Rare element concentrations measured on filtered seawater of water bottle samples during POLARSTRERN cruise ANT-XXIV/3 (GIPY5)

The concentrations of rare earth elements (REEs) in seawater display systematic variations related to weathering inputs, particle scavenging and water mass histories. Here we investigate the REE concentrations of water column profiles in the Atlantic sector of the Southern Ocean, a key region of the global circulation and primary production. The data reveal a pronounced contrast between the vertical profiles in the Antarctic Circumpolar Current (ACC) and those to the south of the ACC in the Weddell Gyre (WG). The ACC profiles exhibit the typical increase of REE concentrations with water depth and a change in the shape of the profiles from near linear for the light REEs to more convex for the heavy REEs. In contrast, the WG profiles exhibit high REE concentrations throughout the water column with only the near surface samples showing slightly reduced concentrations indicative of particle scavenging. Seawater normalised REE patterns reveal the strong remineralisation signal in the ACC with the light REEs preferentially removed in surface waters and the mirror image pattern of their preferential release in deep waters. In the WG the patterns are relatively homogenous reflecting the prevalence of well-mixed Lower Circumpolar Deep Water (LCDW) that follows shoaling isopycnals in the region. In the WG particle scavenging of REEs is comparatively small and limited to the summer months by light limitation and winter sea ice cover. Considering the surface water depletion compared to LCDW and that the surface waters of the WG are replaced every few years, the removal rate is estimated to be on the order of 1 nmol/m3/yr for La and Nd. The negative cerium anomalies observed in deep waters are some of the strongest found globally with only the deepest waters in parts of the Pacific having stronger anomalies. These deep waters have been isolated from fresh continental REE inputs during their long journey through the abyssal Indo-Pacific ocean and suggests that the high REE concentrations found in the ACC and WG reflect contributions from old deep waters.

Sinking rates of particles measured from deployments in the Atlantic Ocean based on seasonal data

The flux of materials to the deep sea is dominated by larger, organic-rich particles with sinking rates varying between a few meters and several hundred meters per day. Mineral ballast may regulate the transfer of organic matter and other components by determining the sinking rates, e.g. via particle density. We calculated particle sinking rates from mass flux patterns and alkenone measurements applying the results of sediment trap experiments from the Atlantic Ocean. We have indication for higher particle sinking rates in carbonate-dominated production systems when considering both regional and seasonal data. During a summer coccolithophorid bloom in the Cape Blanc coastal upwelling off Mauritania, particle sinking rates reached almost 570 m per day, most probably due the fast sedimentation of densely packed zooplankton fecal pellets, which transport high amounts of organic carbon associated with coccoliths to the deep ocean despite rather low production. During the recurring winter-spring blooms off NW Africa and in opal-rich production systems of the Southern Ocean, sinking rates of larger particles, most probably diatom aggregates, showed a tendency to lower values. However, there is no straightforward relationship between carbonate content and particle sinking rates. This could be due to the unknown composition of carbonate and/or the influence of particle size and shape on sinking rates. It also remains noticeable that the highest sinking rates occurred in dust-rich ocean regions off NW Africa, but this issue deserves further detailed field and laboratory investigations. We obtained increasing sinking rates with depth. By using a seven-compartment biogeochemical model, it was shown that the deep ocean organic carbon flux at a mesotrophic sediment trap site off Cape Blanc can be captured fairly well using seasonal variable particle sinking rates. Our model provides a total organic carbon flux of 0.29 Tg per year down to 3000 m off the NW African upwelling region between 5 and 35° N. Simple parameterisations of remineralisation and sinking rates in such models, however, limit their capability in reproducing the flux variation in the water column.

Global database of surface ocean particulate organic carbon export fluxes diagnosed from the 234Th technique

Through the processes of the biological pump, carbon is exported to the deep ocean in the form of dissolved and particulate organic matter. There are several ways by which downward export fluxes can be estimated. The great attraction of the 234Th technique is that its fundamental operation allows a downward flux rate to be determined from a single water column profile of thorium coupled to an estimate of POC/234Th ratio in sinking matter. We present a database of 723 estimates of organic carbon export from the surface ocean derived from the 234Th technique. Data were collected from tables in papers published between 1985 and 2013 only. We also present sampling dates, publication dates and sampling areas. Most of the open ocean Longhurst provinces are represented by several measurements. However, the Western Pacific, the Atlantic Arctic, South Pacific and the South Indian Ocean are not well represented. There is a variety of integration depths ranging from surface to 220m. Globally the fluxes ranged from -22 to 125 mmol of C/m**2/d. We believe that this database is important for providing new global estimate of the magnitude of the biological carbon pump.

Total organic carbon content and redox-sensitiv trace metal concentrations of selected late Cenoman claystones from DSDP Hole 93-603B

The Cenomanian/Turonian (C/T) intervals at DSDP Sites 105 and 603B from the northern part of the proto-North Atlantic show high amplitude, short-term cyclic variations in total organic carbon (TOC) content. The more pronounced changes in TOC are also reflected by changes in lithology from green claystones (TOC<1%) to black claystones (TOC>1%). Although their depositional history was different, the individual TOC cycles at Sites 105 and 603B can be correlated using stable carbon isotope stratigraphy. Sedimentation rates obtained from the isotope stratigraphy and spectral analyses indicate that these cycles were predominately precession controlled. The coinciding variations in HI, OI, delta13Corg and the abundance of marine relative to terrestrial biomarkers, as well as the low abundance of lignin pyrolysis products generated from the kerogen of the black claystones, indicate that these cyclic variations reflect changes in the contribution of marine organic matter (OM). The cooccurrence of lamination, enrichment of redox-sensitive trace metals and presence of molecular fossils of pigments from green sulfur bacteria indicate that the northern proto-North Atlantic Ocean water column was periodically euxinic from the bottom to at least the base of the photic zone (<150 m) during the deposition of the black claystones. In contrast, the green claystones are bioturbated, are enriched in Mn, do not show enrichments in redox-sensitive trace metals and show biomarker distributions indicative of long oxygen exposure times, indicating more oxic water conditions. At the same time, there is evidence (e.g., abundance of biogenic silica and significant 13C-enrichment for OC of phytoplanktic origin) for enhanced primary productivity during the deposition of the black claystones. We propose that increased primary productivity periodically overwhelmed the oxic OM remineralisation potential of the bottom waters resulting in the deposition of OM-rich black claystones. Because the amount of oxygen used for OM remineralisation exceeded the amount supplied by diffusion and deep-water circulation, the northern proto-North Atlantic became euxinic during these periods. Both Sites 105 and 603B show trends of continually increasing TOC contents and HI values of the black claystones up section, which most likely resulted from both enhanced preservation due to increased anoxia and increased production of marine OM during oceanic anoxic event 2 (OAE2).

The behaviour of the rare earth elements during estuarine mixing-revisited

Complete rare earth element (except Eu) and Y concentrations from the estuarine mixing zone (salinity =0.2 to 33) of Elimbah Creek, Queensland, Australia, were measured by quadrupole ICP-MS without preconcentration. High sampling density in the low salinity regime along with high quality data allow accurate tracing of the development of the typical marine rare earth element anomalies as well as Y/Ho fractionation. Over the entire estuary, the rare earth elements are strongly removed relative to a freshwater endmember (60-80% removal). This large overall removal occurs despite a strong remineralisation peak (190% for La, 130% for Y relative to the freshwater endmember) in the mid-salinity zone. Removal and remineralisation are accompanied by fractionation of the original (freshwater) rare earth element pattern, resulting in light rare earth element depletion. Estuarine fractionation generates a large positive La anomaly and a superchondritic Y/Ho ratio. Conversely, we observe no evidence to support the generation of the negative Ce anomaly in the estuary. With the exception of Ce, the typical marine rare earth element features can thus be attributed to estuarine mixing processes. The persistence of these features in hydrogenous sediments for at least 3.71 Ga highlights the importance of estuarine processes for marine chemistry on geological timescales. (c) 2005 Elsevier B.V. All rights reserved.

Table 1: Station list with macrobenthos biomass results from the ocean floor

Among the Siberian shelf seas the Kara Sea is most strongly influenced by riverine runoff with nearly 1500 km fresh water discharge per year. This fresh water, discharged mainly by Ob and Yenisei, contains about 3.1 * 106 and 4.6 * 106 tons of total organic carbon per year, respectively (Gordeev et al. 1996). Little is known about the relevance of this organic material for biological communities, neither for the Kara Sea nor for the adjacent deep basins of the central Arctic Ocean. Aiming at elucidating the fate of fluvial matter transported from the rivers via estuaries into the central Arctic Ocean and the relative importance of marine organic matter being produced such information is crucial. Here we present calculations on the organic carbon demand of the Kara Sea macrozoobenthos based on measured biomass (total wet weight [ww] per 0.25 m ) from quantitative box corer samples and empirical relationships between biomass, annual production, annual respiration, and carbon remineralisation. This bottom-up approach may serve as a first estimate of the carbon remineralization potential of a given zoobenthos community (or area) as long as no data on in situ respiration rates are available. Our data basis comprises 54 stations sampled in summer seasons 1997, 1999 and 2000 in the Kara Sea at water depths between 10 and 68 m. The geographical area represented by stations analysed covers roughly 178 000 km**2, which is about one fifth of the total Kara Sea area. In this area, 290 species of invertebrate macrozoobenthos were identified with polychaeta, Crustacea, mollusca and echinodermata being the most abundant. For all stations analysed, mean biomass values ranged between 4.3 and 778.1 g ww/m**2 with organic carbon demands between 3.5 and 43.2 mg C/m**2/d. For the area of 178 000 km2 a preliminary total consumption of 1.4 * 10**6t Corg/y (equivalent to 21.5 mg C/m**2/d) was calculated for the macrozoobenthos. An extrapolation of our data would lead to an annual carbon demand of about 5-7 * 106 t for the whole Kara Sea macrozoobenthos (or 15.5-21.7 mg C/m2/d).

Particle flux in the NE Atlantic as recorded by sediment traps

Downward particle flux was measured using sediment traps at various depths over the Porcupine Abyssal Plain (water depth ab. 4850 m) for prolonged periods from 1989 to 1999. A strong seasonal pattern of flux was evident reaching a maximum in mid-summer. The composition of the material changed with depth, reflecting the processes of remineralisation and dissolution as the material sank through the water column. However, there was surprisingly little seasonal variation in its composition to reflect changes in the biology of the euphotic zone. Currents at the site have a strong tidal component with speeds almost always less than 15 cm/sec. In the deeper part of the water column they tend to be northerly in direction, when averaged over periods of several months. A model of upper ocean biogeochemistry forced by meteorology was run for the decade in order to provide an estimate of flux at 3000 m depth. Agreement with measured organic carbon flux is good, both in terms of the timings of the annual peaks and in the integrated annual flux. Interannual variations in the integrated flux are of similar magnitude for both the model output and sediment trap measurements, but there is no significant relationship between these two sets of estimates. No long-term trend in flux is evident, either from the model, or from the measurements. During two spring/summer periods, the marine snow concentration in the water column was assessed by time-lapse photography and showed a strong peak at the start of the downward pulse of material at 3000 m. This emphasises the importance of large particles during periods of maximum flux and at the start of flux peaks. Time lapse photographs of the seabed show a seasonal cycle of coverage of phytodetrital material, in agreement with the model output both in terms of timing and magnitude of coverage prior to 1996. However, after a change in the structure of the benthic community in 1996 no phytodetritus was evident on the seabed. The model output shows only a single peak in flux each year, whereas the measured data usually indicated a double peak. It is concluded that the observed double peak may be a reflection of lowered sediment trap efficiency when flux is very high and is dominated by large marine snow particles. Resuspension into the trap 100 m above the seabed, when compared to the primary flux at 3000 m depth (1800 mab) was lower during periods of high primary flux probably because of a reduction in the height of resuspension when the material is fresh. At 2 mab, the picture is more complex with resuspension being enhanced during the periods of higher flux in 1997, which is consistent with this hypothesis. However there was rather little relationship to flux at 3000 m in 1998. At 3000 m depth, the Flux Stability Index (FSI), which provides a measure of the constancy of the seasonal cycle of flux, exhibited an inverse relationship with flux, such that the highest flux of organic carbon was recorded during the year with the greatest seasonal variation.

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.

Particle fluxes of the bathypelagic sediment trap CVOO-3 in the eastern tropical North Atlantic for the period December 2009 until May 2011

Particle fluxes at the Cape Verde Ocean Observatory (CVOO) in the eastern tropical North Atlantic for the period December 2009 until May 2011 are discussed based on bathypelagic sediment trap time-series data collected at 1290 and 3439 m water depth. The typically oligotrophic particle flux pattern with weak seasonality is modified by the appearance of a highly productive and low oxygen (minimum concentration below 2 µmol kg**-1 at 40 m depth) anticyclonic modewater eddy (ACME) in winter 2010. The eddy passage was accompanied by unusually high mass fluxes of up to 151 mg m**-2 d**-1, lasting from December 2009 to May 2010. Distinct biogenic silica (BSi) and organic carbon flux peaks of ~15 and 13.3 mg m**-2 d**-1, respectively, were observed in February-March 2010 when the eddy approached the CVOO. The flux of the lithogenic component, mostly mineral dust, was well correlated with that of organic carbon, in particular in the deep trap samples, suggesting a tight coupling. The lithogenic ballasting obviously resulted in high particle settling rates and, thus, a fast transfer of epi-/meso-pelagic signatures to the bathypelagic traps. We suspect that the two- to three-fold increase in particle fluxes with depth as well as the tight coupling of mineral dust and organic carbon in the deep trap samples might be explained by particle focusing processes within the deeper part of the eddy. Molar C : N ratios of organic matter during the ACME passage were around 18 and 25 for the upper and lower trap samples, respectively. This suggests that some productivity under nutrient (nitrate) limitation occurred in the euphotic zone of the eddy in the beginning of 2010 or that a local nitrogen recycling took place. The d15N record showed a decrease from 5.21 to 3.11 per mil from January to March 2010, while the organic carbon and nitrogen fluxes increased. The causes of enhanced sedimentation from the eddy in February/March 2010 remain elusive, but nutrient depletion and/or an increased availability of dust as a ballast mineral for organic-rich aggregates might have contributed. Rapid remineralisation of sinking organic-rich particles could have contributed to oxygen depletion at shallow depth. Although the eddy formed in the West African coastal area in summer 2009, no indications of coastal flux signatures (e.g. from diatoms) were found in the sediment trap samples, confirming the assumption that the suboxia developed within the eddy en route. However, we could not detect biomarkers indicative of the presence of anammox (anaerobic ammonia oxidation) bacteria or green sulfur bacteria thriving in photic zone suboxia/hypoxia, i.e. ladderane fatty acids and isorenieratene derivatives, respectively. This could indicate that suboxic conditions in the eddy had recently developed and/or the respective bacterial stocks had not yet reached detection thresholds. Another explanation is that the fast-sinking organic-rich particles produced in the surface layer did not interact with bacteria from the suboxic zone below. Carbonate fluxes dropped from -52 to 21.4 mg m**-2 d**-1 from January to February 2010, respectively, mainly due to reduced contribution of shallow-dwelling planktonic foraminifera and pteropods. The deep-dwelling foraminifera Globorotalia menardii, however, showed a major flux peak in February 2010, most probably due to the suboxia/hypoxia. The low oxygen conditions forced at least some zooplankton to reduce diel vertical migration. Reduced "flux feeding" by zooplankton in the epipelagic could have contributed to the enhanced fluxes of organic materials to the bathypelagic traps during the eddy passage. Further studies are required on eddy-induced particle production and preservation processes and particle focusing.