Long-lived Ra isotopes by counting or by mass spectrometry: What’s the better method?

The radium isotopes 226Ra and 228Ra have traditionally been determined by counting methods, mostly by gamma counting, or via their shorter-lived daughter isotopes. With increasing sensitivity of mass spectrometers, in particular ICP-MS, attempts have been made to measure 226Ra and 228Ra via mass spectrometry. While the more abundant (in terms of atoms) 226Ra is relatively well established and several datasets have been published, only a few analyses have been published for 228Ra. ICP-MS methods, if fully developed, promise improved precision and therefore an extended applicability of radium isotopes. However, there are still a number of unresolved issues that prevent mass spectrometric techniques from being used more widely. Complications often arise from (1) pre-concentration methods, often including manganese dioxide, and strontium or barium salts. (2) Separation of adsorbers and carriers from the Ra-containing solution (3) Availability of a 228Ra-spike for isotope dilution methods and (d) Sensitivity of the mass spectrometer, which also needs to allow controlling possible interferences. Here I will give an overview of the pros cons of counting vs. mass spectrometry, and discuss possible ways to address some of the key problems for radium measurements via ICP-MS

Progress in the determination of Ac-227 in sea water

Ac-227 is a naturally occurring radioisotope with a unique combination of properties that make it suitable for the determination of deep ocean mixing and upwelling rates. Here, we present a method for the determination of Ac-227 in sea water on sample sizes of 20-80 L. The measurement is based on co-precipitation of Ac-227 with MnO2, followed by chemical isolation of actinium in the presence of an artificial Ac isotope. Actinium is then electrodeposited onto silver discs. In two alpha-spectrometric counting periods, first the artificial Ac-225 isotope is counted, then after &gt; 100 days five daughters of Ac-227. The first counting period gives a total yield for the procedure, integrating chemical recovery and detector efficiency. The total yield was found here to be on average 15 +/- 5%, the chemical yield on average about 50%. The counting of five decay products of Ac-227 in the second period makes the method particularly sensitive. Using appropriate decay corrections, the initial Ac-227 activity can be determined to better than 10% relative error for concentrations &lt; 10,000 atoms/L. We compare data acquired by the new method to a data set from in-situ pumps, from a parallel sampling campaign in the Eastern Weddell Gyre, and we can show excellent agreement. Repeated determinations of Ac-227 in a uranium reference material (UREM-11) demonstrate the accuracy of the method. (c) 2007 Elsevier B.V All rights reserved.</p

Benthic element cycling on the Antarctic shelf and its potential control by sea ice cover

Antarctic shelf regions are potential carbon and nutrient cycling hotspots where rapid climatic changes are projected to affect seasonal sea ice cover, water column stratification, and thus surface primary production and associated fluxes of organic carbon to the seafloor. Here, we report on surface sediment oxygen profiles and respective fluxes in combination with pore water profiles of dissolved iron (DFe) and phosphate (PO43-) from 7 stations along a 400 mile transect with variable sea ice cover and water column stratification from the East Antarctic Peninsula to the west of South Orkney Islands. Our results show that sea ice concentrations and stratification of the upper water column decreased across the transect. We defined a marginal sea ice index of 5-35% sea ice cover which was positively correlated with the benthic carbon mineralization rate. C-mineralization rates increased gradually between the heavy ice-covered station and the marginal sea ice stations from 1.1 to 7.3 mmol C m-2 d-1, respectively. The rates decreased again to 1.8 mmol C m-2 d-1 at the ice-free station, likely attributed to a deeper water column mixed layer depth, which decreases primary production and thus organic carbon export to the sediment. Iron cycling in the sediment was elevated at the marginal sea ice stations where Fe-reduction led to DFe fluxes in the pore water of up to 0.379 mmol DFe m-2 d-1, while moderate (0.068 mmol DFe m-2 d-1) and negligible fluxes were observed at ice-free and ice-covered stations, respectively. In pore waters, concentrations of DFe and PO43- were significantly correlated with almost identical flux ratios of 0.33 mol PO43- per mol DFe for most of the stations, indicating a strong control of the iron cycling on the phosphate release to the water column. The high benthic DFe and PO43- fluxes highlight the importance of sediments underlying the marginal ice zone as source for limiting nutrients to the shelf waters

Marine Ice: A sleeping iron giant in the Southern Ocean?

The Polar Southern Ocean (PSO) provides an excess amount of macro-nutrients but productivity is largely limited by the availability of essential micro-nutrients, namely iron, manganese, zinc and others. Seasonal patches of increased productivity off major ice shelfs around Antarctica suggest that local sources of these deficient micro-nutrients must be present. With this session contribution we present a new study on marine ice from the Filchner-Ronne Ice Shelf (FRIS) as a potential source of iron and other limiting micro-nutrients for the Atlantic sector of the PSO. Marine ice is formed via partial melting of meteoric shelf ice near the grounding line of large ice shelves (e.g. FRIS). During this process small refrozen ice platelets accumulate in a layer of over 100 m thickness underneath the ice shelf to form marine ice containing high amounts of particulate material. In a project funded by the German Research Foundation (DFG) within the priority program SPP1158, we analyse 2 marine ice cores (B13: 62m, B15: 167m of marine ice) recovered in the 1990’s from the FRIS on their geochemical compositions. The coring location of B13 was about 40 km away from the shelf ice edge and B15 was drilled another 136 km further inland along the reconstructed flow line of B13. Due to shelf ice migration over the last 30 years, their locations have shifted about 30 km towards the shelf ice edge. First results show dissolved Fe (dFe) and Mn (dMn) concentrations ranging between 30 and 300 nMol and particulate Fe (pFe) of 20 to 120 µMol (0.2 to 1.4 µMol for pMn). These concentrations are orders of magnitude higher than the ones currently found in the PSO for those elements. Basal melting and ice-berg calving of marine ice with the accompanied release of these essential trace metals could therefore fuel local productivity in regions with large extent of shelf ice. With our study we aim to evaluate marine ice as potentially overlooked source for limiting micro-nutrients that could explain high productivity areas within an otherwise relatively low productive PSO

Geochemical evidence of a floating Arctic ice sheet and underlying freshwater in the Arctic Mediterranean in glacial periods

Numerous studies have addressed the possible existence of large floating ice sheets in the glacial Arctic Ocean from theoretical, modelling, or seafloor morphology perspectives. Here, we add evidence from the sediment record that support the existence of such freshwater ice caps in certain intervals, and we discuss their implications for possible non-linear and rapid behaviour of such a system in the high latitudes. We present sedimentary activities of 230Th together with 234U/238U ratios, the concentrations of manganese, sulphur and calcium in the context of lithological information and records of microfossils and their isotope composition. New analyses (PS51/038, PS72/396) and a re-analysis of existing marine sediment records (PS1533, PS1235, PS2185, PS2200, amongst others) in view of the naturally occurring radionuclide 230Thex and, where available, 10Be from the Arctic Ocean and the Nordic Seas reveal the widespread occurrence of intervals with a specific geochemical signature. The pattern of these parameters in a pan-Arctic view can best be explained when assuming the repeated presence of freshwater in frozen and liquid form across large parts of the Arctic Ocean and the Nordic Seas. Based on the sedimentary evidence and known environmental constraints at the time, we develop a glacial scenario that explains how these ice sheets, together with eustatic sea-level changes, may have affected the past oceanography of the Arctic Ocean in a fundamental way that must have led to a drastic and non-linear response to external forcing. This concept offers a possibility to explain and to some extent reconcile contrasting age models for the Late Pleistocene in the Arctic Ocean. Our view, if adopted, offers a coherent dating approach across the Arctic Ocean and the Nordic Seas, linked to events outside the Arctic

Alpha radiation from polymetallic nodules and potential health risks from deep-sea mining

In search for critical elements, polymetallic nodules at the deep abyssal seafloor are targeted for mining operations. Nodules efficiently scavenge and retain several naturally occurring uranium-series radioisotopes, which predominantly emit alpha radiation during decay. Here, we present new data on the activity concentrations of thorium-230, radium-226, and protactinium-231, as well as on the release of radon-222 in and from nodules from the NE Pacific Ocean. In line with abundantly published data from historic studies, we demonstrate that the activity concentrations for several alpha emitters are often higher than 5 Bq g−1 at the surface of the nodules. These observed values can exceed current exemption levels by up to a factor of 1000, and even entire nodules commonly exceed these limits. Exemption levels are in place for naturally occurring radioactive materials (NORM) such as ores and slags, to protect the public and to ensure occupational health and radiation safety. In this context, we discuss three ways of radiation exposure from nodules, including the inhalation or ingestion of nodule fines, the inhalation of radon gas in enclosed spaces and the potential concentration of some radioisotopes during nodule processing. Seen in this light, inappropriate handling of polymetallic nodules poses serious health risks

Natural variability of geochemical conditions, biogeochemical processes and element fluxes in sediments of the CCZ

During RV SONNE cruise SO239 in March/April 2015 five sites in the area of the Clarion-Clipperton Fracture Zone (CCZ) in the eastern equatorial Pacific were visited as part of the JPI Oceans pilot action Ecological Aspects of Deep-Sea Mining“. Here, we present a comparable study on (1) the redox zonation in the sediments induced by the input flux of organic matter, (2) biogeochemical reactions including the driver of organic matter degradation and (3) diagenetic manganese redistribution and implications for manganese nodule formation

Deglacial patterns of South Pacific overturning inferred from 231Pa and 230Th

The millennial‐scale variability of the Atlantic Meridional Overturning Circulation (AMOC) is well documented for the last glacial termination and beyond. Despite its importance for the climate system, the evolution of the South Pacific overturning circulation (SPOC) is by far less well understood. A recently published study highlights the potential applicability of the 231Pa/230Th‐proxy in the Pacific. Here, we present five sedimentary down‐core profiles of 231Pa/230Th‐ratios measured on a depth transect from the Pacific sector of the Southern Ocean to test this hypothesis using downcore records. Our data are consistent with an increase in SPOC as early as 20 ka that peaked during Heinrich Stadial 1. The timing indicates that the SPOC did not simply react to AMOC changes via the bipolar seesaw but were triggered via Southern Hemisphere processes

The release of dissolved actinium to the ocean : A global comparison of different end-members

Author Posting. © Elsevier B.V., 2007. 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 109 (2008): 409-420, doi:10.1016/j.marchem.2007.07.005.The measurement of short-lived 223Ra often involves a second measurement for supported activities, which represents 227Ac in the sample. Here we exploit this fact, presenting a set of 284 values on the oceanic distribution of 227Ac, which was collected when analyzing water samples for short-lived radium isotopes by the radium delayed coincidence counting system. The present work compiles 227Ac data from coastal regions all over the northern hemisphere, including values from ground water, from estuaries and lagoons, and from marine endmembers. Deep-sea samples from a continental slope off Puerto Rico and from an active vent site near Hawaii complete the overview of 227Ac near its potential sources. The average 227Ac activities of nearshore marine end-members range from 0.4 dpm * m-3 at the Gulf of Mexico to 3.0 dpm *m-3 in the coastal waters of the Korean Strait. In analogy to 228Ra, we find the extension of adjacent shelf regions to play a substantial role for 227Ac activities, although less pronounced than for radium, due to its weaker shelf source. Based on previously published values, we calculate an open ocean 227Ac inventory of 1.35 * 1018 dpm 227Acex in the ocean, which corresponds to 37 moles, or 8.4 kg. This implies a flux of 127 dpm*m-2*y-1 from the deep-sea floor. For the shelf regions, we obtain a global inventory of 227Ac of 4.5 * 1015 dpm, which cannot be converted directly into a flux value, as the regional loss term of 227Ac to the open ocean would have to be included. Ac has so far been considered to behave similarly to Ra in the marine environment, with the exception of a strong Ac source in the deep-sea due to 231Paex. Here, we present evidence of geochemical differences between Ac, which is retained in a warm vent system, and Ra, which is readily released (Moore et al., submitted). Another potential mechanism of producing deviations in 227Ac/228Ra and daughter isotope ratios from the expected production value of lithogenic material is observed at reducing environments, where enrichment in uranium may occur. The presented data here may serve as a reference for including 227Ac in circulation models, and the overview provides values for some end-members that contribute to the global Ac distribution