Organic carbon and humic substances contents, carbon isotope composition and peroxidase activity in sediments from DSDP Sites 15-147 and 75-532

Sediment samples from the Cariaco Trench (DSDP Leg 15) and the Walvis Ridge (DSDP Leg 75) ranging in age from Holocene to Upper Miocene (approximately 8 million years BP) and in depth from 5 to 258 m were extracted with basic sodium pyrophosphate and the extract analyzed for enzymic activity. Since no dehydrogenase, alkaline phosphatase or esterase activity was found, it is estimated from these data that the maximum bacterial population does not exceed 1000 cells per gram dry sediment. Peroxidase activity was, however, found in most samples: this showed marked dependence on the humic substance concentration (expressed as percent of the organic carbon content) and increased with depth at a rate of 33 units per meter. To explain this observation, we favor an hypothesis based on the presence of active humic-enzyme association. The humic substances absorb and stabilize peroxidase which is liberated throughout the sediment column by lysis of cells. The association of the enzyme with the humic substances protects it from biodegradation and denaturation. This hypothesis agrees with laboratory experiments which show the enhanced stability of humic-enzyme complexes towards degradation by biological, chemical and thermal effects.

(Appendix A) Dissolved manganese concentrations during POLARSTERN Cruise ARK-XXII/2

A total of 773 samples were analysed for dissolved manganese (Mn) in the Arctic Ocean aboard R.V. Polarstern during expedition ARK XXII/2 from 28 July until 07 October 2007 from Tromsø (Norway) to Bremerhaven. Concentrations of Mn were elevated in the surface layer with concentrations of up to 6 nM over the deep Basins and over 20 nM in the Laptev Sea. The general distribution of Mn through the water column is consistent with previous studies, but there are differences in the absolute concentrations that are most likely related to differences in sample area, sampling and filtration. The elevated concentrations of Mn in the surface layer are related to fresh water input. This was visible in the strong negative correlations observed between dissolved Mn and salinity. The correlation between Mn and salinity and the correlation between Mn and the quasi conservative trace water mass tracer PO4*, showed fluvial and melt water input and the Pacific and Atlantic origin of the surface waters. A large portion of the Mn delivered by the Arctic rivers is removed in the shelf seas and does not pass into the central basins. Most likely a benthic flux is at the origin of the elevated concentrations of Mn near the sediments in the Barents and Kara Seas. These elevated concentrations of Mn apparently affected the deep basins as well, as maxima in the concentrations of Mn were observed that corresponded with lowered transmission over the continental slope. A maximum in the concentration of Mn in the deep basin corresponded with anomalies in light transmission, potential temperature and dissolved iron, confirming the hydrothermal origin. The hydrothermal plume was observed throughout the Nansen Basin and over the deep Gakkel Ridge around 2500 m depth and a smaller plume was observed around 3200 m. The concentration of Mn at the Mn maximum around 2500 m depth decreased exponentially, consistent with a first order scavenging model. The concentrations of Mn were extremely low in the deep Makarov Basin (~0.05 nM) and slightly higher in the Eurasian Basin (~0.1 nM) outside the influence of the hydrothermal activity.

Dissolved aluminium measured on water bottle samples during POLARSTERN cruise ARK-XXII/2 (SPACE)

Concentrations of dissolved (0.2 µm filtered) aluminium (Al) have been determined for the first time in the Eurasian part of the Arctic Ocean over the entire water column during expedition ARK XXII/2 aboard R.V. Polarstern (2007). An unprecedented number of 666 samples was analysed for 44 stations along 5 ocean transects. Dissolved Al in surface layer water (SLW) was very low, close to 1 nM, with lowest SLW concentrations towards the Canadian part of the Arctic Ocean and higher values adjacent to and in the shelf seas. The low SLW concentrations indicate no or little influence from aeolian dust input. Dissolved Al showed a nutrient-type increase with depth up to 28 nM, but large differences existed between the different deep Arctic basins. The differences in concentrations of Al between water masses and basins could largely be related to the different origins of the water masses. In the SLW and intermediate water layers, Atlantic and Pacific inflows were of importance. Deep shelf convection appeared to influence the Al distribution in the deep Eurasian Basin. The Al distribution of the deep Makarov Basin provides evidence for Eurasian Basin water inflow into the deep Makarov Basin. A strong correlation between Al and Silicon (Si) was observed in all basins. This correlation and the nutrient-like profile indicate a strong biological influence on the cycling and distribution of Al. The biological influence can be direct by the incorporation of Al in biogenic silica, indirect by preferential scavenging of Al onto biogenic siliceous particles, or by a combination of both processes. From the slope of the overall Al-Si relationship in the intermediate water layer (AIDW; ~ 200-2000 m depth), an Al/Si ratio of 2.2 atoms Al per 1000 atoms Si was derived. This ratio is consistent with the range of previously reported Al/Si uptake ratio in biogenic opal frustules of diatoms. In the deepest waters (>2000 m depth) a steeper slope of the Al-Si relationship of 7.4 to 13 atoms Al per 1000 atoms Si likely results from entrainment of cold shelf water into the deep basins, carrying the signal of dissolution of terrigenous particles with a much higher Al:Si ratio of crustal abundance. Only a small enrichment with such crustal Al and Si component may readily account for the higher Al:Si slope in the deepest waters.

Barium measured on water bottle samples during POLARSTERN cruise ARK-XXII/2 (SPACE)

Dissolved barium has been shown to have the potential to distinguish Eurasian from North American (NA) river runoff. As part of the ARK-XXII/2 Polarstern expedition in summer 2007, Ba was analyzed in the Barents, Kara, Laptev seas, and the Eurasian Basins as well as the Makarov Basin up to the Alpha and Mendeleyev Ridges. By combining salinity, d18O and initial phosphate corrected for mineralization with oxygen (PO4*) or N/P ratios we identified the water mass fractions of meteoric water, sea ice meltwater, and marine waters of Atlantic as well as Pacific origin in the upper water column. In all basins inside the lower halocline layer and the Arctic intermediate waters we find Ba concentrations close to those of the Fram Strait branch of the lower halocline (41-45 nM), reflecting the composition of the incoming Atlantic water. A layer of upper halocline water (UHW) with higher Ba concentrations (45-55 nM) is identified in the Makarov Basin. Atop of the UHW, the Surface Mixed Layer (SML), including the summer and winter mixed layers, has high concentrations of Ba (58-67 nM). In the SML of the investigated area of the central Arctic the meteoric fraction can be identified by assuming a conservative behavior of Ba to be primarily of Eurasian river origin. However, in productive coastal regions biological removal compromises the use of Ba to distinguish between Eurasian and NA rivers. As a consequence, the NA river water fraction is underestimated in productive surface waters or waters that have passed a productive region, whereas this fraction is overestimated in subsurface waters containing remineralised Ba, particularly when these waters have passed productive shelf regions. Especially in the Laptev Sea and small regions in the Barents Sea, Ba concentrations are low in surface waters. In the Laptev Sea exceptionally high Ba concentrations in shelf bottom waters indicate that Ba is removed from surface waters to deep waters by biological activity enhanced by increasing ice-free conditions as well as by scavenging by organic matter of terrestrial origin. We interpret high Ba concentrations in the UHW of the Makarov Basin to result from enrichment by remineralisation in bottom waters on the shelf of the Chukchi Sea and therefore the calculated NA runoff is an artefact. We conclude that no NA runoff can be demonstrated unequivocally anywhere during our expedition with the set of tracers considered here. Small contributions of NA runoff may have been masked by Ba depletion and could only be resolved by supportive tracers on the uptake history. We thus suggest that Ba has to be used with care as it can put limits but not yield quantitative water mass distributions. Only if the extra Ba inputs exceed the cumulative biological uptake the signal can be unequivocally attributed to NA runoff.

Oxygen consumption in Arctic sediments

Total sediment oxygen consumption rates (TSOC or Jtot), measured during sediment-water incubations, and sediment oxygen microdistributions were studied at 16 stations in the Arctic Ocean (Svalbard area). The oxygen consumption rates ranged between 1.85 and 11.2 mmol m**-2 d**-1, and oxygen penetrated from 5.0 to >59 mm into the investigated sediments. Measured TSOC exceeded the calculated diffusive oxygen fluxes (Jdiff) by 1.1-4.8 times. Diffusive fluxes across the sediment-water interface were calculated using the whole measured microprofiles, rather than the linear oxygen gradient in the top sediment layer. The lack of a significant correlation between found abundances of bioirrigating meiofauna and high Jtot/Jdiff ratios as well as minor discrepancies in measured TSOC between replicate sediment cores, suggest molecular diffusion, not bioirrigation, to be the most important transport mechanism for oxygen across the sediment-water interface and within these sediments. The high ratios of Jtot/Jdiff obtained for some stations were therefore suggested to be caused by topographic factors, i.e. underestimation of the actual sediment surface area when one-dimensional diffusive fluxes were calculated, or sampling artifacts during core recovery from great water depths. Measured TSOC correlated to water depth raised to the -0.4 to -0.5 power (TSOC = water depth**-0.4 to -0.5) for all investigated stations, but they could be divided into two groups representing different geographical areas with different sediment oxygen consumption characteristics. The differences in TSOC between the two areas were suggested to reflect hydrographic factors (such as ice coverage and import/production of reactive particulate organic material) related to the dominating water mass (Atlantic or polar) in each of the two areas. The good correlation between TSOC and water depth**-0.4 to -0.5 rules out any of the stations investigated to be topographic depressions with pronounced enhanced sediment oxygen consumption.