Beschreibung: To investigate the biogeochemistry of iron in the waters of the European continental margin, we determined the dissolved iron distribution and redox speciation in filtered (〈0.2 μm) open-ocean and shelf waters. Depth profiles were sampled over the shelf slope southeast of the Chapelle Bank area (47.61°N, 4.24°W to 46.00°N, 8.01°W) and a horizontal surface-water transect over the shelf and through the English Channel (la Manche) and the southern North Sea (46°N, 8°W to 52°N, 4°E). An abrupt trace-metal front was found near the shelf slope, indicated by a horizontal gradient of dissolved iron (DFe) and aluminium (DAl), which correlated with changing salinities (r2 = 0.572 and 0.528, respectively, n = 92). Labile Fe(II) concentrations varied from 〈12 pmol L-1 in North Atlantic surface waters to >200 pmol L-1 in the near bottom waters of the shelf break. Labile Fe(II) accounted for ∼5 of the dissolved iron species in surface shelf waters (mean 5.0 ± 2.7), whereas higher Fe(II) fractions (i.e., >8) were observed near the sea bottom on the shelf break and during a midday solar maximum in surface waters in the vicinity of the Scheldt river plume. Benthic processes (resuspension and diagenesis) constituted important sources of Fe(II) and DFe in this region, and photoreduction of Fe(III) species in shelf waters caused enhanced labile Fe(II) concentrations. These processes increased the lability of iron and its potential availability to marine organisms in the shelf ecosystem. © 2007, by the American Society of Limnology and Oceanography, Inc.

Beschreibung: Dissolved iron (DFe; 〈0.2 µm) and dissolved manganese (DMn; 〈0.2 µm) concentrations were determined in the water column of the Bay of Biscay (eastern North Atlantic Ocean) in March 2002. The samples were collected along a transect traversing from the European continental shelf over the continental slope. The highest DFe and DMn concentrations (2.39 nM and 6.10 nM, respectively) were observed in the bottom waters on the shelf at stations closest to the coast. The release of trace metal from resuspended particles and the diffusion from pore waters were probably at the origin of elevated DFe and DMn concentrations in the Bottom Boundary Layer (BBL). In the slope region, the highest total dissolvable iron (TDFe), DFe and DMn values (24.6 nM, 1.58 nM and 2.12 nM, respectively) were observed close to the bottom at depth of ca.~600–700 m. Internal wave activity and slope circulation are thought to be at the origin of this phenomenon. These processes were also very likely the cause of elevated concentrations (DFe: 1.27 nM, DMn: 2.34 nM) measured in surface waters of stations located in the same area. At stations off the continental slope, the vertical distribution of both metals were typical of open ocean conditions, indicating that inputs from the continental margin did not impact the metal distributions in the offshore waters.

Beschreibung: The first large-scale international intercomparison of analytical methods for the determination of dissolved iron in seawater was carried out between October 2000 and December 2002. The exercise was conducted as a rigorously "blind" comparison of 7 analytical techniques by 24 international laboratories. The comparison was based on a large volume (700 L), filtered surface seawater sample collected from the South Atlantic Ocean (the "IRONAGES" sample), which was acidified, mixed and bottled at sea. Two 1-L sample bottles were sent to each participant. Integrity and blindness were achieved by having the experiment designed and carried out by a small team, and overseen by an independent data manager. Storage, homogeneity and time-series stability experiments conducted over 2.5 years showed that inter-bottle variability of the IRONAGES sample was good (〈 7), although there was a decrease in iron concentration in the bottles over time (0.8-0.5 nM) before a stable value was observed. This raises questions over the suitability of sample acidification and storage. For the complete dataset of 45 results (after excluding 3 outliers not passing the screening criteria), the mean concentration of dissolved iron in the IRONAGES sample was 0.59 ± 0.21 nM, representing a coefficient of variation (CV) for analytical comparability ("community precision") of 36 (1s), a significant improvement over earlier exercises. Within-run precision (5-10), inter-run precision (15) and inter-bottle homogeneity (〈 7) were much better than overall analytical comparability, implying the presence of: (1) random variability (inherent to all intercomparison exercises); (2) errors in quantification of the analytical blank; and (3) systematic inter-method variability, perhaps related to secondary sample treatment (e.g. measurement of different physicochemical fractions of iron present in seawater) in the community dataset. By grouping all results for the same method, analyses performed using flow injection-luminol chemiluminescence (with FeII detection after sample reduction) Bowie, A.R., Achterberg, E.P., Mantoura, R.F.C., Worsfold, P.J., 1998. Determination of sub-nanomolar levels of iron in seawater using flow injection with chemiluminescence detection. Anal. Chim. Acta 361, 189-200 and flow injection-catalytic spectrophotometry (using the reagent DPD) Measures, C.I., Yuan, J., Resing, J.A., 1995. Determination of iron in seawater by flow injection analysis using in-line preconcentration and spectrophotometric detection. Mar. Chem. 50, 3-12 gave significantly (P = 0.05) higher dissolved iron concentrations than analyses performed using isotope dilution ICPMS Wu, J.F., Boyle, E.A., 1998. Determination of iron in seawater by high-resolution isotope dilution inductively coupled plasma mass spectrometry after Mg(OH) 2 co-precipitation. Anal. Chim. Acta 367, 183-191. There was, however, evidence of scatter within each method group (CV up to 59%), implying that better uniformity in procedures may be required. This paper does not identify individual data and should not be viewed as an evaluation of single laboratories. Rather it summarises the status of dissolved iron analysis in seawater by the international community at the start of the 21st century, and can be used to inform future exercises including the SAFE iron intercomparison study in the North Pacific in October 2004. © 2005 Elsevier B.V. All rights reserved.

Beschreibung: Aerosol (soluble and total) iron and water-column dissolved (DFe, 〈 0.2 μm) and total dissolvable (TDFe, unfiltered) iron concentrations were determined in the Canary Basin and along a transect towards the Strait of Gibraltar, in order to sample across the Saharan dust plume. Cumulative dust deposition fluxes estimated from direct aerosol sampling during our one-month cruise are representative of the estimated deposition fluxes based on near surface water dissolved aluminium concentrations measured on board. Iron inventories in near surface waters combined with flux estimates confirmed the relatively short residence time of DFe in waters influenced by the Saharan dust plume (6-14 months). Enhanced near surface water concentrations of DFe (5.90-6.99 nM) were observed at the Strait of Gibraltar mainly due to inputs from metal-rich rivers. In the Canary Basin and the transect towards Gibraltar, DFe concentrations (0.07-0.76 nM) were typical of concentrations observed in the surface North Atlantic Waters, with the highest concentrations associated with higher atmospheric inputs in the Canary Basin. Depth profiles showed that DFe and TDFe were influenced by atmospheric inputs in this area with an accumulation of aeolian Fe in the surface waters. The sub-surface minimum of both DFe and TDFe suggests that a simple partitioning between dissolved and particulate Fe is not obvious there and that export may occur for both phases. At depths of around 1000-1300 m, both regeneration and Meddies may explain the observed maximum. Our data suggest that, in deep waters, higher particle concentrations likely due to dust storms may increase the scavenging flux and thus decrease DFe concentrations in deep waters. © 2007 Elsevier B.V. All rights reserved.

Beschreibung: The coastal ocean is a crucial link between land, the open ocean and the atmosphere. The shallowness of the water column permits close interactions between the sedimentary, aquatic and atmospheric compartments, which otherwise are decoupled at long time scales (≅ 1000 yr) in the open oceans. Despite the prominent role of the coastal oceans in absorbing atmospheric CO2 and transferring it into the deep oceans via the continental shelf pump, the underlying mechanisms remain only partly understood. Evaluating observations from the North Sea, a NW European shelf sea, we provide evidence that anaerobic degradation of organic matter, fuelled from land and ocean, generates total alkalinity (AT) and increases the CO2 buffer capacity of seawater. At both the basin wide and annual scales anaerobic AT generation in the North Sea's tidal mud flat area irreversibly facilitates 7–10%, or taking into consideration benthic denitrification in the North Sea, 20–25% of the North Sea's overall CO2 uptake. At the global scale, anaerobic AT generation could be accountable for as much as 60% of the uptake of CO2 in shelf and marginal seas, making this process, the anaerobic pump, a key player in the biological carbon pump. Under future high CO2 conditions oceanic CO2 storage via the anaerobic pump may even gain further relevance because of stimulated ocean productivity.

Beschreibung: An in situ iron enrichment experiment was carried out in the Southern Ocean Polar Frontal Zone and fertilized a patch of water within an eddy of the Antarctic Circumpolar Current (EisenEx, Nov. 2000). During the experiment, a physical speciation technique was used for iron analysis in order to understand the changes in iron distribution and size-fractionations, including soluble Fe (〈200 kDa), colloidal Fe (200 kDa–0.2 μm) and labile particle Fe (〉0.2 μm), throughout the development of the phytoplankton bloom. Prior to the first infusion of iron, dissolved (〈0.2 μm) iron concentrations in the ambient surface seawater were extremely low (0.06±0.015 nM) with colloidal iron being a minor fraction. For the iron addition, an acidified FeSO4 solution was released three times over a 23-day period to the eddy. High levels of dissolved iron concentrations (2.0±1.1 nM) were measured in the surface water until 4 days after the first iron infusion. After every iron infusion, when high iron concentrations were observed before storm events, there was a significant correlation between colloidal and dissolved iron concentrations ([Colloidal Fe]=0.7627[Dissolved Fe]+0.0519, R2=0.9346). These results indicate that a roughly constant proportion of colloidal vs. dissolved iron was observed after iron infusion (∼76%). Storm events caused a significant decrease in iron concentrations (〈0.61 nM in dissolved iron) and changed the proportions of the three iron size-fractions (soluble, colloidal and labile particle). The changes in each iron size-fraction indicate that colloidal iron was eliminated from surface mixed layer more easily than particulate and soluble fractions. Therefore, particle and soluble iron efficiently remain in the mixed layer, probably due to the presence of suspended particles and naturally dissolved organic ligands. Our data suggest that iron removal through colloidal aggregation during phytoplankton bloom should be considered in the oceanic iron cycle.

Beschreibung: The speciation of strongly chelated iron during the 22-day course of an iron enrichment experiment in the Atlantic sector of the Southern Ocean deviates strongly from ambient natural waters. Three iron additions (ferrous sulfate solution) were conducted, resulting in elevated dissolved iron concentrations (Nishioka, J., Takeda, S., de Baar, H.J.W., Croot, P.L., Boye, M., Laan, P., Timmermans, K.R., in press. Changes in the concentration of iron in different size fractions during an iron enrichment experiment in the open Southern Ocean. Marine Chemistry.) and significant Fe(II) levels (Croot, P.L., Laan, P., Nishioka, J., Strass, V., Cisewski, B., Boye, M., Timmermans, K.R., Bellerby, R.G., Goldson, L., Nightingale, P., de Baar, H.J.W., in press. Spatial and Temporal distribution of Fe(II) and H2O2 during EisenEx, an open ocean mescoscale iron enrichment. Marine Chemistry.). Repeated vertical profiles for dissolved (filtrate 〈 0.2 μm) Fe(III)-binding ligands indicated a production of chelators in the upper water column induced by iron fertilizations. Abiotic processes (chemical reactions) and an inductive biologically mediated mechanism were the likely sources of the dissolved ligands which existed either as inorganic amorphous phases and/or as strong organic chelators. Discrete analysis on ultra-filtered samples (〈 200 kDa) suggested that the produced ligands would be principally colloidal in size (〉 200 kDa–〈 0.2 μm), as opposed to the soluble fraction (〈 200 kDa) which dominated prior to the iron infusions. Yet these colloidal ligands would exist in a more transient nature than soluble ligands which may have a longer residence time. The production of dissolved Fe-chelators was generally smaller than the overall increase in dissolved iron in the surface infused mixed layer, leaving a fraction (about 13–40%) of dissolved Fe not bound by these dissolved Fe-chelators. It is suggested that this fraction would be inorganic colloids. The unexpected persistence of such high inorganic colloids concentrations above inorganic Fe-solubility limits illustrates the peculiar features of the chemical iron cycling in these waters. Obviously, the artificial about hundred-fold increase of overall Fe levels by addition of dissolved inorganic Fe(II) ions yields a major disruption of the natural physical–chemical abundances and reactivity of Fe in seawater. Hence the ensuing responses of the plankton ecosystem, while in itself significant, are not necessarily representative for a natural enrichment, for example by dry or wet deposition of aeolian dust. Ultimately, the temporal changes of the Fe(III)-binding ligand and iron concentrations were dominated by the mixing events that occurred during EISENEX, with storms leading to more than an order of magnitude dilution of the dissolved ligands and iron concentrations. This had strongest impact on the colloidal size class (〉 200 kDa–〈 0.2 μm) where a dramatic decrease of both the colloidal ligand and the colloidal iron levels (Nishioka, J., Takeda, S., de Baar, H.J.W., Croot, P.L., Boye, M., Laan, P., Timmermans, K.R., in press. Changes in the concentration of iron in different size fractions during an iron enrichment experiment in the open Southern Ocean. Marine Chemistry.) was observed.

Beschreibung: A climatological mean distribution for the surface water pCO2 over the global oceans in non-El Niño conditions has been constructed with spatial resolution of 4° (latitude) ×5° (longitude) for a reference year 2000 based upon about 3 million measurements of surface water pCO2 obtained from 1970 to 2007. The database used for this study is about 3 times larger than the 0.94 million used for our earlier paper [Takahashi et al., 2002. Global sea–air CO2 flux based on climatological surface ocean pCO2, and seasonal biological and temperature effects. Deep-Sea Res. II, 49, 1601–1622]. A time-trend analysis using deseasonalized surface water pCO2 data in portions of the North Atlantic, North and South Pacific and Southern Oceans (which cover about 27% of the global ocean areas) indicates that the surface water pCO2 over these oceanic areas has increased on average at a mean rate of 1.5 μatm y−1 with basin-specific rates varying between 1.2±0.5 and 2.1±0.4 μatm y−1. A global ocean database for a single reference year 2000 is assembled using this mean rate for correcting observations made in different years to the reference year. The observations made during El Niño periods in the equatorial Pacific and those made in coastal zones are excluded from the database. Seasonal changes in the surface water pCO2 and the sea-air pCO2 difference over four climatic zones in the Atlantic, Pacific, Indian and Southern Oceans are presented. Over the Southern Ocean seasonal ice zone, the seasonality is complex. Although it cannot be thoroughly documented due to the limited extent of observations, seasonal changes in pCO2 are approximated by using the data for under-ice waters during austral winter and those for the marginal ice and ice-free zones. The net air–sea CO2 flux is estimated using the sea–air pCO2 difference and the air–sea gas transfer rate that is parameterized as a function of (wind speed)2 with a scaling factor of 0.26. This is estimated by inverting the bomb 14C data using Ocean General Circulation models and the 1979–2005 NCEP-DOE AMIP-II Reanalysis (R-2) wind speed data. The equatorial Pacific (14°N–14°S) is the major source for atmospheric CO2, emitting about +0.48 Pg-C y−1, and the temperate oceans between 14° and 50° in the both hemispheres are the major sink zones with an uptake flux of −0.70 Pg-C y−1 for the northern and −1.05 Pg-C y−1 for the southern zone. The high-latitude North Atlantic, including the Nordic Seas and portion of the Arctic Sea, is the most intense CO2 sink area on the basis of per unit area, with a mean of −2.5 tons-C month−1 km−2. This is due to the combination of the low pCO2 in seawater and high gas exchange rates. In the ice-free zone of the Southern Ocean (50°–62°S), the mean annual flux is small (−0.06 Pg-C y−1) because of a cancellation of the summer uptake CO2 flux with the winter release of CO2 caused by deepwater upwelling. The annual mean for the contemporary net CO2 uptake flux over the global oceans is estimated to be −1.6±0.9 Pg-C y−1, which includes an undersampling correction to the direct estimate of −1.4±0.7 Pg-C y−1. Taking the pre-industrial steady-state ocean source of 0.4±0.2 Pg-C y−1 into account, the total ocean uptake flux including the anthropogenic CO2 is estimated to be −2.0±1.0 Pg-C y−1 in 2000.

Beschreibung: The mechanisms driving the air–sea exchange of carbon dioxide (CO2CO2) in the North Sea are investigated using the three-dimensional coupled physical–biogeochemical model ECOHAM (ECOlogical-model, HAMburg). We validate our simulations using field data for the years 2001–2002 and identify the controls of the air–sea CO2CO2 flux for two locations representative for the North Sea's biogeochemical provinces. In the seasonally stratified northern region, net CO2CO2 uptake is high (View the MathML source2.06molm-2a-1) due to high net community production (NCP) in the surface water. Overflow production releasing semi-labile dissolved organic carbon needs to be considered for a realistic simulation of the low dissolved inorganic carbon (DIC) concentrations observed during summer. This biologically driven carbon drawdown outcompetes the temperature-driven rise in CO2CO2 partial pressure (pCO2pCO2) during the productive season. In contrast, the permanently mixed southern region is a weak net CO2CO2 source (View the MathML source0.78molm-2a-1). NCP is generally low except for the spring bloom because remineralization parallels primary production. Here, the pCO2pCO2 appears to be controlled by temperature.