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We present high-resolution profiles of dissolved, labile and total particulate trace metals (TMs) on the Northeast Greenland shelf from GEOTRACES cruise GN05 in August 2016. Combined with radium isotopes, stable oxygen isotopes, and noble gas measurements, elemental distributions suggest that TM dynamics were mainly regulated by the mixing between North Atlantic-derived Intermediate Water, enriched in labile particulate TMs (LpTMs), and Arctic surface waters, enriched in Siberian shelf-derived dissolved TMs (dTMs; Co, Cu, Fe, Mn, and Ni) carried by the Transpolar Drift. These two distinct sources were delineated by salinity-dependent variations of dTM and LpTM concentrations and the proportion of dTMs relative to the total dissolved and labile particulate ratios. Locally produced meltwater from the Nioghalvfjerdsbræ (79NG) glacier cavity, distinguished from other freshwater sources using helium excess, contributed a large pool of dTMs to the shelf inventory. Localized peaks in labile and total particulate Cd, Co, Fe, Mn, Ni, Cu, Al, V, and Ti in the cavity outflow, however, were not directly contributed by submarine melting. Instead, these particulate TMs were mainly supplied by the re-suspension of cavity sediment particles. Currently, Arctic Ocean outflows are the most important source of dFe, dCu and dNi on the shelf, while LpTMs and up to 60% of dMn and dCo are mainly supplied by subglacial discharge from the 79NG cavity. Therefore, changes in the cavity-overturning dynamics of 79NG induced by glacial retreat, and alterations in the transport of Siberian shelf-derived materials with the Transport Drift may shift the shelf dTM-LpTM stoichiometry in the future. Key Points The overall dissolved and particulate trace metal dynamics were mainly regulated by the mixing with Arctic surface waters Resuspension of cavity sediments is a major localized source of labile and total particulate Cd, Co, Fe, Mn, Ni, Cu, Al, V, and Ti Whilst dissolved and particulate trace metal

The Arctic Ocean is considered a source of micronutrients to the Nordic Seas and the North Atlantic Ocean through the gateway of Fram Strait. However, there is a paucity of trace element data from across the Arctic Ocean gateways, and so it remains unclear how Arctic and North Atlantic exchange shapes micronutrient availability in the two ocean basins. In 2015 and 2016, GEOTRACES cruises sampled the Barents Sea Opening (GN04, 2015) and Fram Strait (GN05, 2016) for dissolved iron (dFe), manganese (dMn), cobalt (dCo), nickel (dNi), copper (dCu) and zinc (dZn). Together with the most recent synopsis of Arctic-Atlantic volume fluxes, the observed trace element distributions suggest that Fram Strait is the most important gateway for Arctic-Atlantic dissolved micronutrient exchange as a consequence of Intermediate and Deep Water transport. Combining fluxes from Fram Strait and the Barents Sea Opening with estimates for Davis Strait (GN02, 2015) suggests an annual net southward flux of 2.7 ± 2.4 Gg·a-1 dFe, 0.3 ± 0.3 Gg·a-1 dCo, 15.0 ± 12.5 Gg·a-1 dNi and 14.2 ± 6.9 Gg·a-1 dCu from the Arctic towards the North Atlantic Ocean. Arctic-Atlantic exchange of dMn and dZn were more balanced, with a net southbound flux of 2.8 ± 4.7 Gg·a-1 dMn and a net northbound flux of 3.0 ± 7.3 Gg·a-1 dZn. Our results suggest that ongoing changes to shelf inputs and sea ice dynamics in the Arctic, especially in Siberian shelf regions, affect micronutrient availability in Fram Strait and the high latitude North Atlantic Ocean.

The precise determination of radium‐226 (226Ra) in environmental samples is challenging due to its low concentration. Seawater typically contains between 0.03 and 0.1 fg g−1 226Ra. Thus, this work addresses the need for an easy and precise methodology for 226Ra determination in seawater that may be applied routinely to a large number of samples. For this reason, a new analytical approach has been developed for the quantification of 226Ra in seawater via inductively coupled plasma mass spectrometry (ICP‐MS). Analysis by single collector sector‐field ICP‐MS was shown to be convenient and reliable for this purpose once potential molecular interferences were excluded by a combination of chemical separation and intermediate mass resolution analysis. The proposed method allows purification of Ra from the sample matrix based on preconcentration by MnO2 precipitation, followed by two‐column separation using a cation exchange resin and an extraction chromatographic resin. The method can be applied to acidified and unacidified seawater samples. The recovery efficiency for Ra ranged between 90% and 99.8%, with precision of 5%, accuracy of 95.7% to 99.9%, and a detection limit of 0.033 fg g−1 (referring to the original concentration of seawater). The method has been applied to measure 226Ra concentrations from the North Sea and validated by analyzing samples from the central Arctic (GEOTRACES GN04). Samples from a crossover station (from GEOTRACES GN04 and GEOTRACES GN01 research cruises) were analyzed using alternative methods, and our results are in good agreement with published values.

© The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Journal of Geophysical Research: Oceans 123 (2018): 4853-4873, doi:10.1029/2018JC013888., The first full transarctic section of 228Ra in surface waters measured during GEOTRACES cruises PS94 and HLY1502 (2015) shows a consistent distribution with maximum activities in the transpolar drift. Activities in the central Arctic have increased from 2007 through 2011 to 2015. The increased 228Ra input is attributed to stronger wave action on shelves resulting from a longer ice‐free season. A concomitant decrease in the 228Th/228Ra ratio likely results from more rapid transit of surface waters depleted in 228Th by scavenging over the shelf. The 228Ra activities observed in intermediate waters (<1,500 m) in the Amundsen Basin are explained by ventilation with shelf water on a time scale of about 15–18 years, in good agreement with estimates based on SF6 and 129I/236U. The 228Th excess below the mixed layer up to 1,500 m depth can complement 234Th and 210Po as tracers of export production, after correction for the inherent excess resulting from the similarity of 228Ra and 228Th decay times. We show with a Th/Ra profile model that the 228Th/228Ra ratio below 1,500 m is inappropriate for this purpose because it is a delicate balance between horizontal supply of 228Ra and vertical flux of particulate 228Th. The accumulation of 226Ra in the deep Makarov Basin is not associated with an accumulation of Ba and can therefore be attributed to supply from decay of 230Th in the bottom sediment. We estimate a ventilation time of 480 years for the deep Makarov‐Canada Basin, in good agreement with previous estimates using other tracers., U.S. National Science Foundation Grant Numbers: OCE‐1458305, OCE‐1458424; US NSF Grant Number: OCE‐1433922

Author Posting. © American Geophysical Union, 2017. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Oceans 122 (2017): 3696–3714, doi:10.1002/2016JC012460., We present 34 profiles of radon-deficit from the ice-ocean boundary layer of the Beaufort Sea. Including these 34, there are presently 58 published radon-deficit estimates of air-sea gas transfer velocity (k) in the Arctic Ocean; 52 of these estimates were derived from water covered by 10% sea ice or more. The average value of k collected since 2011 is 4.0 ± 1.2 m d−1. This exceeds the quadratic wind speed prediction of weighted kws = 2.85 m d−1 with mean-weighted wind speed of 6.4 m s−1. We show how ice cover changes the mixed-layer radon budget, and yields an “effective gas transfer velocity.” We use these 58 estimates to statistically evaluate the suitability of a wind speed parameterization for k, when the ocean surface is ice covered. Whereas the six profiles taken from the open ocean indicate a statistically good fit to wind speed parameterizations, the same parameterizations could not reproduce k from the sea ice zone. We conclude that techniques for estimating k in the open ocean cannot be similarly applied to determine k in the presence of sea ice. The magnitude of k through gaps in the ice may reach high values as ice cover increases, possibly as a result of focused turbulence dissipation at openings in the free surface. These 58 profiles are presently the most complete set of estimates of k across seasons and variable ice cover; as dissolved tracer budgets they reflect air-sea gas exchange with no impact from air-ice gas exchange., NSF Arctic Natural Sciences program Grant Number: 1203558, 2017-11-05

Author Posting. © The Author(s), 2014. This is the author's version of the work. It is posted here by permission of Elsevier for personal use, not for redistribution. The definitive version was published in Progress in Oceanography 133 (2015):6-16, doi:10.1016/j.pocean.2014.12.018., Particles determine the residence time of many dissolved elements in seawater. Although a substantial number of field studies were conducted in the framework of major oceanographic programs as GEOSECS and JGOFS, knowledge about particle dynamics is still scarce. Moreover, the particulate trace metal behavior remains largely unknown. The GEOSECS sampling strategy during the 1970’s focused on large sections across oceanic basins, where particles were collected by membrane filtration after Niskin bottle sampling, biasing the sampling towards the small particle pool. Late in this period, the first in situ pumps allowing large volume sampling were also developed. During the 1990’s, JGOFS focused on the quantification of the “exported carbon flux” and its seasonal variability in representative biogeochemical provinces of the ocean, mostly using sediment trap deployments. Although scarce and discrete in time and space, these pioneering studies allowed an understanding of the basic fate of marine particles. This understanding improved considerably, especially when the analysis of oceanic tracers such as natural radionuclides allowed the first quantification of processes such as dissolved-particle exchange and particle settling velocities. Because the GEOTRACES program emphasizes the importance of collecting, characterizing and 39 analyzing marine particles, this paper reflects our present understanding of the sources, fate and sinks of oceanic particles at the early stages of the program., This paper arose from a workshop that was co-sponsored by ESF COST Action ES0801, "The ocean chemistry of bioactive trace elements and paleoproxies". Additional support for that workshop came from SCOR, through support to SCOR from the U.S. National Science Foundation (Grant OCE- 0938349 and OCE-1243377). Support for PJL from U.S. NSF grant OCE-0963026.

Particles determine the residence time of many dissolved elements in seawater. Although a substantial number of field studies were conducted in the framework of major oceanographic programs as GEOSECS and JGOFS, knowledge about particle dynamics is still scarce. Moreover, the particulate trace metal behavior remains largely unknown. The GEOSECS sampling strategy during the 1970’s focused on large sections across oceanic basins, where particles were collected by membrane filtration after Niskin bottle sampling, biasing the sampling towards the small particle pool. Late in this period, the first in situ pumps allowing large volume sampling were also developed. During the 1990’s, JGOFS focused on the quantification of the “exported carbon flux” and its seasonal variability in representative biogeochemical provinces of the ocean, mostly using sediment trap deployments. Although scarce and discrete in time and space, these pioneering studies allowed an understanding of the basic fate of marine particles. This understanding improved considerably, especially when the analysis of oceanic tracers such as natural radionuclides allowed the first quantification of processes such as dissolved-particle exchange and particle settling velocities. Because the GEOTRACES program emphasizes the importance of collecting, characterizing and 39 analyzing marine particles, this paper reflects our present understanding of the sources, fate and sinks of oceanic particles at the early stages of the program.

Natural radioactivity provides tracers in a wide range of characteristic timescales and reactivities, which can be used as tools to study the rate of reaction and transport processes in the ocean. Apart from cosmogenic nuclides and the long-lived radioisotope K-40, the natural radioactivity in the ocean is primarily derived from the decay series of three radionuclides that were produced in the period of nucleosynthesis preceding the birth of our solar system: Uranium-238, Thorium-232, and Uranium-235 (a fourth series, including Uranium-233, has already decayed away). The remaining activity of these so-called primordial nuclides in the Earth's crust, and the range of half-lives and reactivities of the elements in their decay schemes, control the present distribution of U-series nuclides in the ocean

Air-sea gas exchange plays a key role in the cycling of greenhouse and other biogeochemically important gases. Although air-sea gas transfer is expected to change as a consequence of the rapid decline in summer Arctic sea ice cover, little is known about the effect of sea-ice cover on gas exchange fluxes, especially in the marginal ice zone. During the Polarstern expedition ARK-XXVI/3 (TransArc, Aug/Sep 2011) to the central Arctic Ocean, we compared 222Rn/226Ra ratios in the upper 50m of 14 ice-covered and 4 ice-free stations. At three of the ice-free stations, we find 222Rn-based gas transfer coefficients in good agreement with expectation based on published relationships between gas transfer and wind speed over open water when accounting for wind history from wind reanalysis data. We hypothesize that the low gas transfer rate at the fourth station results from reduced fetch due to the proximity of the ice edge, or lateral exchange across the front at the ice edge by restratification. No significant radon deficit could be observed at the ice-covered stations. At these stations, the average gas transfer velocity was less than 0.1 m/d (97.5% confidence), compared to 0.5-2.2 m/d expected for open water. Our results show that air-sea gas exchange in an ice-covered ocean is reduced by at least an order of magnitude compared to open water. In contrast to previous studies, we show that in partially ice-covered regions, gas exchange is lower than expected based on a linear scaling to percent ice cover.

Author Posting. © American Geophysical Union, 2004. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 19 (2004): PA1018, doi:10.1029/2003PA000939., There is increasing evidence indicating that syndepositional redistribution of sediment on the seafloor by bottom currents is common and can significantly affect sediment mass accumulation rates. Notwithstanding its common incidence, this process (generally referred to as sediment focusing) is often difficult to recognize. If redistribution is near synchronous to deposition, the stratigraphy of the sediment is not disturbed and sediment focusing can easily be overlooked. Ignoring it, however, can lead to serious misinterpretations of sedimentary fluxes, particularly when past changes in export flux from the overlying water are inferred. In many instances, this problem can be resolved, at least for sediments deposited during the late Quaternary, by normalizing to the flux of 230Th scavenged from seawater, which is nearly constant and equivalent to the known rate of production of 230Th from the decay of dissolved 234U. We review the principle, advantages and limitations of this method. Notwithstanding its limitations, it is clear that 230Th normalization does provide a means of achieving more accurate interpretations of sedimentary fluxes and eliminates the risk of serious misinterpretations of sediment mass accumulation rates., R. Francois and M. P. Bacon acknowledge support from the National Science Foundation. M. Frank thanks the Swiss Science Foundation for support.

Author Posting. © American Geophysical Union, 2007. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 22 (2007): PA1216, doi:10.1029/2005PA001235.

Author Posting. © Sears Foundation for Marine Research, 2007. This article is posted here by permission of Sears Foundation for Marine Research for personal use, not for redistribution. The definitive version was published in Journal of Marine Research 65 (2007): 345–416, doi: 10.1357/002224007781567621, This review provides an assessment of sediment trap accuracy issues by gathering data to address trap hydrodynamics, the problem of zooplankton "swimmers," and the solubilization of material after collection. For each topic, the problem is identified, its magnitude and causes reviewed using selected examples, and an update on methods to correct for the potential bias or minimize the problem using new technologies is presented. To minimize hydrodynamic biases due to flow over the trap mouth, the use of neutrally buoyant sediment traps is encouraged. The influence of swimmers is best minimized using traps that limit zooplankton access to the sample collection chamber. New data on the impact of different swimmer removal protocols at the US time-series sites HOT and BATS are compared and shown to be important. Recent data on solubilization are compiled and assessed suggesting selective losses from sinking particles to the trap supernatant after collection, which may alter both fluxes and ratios of elements in long term and typically deeper trap deployments. Different methods are needed to assess shallow and short- term trap solubilization effects, but thus far new incubation experiments suggest these impacts to be small for most elements. A discussion of trap calibration methods reviews independent assessments of flux, including elemental budgets, particle abundance and flux modeling, and emphasizes the utility of U-Th radionuclide calibration methods., WG meetings and production of this report was partially supported by the U.S. National Science Foundation via grants to the SCOR. Individuals and science efforts discussed herein were supported by many national science programs, including the U.S. National Science Foundation, Swedish Research Council, the International Atomic Energy Agency through its support of the Marine Environmental Laboratory that also receives support from the Government of the Principality of Monaco, and the Australian Antarctic Science Program. K.B. was supported in part by a WHOI Ocean Life Institute Fellowship.

Author Posting. © The Authors, 2005. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Marine Chemistry 100 (2006): 190-212, doi:10.1016/j.marchem.2005.10.012., The short-lived thorium isotope 234Th (half-life 24.1 days) has been used as a tracer for a variety of transport processes in aquatic systems. Its use as a tracer of oceanic export via sinking particles has stimulated a rapidly increasing number of studies that require analyses of 234Th in both marine and freshwater systems. The original 234Th method is labour intensive. Thus, there has been a quest for simpler techniques that require smaller sample volumes. Here, we review current methodologies in the collection and analysis of 234Th from the water column, discuss their individual strengths and weaknesses, and provide an outlook on possible further improvements and future challenges. Also included in this review are recommendations on calibration procedures and the production of standard reference materials as well as a flow chart designed to help researchers find the most appropriate 234Th analytical technique for a specific aquatic regime and known sampling constraints., Individuals and science efforts discussed herein were supported by many national science programs, including the U.S. National Science Foundation and U.S. Department of Energy and the Ministerio de Educación y Ciencia of Spain. The Agency is grateful for the support provided to its Marine Environment Laboratory by the Government of the Principality of Monaco".

Production of biogenic silica and dissolution processes in the water column and surface sediment are important aspects for the investigation and reconstruction of present and past productivity of the ocean. Although the geological record of biogenic silica is often used as a proxy for paleoceanographic processes in the Southern Ocean, little is known about the present regional distribution of biogenic silica flux and accumulation and their relation to primary production in surface waters. Based on more than 130 sediment and pore water samples, the regional differences of the biogenic silica flux to the sea floor of the southern South Atlantic were investigated. In contrast to biogenic silica content, the dissolved Si-flux through the sediment/water interface, caused by intense dissolution of BSi in surface sediments, reflects biogenic production in surface waters. This was inferred by observed increases of Si-fluxes in regions of recurrent polynya formation or in the vicinity of Marginal Ice Zones as at the Weddell-Scotia Sea boundary. In the Scotia Sea, where no benthic fluxes were reported before, we found a considerable burial of biogenic silica and biogenic silica fluxes to the sea floor of ∼800–1300 mmol m-2 a-1. This is a significantly higher flux than derived for the known opal accumulation area in the SE Atlantic, further to the east in the Antarctic Circumpolar Current, where a flux of ∼600–767 mmol m-2 a-1 was observed. This shows that the Scotia Sea is not a gap within the Circumpolar Antarctic Opal Belt as previously assumed. The geochemical budget for different sub-regions of the South Atlantic was considered by a Geographic Information System. In contrast to most previous attempts, this ensures the accurate consideration of the spatial distribution of sampling sites, a crucial aspect for the accuracy of geochemical budgets. For the South Atlantic we calculated the flux of biogenic silica to the sea floor as ∼5.1×1012 mol a-1. Only ∼0.84×1012 mol a-1 is