Halocarbons (water) measured during Maria S. Merian cruise MSM18/3

Halocarbons from oceanic sources contribute to halogens in the troposphere, and can be transported into the stratosphere where they take part in ozone depletion. This paper presents distribution and sources in the equatorial Atlantic from June and July 2011 of the four compounds bromoform (CHBr3), dibromomethane (CH2Br2), methyl iodide (CH3I) and diiodomethane (CH2I2). Enhanced biological production during the Atlantic Cold Tongue (ACT) season, indicated by phytoplankton pigment concentrations, led to elevated concentrations of CHBr3 of up to 44.7 and up to 9.2 pmol/L for CH2Br2 in surface water, which is comparable to other tropical upwelling systems. While both compounds correlated very well with each other in the surface water, CH2Br2 was often more elevated in greater depth than CHBr3, which showed maxima in the vicinity of the deep chlorophyll maximum. The deeper maximum of CH2Br2 indicates an additional source in comparison to CHBr3 or a slower degradation of CH2Br2. Concentrations of CH3I of up to 12.8 pmol/L in the surface water were measured. In contrary to expectations of a predominantly photochemical source in the tropical ocean, its distribution was mostly in agreement with biological parameters, indicating a biological source. CH2I2 was very low in the near surface water with maximum concentrations of only 3.7 pmol/L. CH2I2 showed distinct maxima in deeper waters similar to CH2Br2. For the first time, diapycnal fluxes of the four halocarbons from the upper thermocline into and out of the mixed layer were determined. These fluxes were low in comparison to the halocarbon sea-to-air fluxes. This indicates that despite the observed maximum concentrations at depth, production in the surface mixed layer is the main oceanic source for all four compounds and one of the main driving factors of their emissions into the atmosphere in the ACT-region. The calculated production rates of the compounds in the mixed layer are 34 ± 65 pmol/m**3/h for CHBr3, 10 ± 12 pmol/m**3/h for CH2Br2, 21 ± 24 pmol/m**3/h for CH3I and 384 ± 318 pmol/m**3/h for CH2I2 determined from 13 depth profiles.

Grain size distribution, carbon content and wet bulk density of sediment cores in the equatorial Atlantic and the Norwegian Sea

Near-surface sediments from the equatorial east Atlantic and the Norwegian Sea exhibit pronounced shear strength maxima in profiles from the peak Holocene and Pleistocene. These semi-indurated layers start to occur at 8-102 cm below the sediment surface and can be explained neither by the modal composition nor by the effective overburden pressure of the sediments. However, scanning electron microscope and microprobe data exhibit micritic crusts and crystal carpets, which are clearly restricted to (undisturbed) samples from indurated layers and form a manifest explanation for their origin. The minerals precipitated comprise calcite, aragonite, and in samples more proximal to the African continent SiO2 needles, and needles of as yet unidentified K-Mg-Fe-Al silicates, crusts of which dominate the indurated layers in the Norwegian Sea. By their stratigraphic position in deep-sea sediments the carbonate-based shear strength maxima are tentatively ascribed to dissolved adjacent pteropod layers from the early Holocene and hence to short-lived no-analogue events of early diagenesis. Possibly, they have been controlled by a reduced organic carbon flux, leading to increased aragonite preservation in the deep sea.

Nitrogen isotope gradients off Peru and Ecuador related to upwelling, productivity, nutrient uptake and oxygen deficiency

We present new nitrogen isotope data from the water column and surface sediments for paleo-proxy validation collected along the Peruvian and Ecuadorian margins between 1°N and 18°S. Productivity proxies in the bulk sediment (organic carbon, total nitrogen, biogenic opal, C37 alkenone concentrations) and 15N/14N ratios were measured at more than 80 locations within and outside the present-day Peruvian oxygen minimum zone (OMZ). Microbial N-loss to N2 in subsurface waters under O2 deficient conditions leaves a characteristic 15N-enriched signal in underlying sediments. We find that phytoplankton nutrient uptake in surface waters within the high nutrient, low chlorophyll (HNLC) regions of the Peruvian upwelling system influences the sedimentary signal as well. How the d15Nsed signal is linked to these processes is studied by comparing core-top values to the 15N/14N of nitrate and nitrite (d15N[NOx]) in the upper 200 m of the water column. Between 1°N and 10°S, subsurface O2 is still high enough to suppress N-loss keeping d15NNOx values relatively low in the subsurface waters. However d15N[NOx] values increase toward the surface due to partial nitrate utilization in the photic zone in this HNLC portion of the system. d15N[sed] is consistently lower than the isotopic signature of upwelled [NO3]-, likely due to the corresponding production of 15N depleted organic matter. Between 10°S and 15°S, the current position of perennial upwelling cells, HNLC conditions are relaxed and biological production and near-surface phytoplankton uptake of upwelled [NO3]- are most intense. In addition, subsurface O2 concentration decreases to levels sufficient for N-loss by denitrification and/or anammox, resulting in elevated subsurface d15N[NOx] values in the source waters for coastal upwelling. Increasingly higher production southward is reflected by various productivity proxies in the sediments, while the north-south gradient towards stronger surface [NO3]- utilization and subsurface N-loss is reflected in the surface sediment 15N/14N ratios. South of 10°S, d15N[sed] is lower than maximum water column d15N[NOx] values most likely because only a portion of the upwelled water originates from the depths where highest d15N[NOx] values prevail. Though the enrichment of d15N[NOx] in the subsurface waters is unambiguously reflected in d15N[sed] values, the magnitude of d15N[sed] enrichment depends on both the depth of upwelled waters and high subsurface d15N[NOx] values produce by N-loss. Overall, the degree of N-loss influencing subsurface d15N[NOx] values, the depth origin of upwelled waters, and the degree of near-surface nitrate utilization under HNLC conditions should be considered for the interpretation of paleo d15N[sed] records from the Peruvian oxygen minimum zone.

Age models and stable isotope ratios of SO12 and SO35 sediment cores

Based on organic carbon accumulation rates, nine time slices of oceanic export paleoproductivity (Pnew) are presented which depict the variability of Pnew on a global scale through the last 30,000 years and document that the basic distribution patterns did not change through glacial and interglacial times. However, the glacial ocean shows an increased contrast of high- versus low-productivity zones. d13C values of near-surface-dwelling planktonic foraminifera Globigerinoides ruber suggest that the same contrast applies to the glacial nutrient inventories of the ambient surface waters, with a significant glacial transfer of PO4 from low- to high-productivity zones. In this way, glacial Pnew increased by a global average of about 2-4 Gt C/yr and led, via an enhanced CaCO3 dissolution and alkalinity in the deep ocean, to a significant extraction of CO2 from the surface water and the atrnosphere.

Dissolved iron measurements from 32 stations in the Central Arctic Ocean and Arctic Shelf Sea during POLARSTERN expedition ARK-XXII/2

Concentrations of dissolved (<0.2 µm) Fe (DFe) in the Arctic shelf seas and in the surface waters of the central Arctic Ocean are presented. In the Barents and Kara seas, near-surface DFe minima indicate depletion of DFe by phytoplankton growth. Below the surface, lower DFe concentrations in the Kara Sea (~0.4-0.6 nM) than in the Barents Sea (~0.6-0.8 nM) likely reflect scavenging removal or biological depletion of DFe. Very high DFe concentrations (>10 nM) in the bottom waters of the Laptev Sea shelf may be attributed to either sediment resuspension, sinking of brine or regeneration of DFe in the lower layers. A significant correlation (R2 = 0.60) between salinity and DFe is observed. Using d18O, salinity, nutrients and total alkalinity data, the main source for the high (>2 nM) DFe concentrations in the Amundsen and Makarov Basins is identified as (Eurasian) river water, transported with the Transpolar Drift (TPD). On the North American side of the TPD, the DFe concentrations are low (<0.8 nM) and variations are determined by the effects of sea-ice meltwater, biological depletion and remineralization and scavenging in halocline waters from the shelf. This distribution pattern of DFe is also supported by the ratio between unfiltered and dissolved Fe (high (>4) above the shelf and low (<4) off the shelf).

Temperature time series and physical properties of snow samples of a high-arctic permafrost site on Svalbard, Norway

Independent measurements of radiation, sensible and latent heat fluxes and the ground heat flux are used to describe the annual cycle of the surface energy budget at a high-arctic permafrost site on Svalbard. During summer, the net short-wave radiation is the dominant energy source, while well developed turbulent processes and the heat flux in the ground lead to a cooling of the surface. About 15% of the net radiation is consumed by the seasonal thawing of the active layer in July and August. The Bowen ratio is found to vary between 0.25 and 2, depending on water content of the uppermost soil layer. During the polar night in winter, the net long-wave radiation is the dominant energy loss channel for the surface, which is mainly compensated by the sensible heat flux and, to a lesser extent, by the ground heat flux, which originates from the refreezing of the active layer. The average annual sensible heat flux of -6.9 W/m**2 is composed of strong positive fluxes in July and August, while negative fluxes dominate during the rest of the year. With 6.8 W/m**2, the latent heat flux more or less compensates the sensible heat flux in the annual average. Strong evaporation occurs during the snow melt period and particularly during the snow-free period in summer and fall. When the ground is covered by snow, latent heat fluxes through sublimation of snow are recorded, but are insignificant for the average surface energy budget. The near-surface atmospheric stratification is found to be predominantly unstable to neutral, when the ground is snow-free, and stable to neutral for snow-covered ground. Due to long-lasting near-surface inversions in winter, an average temperature difference of approximately 3 K exists between the air temperature at 10 m height and the surface temperature of the snow.