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Diffusive gradients in thin films (DGT) and ultrafiltration were used to measure trace metal concentrations in the Baltic Sea. The results provide the first comparison of these two fundamentally different speciation methods for trace metals. Cd, Cu, Mn, Ni, and Zn were measured at two sites with different total trace metal concentrations. DGT units prepared with APA-gel as diffusive layer and Chelex 100 resin as binding agent were used throughout the study. The ultrafiltration was performed with Millipore Prep/Scale modules with cutoffs of 1 and 10 kDa. Concentration levels of Mn, Zn, and Cd measured by DGT agreed with the concentrations measured in 1 kDa ultrafiltered samples. For Cu and Ni the ultrafiltered concentrations exceeded the DGT-labile concentrations. The ability of DGT to preconcentrate metals was found to be an analytical advantage compared with ultrafiltration. DGT appears to be a good alternative to 1 kDa ultrafiltration for measurement of truly dissolved Mn, Cd, and Zn in the Baltic Sea.

Thawing Arctic permafrost causes massive fluvial and erosional releases of dissolved and particulate organic carbon (DOC and POC) to coastal waters. Here we investigate how different sources and degradation of remobilized terrestrial carbon may affect large‐scale carbon cycling, by comparing molecular and dual‐isotope composition of waterborne high molecular weight DOC (>1 kD, aka colloidal OC), POC, and sedimentary OC (SOC) across the East Siberian Arctic Shelves. Lignin phenol fingerprints demonstrate a longitudinal trend in relative contribution of terrestrial sources to coastal OC. Wax lipids and cutins were not detected in colloidal organic carbon (COC), in contrast to POC and SOC, suggesting that different terrestrial carbon pools partition into different aquatic carrier phases. The Δ14C signal suggests overwhelmingly contemporary sources for COC, while POC and SOC are dominated by old C from Ice Complex Deposit (ICD) permafrost. Monte Carlo source apportionment (δ13C, Δ14C) constrained that COC was dominated by terrestrial OC from topsoil permafrost (65%) and marine plankton (25%) with smaller contribution ICD and other older permafrost stocks (9%). This distribution is likely a result of inherent compositional matrix differences, possibly driven by organomineral associations. Modern OC found suspended in the surface water may be more exposed to degradation, in contrast to older OC that preferentially settles to the seafloor where it may be degraded on a longer timescale. The different sources which partition into DOC, POC, and SOC appear to have vastly different fates along the Eurasian Arctic coastal margin and may possibly respond on different timescales to climate change.

Six different approaches for estimating the upper ocean export of carbon and nitrogen has been assessed using 2-3 years of observations in the open Baltic Sea. The long-term average export ratios, relative to primary production, were similar from approaches based on upper ocean N budget (

Abstract. Iron chemistry measurements were conducted during summer 2007 at two distinct locations in the Baltic Sea (Gotland Deep and Landsort Deep) to evaluate the role of iron for cyanobacterial bloom development in these estuarine waters. Depth profiles of Fe(II) were measured by chemiluminescent flow injection analysis (CL-FIA) and reveal several origins of Fe(II) to the water column. Photoreduction of Fe(III)-complexes and deposition by rain are main sources of Fe(II) (up to 0.9 nmol L−1) in light penetrated surface waters. Indication for organic Fe(II) complexation resulting in prolonged residence times in oxygenated water was observed. Surface dwelling heterocystous cyanobacteria where mainly responsible for Fe(II) consumption in comparison to other phytoplankton. The significant Fe(II) concentrations in surface waters apparently play a major role in cyanobacterial bloom development in the Baltic Sea and are a major contributor to the Fe requirements of diazotrophs. Second, Fe(II) concentrations up to 1.44 nmol L−1 were observed at water depths below the euphotic zone, but above the oxic anoxic interface. Finally, all Fe(III) is reduced to Fe(II) in anoxic deep water. However, only a fraction thereof is present as ferrous ions (up to 28 nmol L−1) and was detected by the CL-FIA method applied. Despite their high concentrations, it is unlikely that ferrous ions originating from sub-oxic waters could be a temporary source of bioavailable iron to the euphotic zone since mixed layer depths after strong wind events are not deep enough in summer time.

Abstract. Iron chemistry measurements were conducted during summer 2007 at two distinct locations in the Baltic Sea (Gotland Deep and Landsort Deep) to evaluate the role of iron for cyanobacterial bloom development in these estuarine waters. Depth profiles of Fe(II) were measured by chemiluminescent flow injection analysis (CL-FIA). Up to 0.9 nmol Fe(II) L −1 were detected in light penetrated surface waters, which constitutes up to 20% to the dissolved Fe pool. This bioavailable iron source is a major contributor to the Fe requirements of Baltic Sea phytoplankton and apparently plays a major role for cyanobacterial bloom development during our study. Measured Fe(II) half life times in oxygenated water exceed predicted values and indicate organic Fe(II) complexation. Potential sources for Fe(II) ligands, including rainwater, are discussed. Fe(II) concentrations of up to 1.44 nmol L −1 were detected at water depths below the euphotic zone, but above the oxic anoxic interface. Mixed layer depths after strong wind events are not deep enough in summer time to penetrate the oxic-anoxic boundary layer. However, Fe(II) from anoxic bottom water may enter the sub-oxic zone via diapycnal mixing and diffusion.Correspondence to: E. Breitbarth (ebreitbarth@chemistry.otago.ac.nz)

Abstract. Riverine Fe input is the primary Fe source for the ocean. This study is focused on the distribution of Fe along the Lena River freshwater plume in the Laptev Sea using samples from a 600 km long transect in front of the Lena River mouth. Separation of the particulate (>0.22 µm), colloidal (0.22 µm–1 kDa), and truly dissolved (<1 kDa) fractions of Fe was carried out. The total Fe concentrations ranged from 0.2 to 57 µM with Fe dominantly as particulate Fe. The loss of >99 % of particulate Fe and about 90 % of the colloidal Fe was observed across the shelf, while the truly dissolved phase was almost constant across the Laptev Sea. Thus, the truly dissolved Fe could be an important source of bioavailable Fe for plankton in the central Arctic Ocean, together with the colloidal Fe. Fe-isotope analysis showed that the particulate phase and the sediment below the Lena River freshwater plume had negative δ56Fe values (relative to IRMM-14). The colloidal Fe phase showed negative δ56Fe values close to the river mouth (about −0.20 ‰) and positive δ56Fe values in the outermost stations (about +0.10 ‰). We suggest that the shelf zone acts as a sink for Fe particles and colloids with negative δ56Fe values, representing chemically reactive ferrihydrites. The positive δ56Fe values of the colloidal phase within the outer Lena River freshwater plume might represent Fe oxyhydroxides, which remain in the water column, and will be the predominant δ56Fe composition in the Arctic Ocean.

Abstract. Measurements of the physiochemical speciation of Fe in the euphotic zone were performed at three different locations, over a well defined salinity gradient, during spring and summer in the Baltic Sea. The average of total Fe changed from 114 nM in the Bothnian Sea, 44 nM at Landsort Deep and 15 nM at Gotland Deep. Particulate Fe (PFe) was the dominating phase at all stations and on average accounted for 75–85% of the total Fe pool. At all three locations, a decrease in total Fe of 80–90% from initial measurements compared to the summer was found. A strong positive correlation between PFe and chl-a was observed. Hence, primary production strongly regulates cycling of suspended Fe. However, this relation is not dominated by active uptake of Fe in phytoplankton; instead this reflects cycling of phosphorus, growth of diatoms, and removal of PFe during phytoplankton sedimentation. The average colloidal iron fraction, CFe, showed decreasing concentrations along the salinity gradient; Bothnian Sea 15 nM; Landsort Deep 1 nM and Gotland Deep 0.5 nM. Field Flow Fractionation data indicate that the main colloidal carrier phase for Fe in the Baltic Sea is a carbon-rich fulvic acid associated compound, likely of riverine origin. The Fe isotope composition (δ56Fe) of the PFe showed constant positive values in the Bothnian Sea surface waters (+0.08 to +0.20‰). Enrichment of heavy Fe in the Bothnian Sea PFe is most likely associated to input of aggregated land derived Fe-oxyhydroxides and a rapid overturn of Fe(II). At the Landsort deep, the fractionation of PFe changed between −0.08‰ to +0.28‰. The negative values, in early spring, probably indicate exchange over the oxic-anoxic boundary at ~80 m depth.