously reported epsilon DEN for fine-grained sediments are much lower (4-8 pro mille). We speculate that high benthic nitrate fractionation is driven by a combination of enhanced porewater-seawater exchange in permeable sediments and the hypoxic, high productivity environment. Although not without uncertainties, the results presented could have important implications for understanding the current state of the marine N cycle.

(Table S1) Age determination of ODP Site 165-1002

A series of 14C measurements in Ocean Drilling Program cores from the tropical Cariaco Basin, which have been correlated to the annual-layer counted chronology for the Greenland Ice Sheet Project 2 (GISP2) ice core, provides a high-resolution calibration of the radiocarbon time scale back to 50,000 years before the present. Independent radiometric dating of events correlated to GISP2 suggests that the calibration is accurate. Reconstructed 14C activities varied substantially during the last glacial period, including sharp peaks synchronous with the Laschamp and Mono Lake geomagnetic field intensity minimal and cosmogenic nuclide peaks in ice cores and marine sediments. Simulations with a geochemical box model suggest that much of the variability can be explained by geomagnetically modulated changes in 14C production rate together with plausible changes in deep-ocean ventilation and the global carbon cycle during glaciation.

Stable isotope record of Cibicidoides wuellerstorfi from Pleistocene sediments of DSDP Site 86-502 in the Caribbean Sea

Variations in the stable isotopic composition of benthic foraminifera from Deep-Sea Drilling Project (DSDP) site 502B in the Caribbean Sea are used to reconstruct Atlantic intermediate water circulation variability over the last 1.2 m.y. Comparison of this record with other North Atlantic benthic isotope records indicates that Atlantic intermediate water circulation was relatively enhanced during glacial maxima when North Atlantic deep water (NADW) production was reduced. However, a simple, compensatory relationship between intermediate and deepwater circulation is not apparent. Geochemical models have shown that such changes in ocean circulation can affect atmospheric CO2 levels by changing vertical nutrient and alkalinity profiles. The Delta delta13C difference between Caribbean site 502B and deep equatorial Pacific site 677 is highly coherent and in phase with ice volume. Like the delta18O record, there is an increase in amplitude (40%) and a large increase in 100 kyr power after 0.7 Ma. The 1.2? Delta delta13C amplitude scales to 70 ppm V in atmospheric CO2 using Boyle's (1986) box model result. The implied increase in CO2 amplitude after 0.7 Ma may suggest a positive feedback role in effecting the higher-amplitude climatic fluctuations which characterize the last 0.7 m.y.

Mean current and temperature data from the Gulf of Cádiz

During "Meteor" cruise 23 in spring 1971 intensive investigations of the Mediterranean outflow in the Gulf of Cidiz were carried out. In order to give a budget of the inflow and outflow numerous CTD-stations were taken. The observations also included six moored current meter arrays deployed in the known outflow channels. The considerations given here are based mainly on three hydrographic sections, current meter records averaged over one month, and geological observations from the bed forms beneath the Mediterranean undercurrent. The results show that the outflow essentially is determined by the bathymetry of the area. At least four separate outflow channels could be confirmed. The volumentric transport rates of three of them were calculated. These channels are the northerly near shelf branch (0.40 * 10**6 m**3 * sec**-1), the main branch (1.39 * 10**6 m**3 * sec**-1) in southwesterly direction, and an intermediate branch (0.24 * 10**6 m**3 * sec**-1) found between both. In a static box model the progressive mixing of 0.95 * 10**6 m**3 * sec**-1 pure Mediterranean Water with 1.97 * 10**6 m**3 * sec**-1 North Atlantic Central Water is demonstrated.

Nutrients of pore water in sediments of the central equatorial Pacific

Shipboard whole-core squeezing was used to measure pore water concentration vs depth profiles of [NO3]-, O2 and SiO2 at 12 stations in the equatorial Pacific along a transect from 15°S to 11°N at 135°W. The [NO3]- and SiO2 profiles were combined with fine-scale resistivity and porosity measurements to calculate benthic fluxes. After using O2 profiles, coupled with the [NO3]- profiles, to constrain the C:N of the degrading organic matter, the [NO3]- fluxes were converted to benthic organic carbon degradation rates. The range in benthic organic carbon degradation rates is 7-30 ?mol cm**-2 y**-1, with maximum values at the equator and minimum values at the southern end of the transect. The zonal trend of benthic degradation rates, with its equatorial maximum and with elevated values skewed to the north of the equator, is similar to the pattern of primary production observed in the region. Benthic organic carbon degradation is 1-2% of primary production. The range of benthic biogenic silica dissolution rates is 6.9-20 µmol cm**-2 y**-1, representing 2.5-5% of silicon fixation in the surface ocean of the region. Its zonal pattern is distinctly different from that of organic carbon degradation: the range in the ratio of silica dissolution to carbon degradation along the transect is 0.44-1.7 mol Si mol C**-1, with maximum values occurring between 12°S and 2°S, and with fairly constant values of 0.5-0.7 north of the equator. A box model calculation of the average lifetime of the organic carbon in the upper 1 cm of the sediments, where 80 +/- 11% of benthic organic carbon degradation occurs, indicates that it is short: from 3.1 years at high flux stations to 11 years at low flux stations. The reactive component of the organic matter must have a shorter lifetime than this average value. In contrast, the average lifetime of biogenic silica in the upper centimeter of these sediments is 55 +/- 28 years, and shows no systematic variations with benthic flux.

(Table 3) Mediterranean core-top d18O values for various planktonic foraminiferal species

A box model is presented to simulate changes in Mediterranean long-term average salinity and d18O over the past 20,000 years. Simulations are validated by comparison with observations. Sensitivity tests illustrate robustness with respect to the main assumptions and uncertainties. The results show that relative humidity over the Mediterranean remained relatively constant around 70%, apparently narrowly constrained to the lower end of the range observed globally over sea surfaces by the basin's land-locked character. Isotopic depletion in run off, relative to the present, is identified as the main potential cause of depletions in the Mediterranean d18O record. Also, slight increases in relative humidity (of the order of 5%) might have caused very pronounced isotopic depletions, such as that in sapropel S5 of the penultimate interglacial maximum. The model shows distinctly non proportional responses of d18O and salinity to environmental change, which argues against the use of isotope residuals in Mediterranean paleosalinity reconstructions.

Methane concentrations and methane oxidation rates from June 2012 - June 2013 in the Elbe Estuary, from Hamburg to Cuxhaven, Germany

Rivers represent a transition zone between terrestric and aquatic environments, and between methane rich and methane poor environments. The Elbe River is one of the important rivers draining into the North Sea and with the Elbe potentially high amounts of methane could be imported into the water column of the North Sea. Twelve cruises from October 2010 until June 2013 were conducted from Hamburg towards the Elbe mouth at Cuxhaven. The dynamic of methane concentration in the water column and its consumption via methane oxidation was measured. In addition, physico-chemical parameters were used to estimate their influence on the methanotrophic activity. We observed high methane concentrations at the stations in the area of Hamburg harbor ("inner estuary") and about 10 times lower concentrations in the outer estuary (median of 416 versus 40 nmol/L). The methane oxidation (MOX) rate mirrowed the methane distribution with high values in the inner estuary and low values in the outer estuary (median of 161 versus 10 nmol/L/d respectively) Methane concentrations were significantly influenced by the river hydrology (falling water level) and the trophic state of the water (biological oxygen demand). In contrast to other studies no clear relation to the amount of suspendended particulate matter (SPM) was found. Methane oxidation rates were significantly influenced by methane concentration and to a weaker extent by temperature. Methane oxidation accounted for 41 ± 12% of the total loss of methane in summer/fall, but only for 5 ± 3% of the total loss in winter/spring. We applied a modified box model taking into account the residence times of a water parcel depending on discharge and tidal impact. We observed almost stable methane concentrations in the outer estuary, despite a strong loss of methane through diffusion and oxidation. Thus we postulate that in the outer Elbe estuary a strong additional input of methane is required, which could be provided by the extensive salt marshes near the river mouth.

Age determination of seven sediment cores from the South Pacific Ocean

During the last deglaciation, the opposing patterns of atmospheric CO2 and radiocarbon activities (D14C) suggest the release of 14C-depleted CO2 from old carbon reservoirs. Although evidences point to the deep Pacific as a major reservoir of this 14C-depleted carbon, its extent and evolution still need to be constrained. Here we use sediment cores retrieved along a South Pacific transect to reconstruct the spatio-temporal evolution of D14C over the last 30,000 years. In ~2,500-3,600 m water depth, we find 14C-depleted deep waters with a maximum glacial offset to atmospheric 14C (DD14C = -1,000 per mil). Using a box model, we test the hypothesis that these low values might have been caused by an interaction of aging and hydrothermal CO2 influx. We observe a rejuvenation of circumpolar deep waters synchronous and potentially contributing to the initial deglacial rise in atmospheric CO2. These findings constrain parts of the glacial carbon pool to the deep South Pacific.

Age determination of ODP Site 165-1002

An expanded Cariaco Basin 14C chronology is tied to 230Th-dated Hulu Cave speleothem records in order to provide detailed marine-based 14C calibration for the past 50,000 years. The revised, high-resolution Cariaco 14C calibration record agrees well with data from 230Th-dated fossil corals back to 33 ka, with continued agreement despite increased scatter back to 50 ka, suggesting that the record provides accurate calibration back to the limits of radiocarbon dating. The calibration data document highly elevated Delta14C during the Glacial period. Carbon cycle box model simulations show that the majority of observed Delta14C change can be explained by increased 14C production. However, from 45 to 15 ka, Delta14C remains anomalously high, indicating that the distribution of radiocarbon between surface and deep ocean reservoirs was different than it is today. Additional observations of the magnitude, spatial extent and timing of deep ocean Delta14C shifts are critical for a complete understanding of observed Glacial Delta14C variability.

Nitrite consumption and associated isotope changes during a river flood event in the Elbe river

In oceans, estuaries, and rivers, nitrification is an important nitrate source, and stable isotopes of nitrate are often used to investigate recycling processes (e.g. remineralisation, nitrification) in the water column. Nitrification is a two-step process, where ammonia is oxidised via nitrite to nitrate. Nitrite usually does not accumulate in natural environments, which makes it difficult to study the single isotope effect of ammonia oxidation or nitrite oxidation in natural systems. However, during an exceptional flood in the Elbe River in June 2013, we found a unique co-occurrence of ammonium, nitrite, and nitrate in the water column, returning towards normal summer conditions within 1 week. Over the course of the flood, we analysed the evolution of d15N-[NH4]+ and d15N-[NO2]- in the Elbe River. In concert with changes in suspended particulate matter (SPM) and d15N SPM, as well as nitrate concentration, d15N-NO3 - and d18O-[NO3] -, we calculated apparent isotope effects during net nitrite and nitrate consumption. During the flood event, > 97 % of total reactive nitrogen was nitrate, which was leached from the catchment area and appeared to be subject to assimilation. Ammonium and nitrite concentrations increased to 3.4 and 4.4 µmol/l, respectively, likely due to remineralisation, nitrification, and denitrification in the water column. d15N-[NH4]+ values increased up to 12 per mil, and d15N-[NO2]- ranged from -8.0 to -14.2 per mil. Based on this, we calculated an apparent isotope effect 15-epsilon of -10.0 ± 0.1 per mil during net nitrite consumption, as well as an isotope effect 15-epsilon of -4.0 ± 0.1 per mil and 18-epsilon of -5.3 ± 0.1 per mil during net nitrate consumption. On the basis of the observed nitrite isotope changes, we evaluated different nitrite uptake processes in a simple box model. We found that a regime of combined riparian denitrification and 22 to 36 % nitrification fits best with measured data for the nitrite concentration decrease and isotope increase.

Underway measurements of dissolved gases along POLARSTERN cruise track ANT-XXVII/2

We present measurements of pCO2, O2 concentration, biological oxygen saturation (Delta O2/Ar) and N2 saturation (Delta N2) in Southern Ocean surface waters during austral summer, 2010-2011. Phytoplankton biomass varied strongly across distinct hydrographic zones, with high chlorophyll a (Chla) concentrations in regions of frontal mixing and sea-ice melt. pCO2 and Delta O2 /Ar exhibited large spatial gradients (range 90 to 450 µatm and -10 to 60%, respectively) and co-varied strongly with Chla. However, the ratio of biological O2 accumulation to dissolved inorganic carbon (DIC) drawdown was significantly lower than expected from photosynthetic stoichiometry, reflecting the differential time-scales of O2 and CO2 air-sea equilibration. We measured significant oceanic CO2 uptake, with a mean air-sea flux (~ -20 mmol m-2 d-1) that significantly exceeded regional climatological values. N2 was mostly supersaturated in surface waters (mean Delta N2 of +2.5 %), while physical processes resulted in both supersaturation and undersaturation of mixed layer O2 (mean Delta O2phys = 2.1 %). Box model calculations were able to reproduce much of the spatial variability of Delta N2 and Delta O2phys along the cruise track, demonstrating significant effects of air-sea exchange processes (e.g. atmospheric pressure changes and bubble injection) and mixed layer entrainment on surface gas disequilibria. Net community production (NCP) derived from entrainment-corrected surface Delta O2 /Ar data, ranged from ~ -40 to > 300 mmol O2 m-2 d-1 and showed good coherence with independent NCP estimates based on seasonal mixed layer DIC deficits. Elevated NCP was observed in hydrographic frontal zones and regions of sea-ice melt with shallow mixed layer depths, reflecting the importance of mixing in controlling surface water light and nutrient availability.

Sr/Ca and Cd/Ca ratios of benthic foraminifera in surface deep-sea sediments

Measurements of Sr/Ca of benthic foraminifera show a linear decrease with water depth which is superimposed upon significant variability identified by analyses of individual foraminifera. New data for Cd/Ca support previous work in defining a contrast between waters shallower and deeper than ~2500 m. Measured element partition coefficients in foraminiferal calcium carbonate relative to sea water (D) have been described by means of a one-box model in which elements are extracted by Rayleigh distillation from a biomineralization reservoir that serves for calcification with a constant fractionation factor (alpha), such that D = (1 - f**alpha)/(l - f), where f is the proportion of Ca remaining after precipitation. A modification to the model recognises differences in element speciation. The model is consistent with differences between D[Sr], D[Ba], and D[Cd] in benthic but not planktonic foraminifera. Depth variations in D for Sr and Ba are consistent with the model, as are differences in depth variation of D[Cd] in calcitic and aragonitic benthic foraminifera. The shallower depth variations may reflect increasing calcification rates with increasing water depth to an optimum of about 2500 m. Observations of unusually lower DCd for some deep waters, not accompanied by similar [Sr], or D[Ba] may be because of dissolution or a calcification response to a lower carbonate saturation state.