Continental margins are, via river sediment discharges, the major source of a number of elements to the ocean. They are also, for several reactive elements, sites of preferential removal from the ...water column, due to enhanced scavenging 1 M.P. Bacon, Tracers of chemical scavenging in the ocean: Boundary effects and large-scale chemical fractionation, Philos. Trans. R. Soc. Lond., A 325 (1988) 147–160.. They can therefore be understood as sources of elements for the ocean, sinks or both. Although exchanges of matter are suspected to occur at the continent/ocean interface 2 P.H. Santschi, L. Guo, I.D. Walsh, M.S. Quigley, M. Baskaran, Boundary exchange and scavenging of radionuclides in continental margin waters of the Middle Atlantic Bight: implications for organic carbon fluxes, Cont. Shelf Res. 19 (1999) 609–636. and despite their probable importance for the ocean chemistry, closed budgets have still yet to be determined. Here, based on neodymium isotopic composition data obtained during the past 6 yr, we document and quantify significant neodymium exchange at ocean boundaries, in areas covering a large spectra of hydrographical, biological and geochemical characteristics : Eastern Indian Ocean, Western Equatorial Pacific, Western Tropical Pacific and Northwestern Atlantic, with neodymium removal fluxes accounting for 74±23%, 100±38%, 62±54% and 84±45% of the neodymium input fluxes, respectively. Recognition of boundary exchange and its potential globalization have important implications for (1) our understanding of margin/ocean interactions and their influence on the oceanic isotopic chemistry, and (2) geochemical cycling of reactive elements (including pollutants) at ocean margins.
Distributions of dissolved and particulate rare earth elements (REEs) and seawater neodymium isotopic composition (εNd) were established in samples from the BONUS GoodHope (BGH) IPY-GEOTRACES cruise ...in the SE Atlantic sector of the Southern Ocean (36°S-13°E to 57°S-0°, Feb.–Mar. 2008). Close to the South African continent in the subtropical domain, particulate REEs show the highest concentrations and flat PAAS-normalized patterns, clearly tracing their lithogenic origin. Active cerium oxidation onto suspended particles is evidenced by the mirror-image relationship of the cerium anomaly between dissolved and particulate phases. Unradiogenic dissolved neodymium in surface waters (εNd= -17.1) traces the influence of old sedimentary material brought by the Agulhas current and rings to the Cape Basin area. A mass balance calculation suggests that the release of Nd from dissolution of lithogenic material corresponds to a remobilization of 154×106T of sediment per year, i.e., 5% of the total sediment delivered to the southeast African coast annually. At open ocean stations, both dissolved and particulate REEs present negative cerium anomalies, indicating that particles have acquired a marine signature. The increasing REE concentrations with depth, and the strong linear correlations of dissolved REE with silica, indicate that surface removal and deep re-mineralisation of REEs are partially related to the biogeochemical cycle of silicate, which involves biogenic silica (diatoms). Combined with marine carbonates, these authigenic phases could explain the observed REE patterns in suspended particles, except for La. We suggest that the positive La anomalies in both phases are linked to the oceanic barium cycle and the partial dissolution of barite crystals, especially in the Polar Frontal Zone.
The εNd composition behaves conservatively in intermediate and deep waters, while input processes affect the isotopic signal of subtropical surface waters and Weddell Gyre bottom waters. An Indian Ocean and an Atlantic variety of AAIW have been isotopically differentiated (εNd=−9.3±0.3 and εNd=−8.0±0.5, respectively). Homogeneous signatures characterize circumpolar waters (εNd from −8.2 to −8.4 for CDW). A binary mixing model has been used to assess the contribution of undiluted NADW reaching southern latitudes.
This work presents iron isotope data in the western equatorial Pacific. Marine aerosols and top core margin sediments display a slightly heavy Fe isotopic composition (δ56Fe) of 0.33 ± 0.11‰ (2SD) ...and 0.14 ± 0.07‰, respectively. Samples reflecting the influence of Papua New Guinea runoff (Sepik River and Rabaul volcano water) are characterized by crustal values. In seawater, Fe is mainly supplied in the particulate form and is found with a δ56Fe between −0.49 and 0.34 ± 0.07‰. The particulate Fe seems to be brought mainly by runoff and transported across continental shelves and slopes. Aerosols are suspected to enrich the surface Vitiaz Strait waters, while hydrothermal activity likely enriched New Ireland waters. Dissolved Fe isotopic ratios are found between −0.03 and 0.53 ± 0.07‰. They are almost systematically heavier than the corresponding particulate Fe, and the difference between the signature of both phases is similar for most samples with Δ56FeDFe – PFe = +0.27 ± 0.25‰ (2SD). This is interpreted as an equilibrium isotopic fractionation revealing exchange fluxes between both phases. The dissolved phase being heavier than the particles suggests that the exchanges result in a net nonreductive release of dissolved Fe. This process seems to be locally significantly more intense than Fe reductive dissolution documented along reducing margins. It may therefore constitute a very significant iron source to the ocean, thereby influencing the actual estimation of the iron residence time and sinks. The underlying processes could also apply to other elements.
Key Points
Isotopic composition of dissolved and particulate Fe in seawaterIsotopic composition of Fe in marine aerosol, Sepik, and margin sedimentsNonreductive release would be an important source of dissolved Fe
The decoupled behaviour observed between Nd isotopic composition (Nd IC, also referred as εNd) and Nd concentration cycles has led to the notion of a "Nd paradox". While εNd behaves in a ...quasi-conservative way in the open ocean, leading to its broad use as a water-mass tracer, Nd concentration displays vertical profiles that increase with depth, together with a deep-water enrichment along the global thermohaline circulation. This non-conservative behaviour is typical of nutrients affected by scavenging in surface waters and remineralisation at depth. In addition, recent studies suggest the only way to reconcile both concentration and Nd IC oceanic budgets, is to invoke a "Boundary Exchange" process (BE, defined as the co-occurrence of transfer of elements from the margin to the sea with removal of elements from the sea by Boundary Scavenging) as a source-sink term. However, these studies do not simulate the input/output fluxes of Nd to the ocean, and therefore prevents from crucial information that limits our understanding of Nd decoupling. To investigate this paradox on a global scale, this study uses for the first time a fully prognostic coupled dynamical/biogeochemical model with an explicit representation of Nd sources and sinks to simulate the Nd oceanic cycle. Sources considered include dissolved river fluxes, atmospheric dusts and margin sediment re-dissolution. Sinks are scavenging by settling particles. This model simulates the global features of the Nd oceanic cycle well, and produces a realistic distribution of Nd concentration (correct order of magnitude, increase with depth and along the conveyor belt, 65% of the simulated values fit in the ±10 pmol/kg envelop when compared to the data) and isotopic composition (inter-basin gradient, characterization of the main water-masses, more than 70% of the simulated values fit in the ±3 εNd envelop when compared to the data), though a slight overestimation of Nd concentrations in the deep Pacific Ocean may reveal an underestimation of the particle fields by the biogeochemical model. Our results indicate 1) vertical cycling (scavenging/remineralisation) is absolutely necessary to simulate both concentration and εNd, and 2) BE is the dominant Nd source to the ocean. The estimated BE flux (1.1×1010 g(Nd)/yr) is much higher than both dissolved river discharge (2.6×108 g(Nd)/yr) and atmospheric inputs (1.0×108 g(Nd)/yr) that both play negligible role in the water column but are necessary to reconcile Nd IC in surface and subsurface waters. This leads to a new calculated residence time of 360 yrs for Nd in the ocean. The BE flux requires the dissolution of 3 to 5% of the annual flux of continental weathering deposited via the solid river discharge to the continental margin.
Phytoplankton productivity and export sequester climatically significant quantities of atmospheric carbon dioxide as particulate organic carbon through a suite of processes termed the biological ...pump. Constraining how the biological pump operated in the past is important for understanding past atmospheric carbon dioxide concentrations and Earth's climate history. However, reconstructing the history of the biological pump requires proxies. Due to their intimate association with biological processes, several bioactive trace metals and their isotopes are potential proxies for past phytoplankton productivity, including iron, zinc, copper, cadmium, molybdenum, barium, nickel, chromium, and silver. Here, we review the oceanic distributions, driving processes, and depositional archives for these nine metals and their isotopes based on GEOTRACES‐era datasets. We offer an assessment of the overall maturity of each isotope system to serve as a proxy for diagnosing aspects of past ocean productivity and identify priorities for future research. This assessment reveals that cadmium, barium, nickel, and chromium isotopes offer the most promise as tracers of paleoproductivity, whereas iron, zinc, copper, and molybdenum do not. Too little is known about silver to make a confident determination. Intriguingly, the trace metals that are least sensitive to productivity may be used to track other aspects of ocean chemistry, such as nutrient sources, particle scavenging, organic complexation, and ocean redox state. These complementary sensitivities suggest new opportunities for combining perspectives from multiple proxies that will ultimately enable painting a more complete picture of marine paleoproductivity, biogeochemical cycles, and Earth's climate history.
Key Points
Distributions, drivers, and depositional archives described for iron, zinc, copper, cadmium, molybdenum, barium, nickel, chromium, and silver
Cadmium, barium, nickel, and chromium isotopes offer the most promise as paleoproductivity tracers, but key uncertainties remain
Future priorities include quantification of “missing” flux terms, constraining circulation influences, and identifying sedimentary archives
Intercomparison of trace metal data is a key aspect of the International GEOTRACES program, allowing data from multiple laboratories and countries to be combined to produce high-resolution datasets ...for the oceans. The use of crossover stations by the GEOTRACES program provides the opportunity both for comparison of analytical techniques and assessment of temporal variability in the cycling of trace metals such as iron (Fe). Here, we present the first comparison of dissolved Fe stable isotope ratio (δ56Fe; relative to IRMM-014) profiles in the oceans, from reoccupations of three locations in the Atlantic Ocean; (1) the Bermuda Atlantic Time Series station (31.75°N 64.17°W) during the US GEOTRACES IC1 cruise (June 2008) and the US GEOTRACES GA03 cruise (Nov. 2011); (2) the Tenatso Time Series station near Cape Verde (17.4°N 24.5°W) during the U.S GEOTRACES GA03 cruises (2010; 2011), and (3) a station in the Cape Basin close to South West Africa (31.1–31.4°S 36.5°W) during the French GEOTRACES GIPY4 Bonus Good Hope Cruise (Feb. 2008) and the UK GEOTRACES GA10 D357 cruise (Oct. 2010). These datasets provided us with the opportunity not only to compare sampling and analysis techniques by two different laboratories (USC and LEGOS), but also the temporal variability of δ56Fe at these locations on a 1–3year timescale. We found that a good agreement between data and profiles generated by different laboratories does allow assessment of temporal variation of δ56Fe in the water column, as well as spatial variability and synthesis of datasets from different regions of the ocean. In fact, comparison of δ56Fe at the three locations in this study demonstrates a remarkable consistency between the shapes of ocean δ56Fe profiles measured 1–3years apart, pointing to the overall stability of Fe cycling at all three locations on these timescales, despite the expected dynamic nature of the Fe cycle. This consistency is highlighted by strong agreement in δ56Fe throughout the whole water-column at Bermuda, and in waters deeper than 500m in the Cape Basin, which suggests that different water masses may carry distinct δ56Fe signatures. In contrast to these stable δ56Fe, we did observe apparent temporal variability in δ56Fe between cruises at other locations and in surface waters, both throughout the water column at Cape Verde, and in Agulhas-leakage influenced surface waters in the Cape Basin. Such temporal variability may thus provide information about changes in internal Fe cycling or external Fe sources on these timescales. Overall, this study highlights the usefulness of repeat δ56Fe measurements to provide information on the variability of Fe cycling throughout the oceans.
•First study of temporal variability of seawater dissolved iron isotope ratios•Excellent comparability between laboratories•Fe isotope profile shape largely stable on at least biennial timescales•Some variability attributed to changes in Fe sources and surface processes•Agulhas leakage may influence Fe cycling in the South Atlantic
To determine which filtering face piece (FFP3) respirators worn throughout the COVID-19 pandemic are safe for magnetic resonance imaging (MRI).
Three clinical MRI sequences were performed to assess ...imaging artefacts, grid distortion, and local heating for eight commercially available FFP3 respirators. All examinations were performed at Cardiff University Brain Research Imaging Centre using a 3 T Siemens Magnetom Prisma with a 64-channel head and neck coil. Each FFP3 mask was positioned on a custom-developed three-dimensional (3D) head phantom for testing.
Five of the eight FFP3 masks contained ferromagnetic components and were regarded as “MRI unsafe”. One mask was considered “MRI conditional” and only two masks were deemed “MRI safe” for both MRI staff and patients. Temperature strips positioned at the nasal bridge of the phantom did not exhibit local heating. A maximum grid distortion of 5 mm was seen in the anterior portion of the head of the ferromagnetic FFP3 masks.
This study has demonstrated the importance of assessing respiratory FFP3 masks for use in and around MRI machines. Future research involving FFP3 masks can be conducted safely by following the procedures laid out in this study.
•There is limited information regarding MR safety for respirators.•Eight commercially available FFP3 masks were evaluated for MR safety at 3T.•Five of the eight masks contained ferromagnetic components and are ‘MR Unsafe’.•Geometric distortion was seen in the ‘MR Unsafe’ masks.•Any future MR studies involving respirator masks must undergo MR safety evaluation.
The North Atlantic Deep Water (NADW) neodymium isotopic composition (Nd IC) is increasingly used in oceanography and paleoceanography to trace large‐scale circulation and weathering processes, ...notably to investigate past variations of the global thermohaline circulation. Although the present‐day NADW Nd IC is well characterized at ɛNd = −13.5, the acquisition of this isotopic signature (in other words, the causes of this value) has so far been very sparsely documented. Such an understanding is, however, fundamental to the interpretation of paleo records. Nd IC and rare earth element concentrations were measured at 9 stations within the North Atlantic Subpolar Gyre (SIGNATURE cruise, summer 1999). The comparison of this data set with our understanding of water mass circulation provides a description of how the three layers constituting the NADW, the Labrador Sea Water (LSW, ɛNd = −13.9 ± 0.4), North East Atlantic Deep Water (NEADW, ɛNd −13.2 ± 0.4), and North West Atlantic Bottom Water (NWABW, ɛNd −14.5 ± 0.4), acquire their Nd IC through distinct water mass mixings and lithogenic inputs. These different mechanisms, acting upon water masses from very diverse sources, seem to bring the Nd IC of the three NADW layers to values close together and similar to that of the NADW. It is suggested that sediment/seawater interactions significantly lower the NEADW and NWABW Nd IC along the South East Greenland margin. Since these interactions do not significantly modify the Nd content of these water masses, sediment remobilizations leading to the Nd IC variations are probably associated with Nd removal fluxes from the water mass toward the sediment, a process called boundary exchange. On the other hand, LSW seems to acquire its Nd IC from the Subpolar Mode Waters from which it is formed by deep convection, and no other mechanism needs to be invoked. Its unradiogenic signature could ultimately be linked to fresh water runoff from the Canadian Shield. These conclusions should allow more precise interpretations of paleoceanographic Nd IC records, taking into account the distinct histories of the three NADW layers, including distinct water mass mixings and distinct lithogenic inputs.
During the 2014 GEOVIDE transect, seawater samples were collected for
dissolved Pb and Pb isotope analysis. These samples provide a high-resolution
“snapshot” of the source regions for the present Pb ...distribution in the
North Atlantic Ocean. Some of these stations were previously occupied for Pb
from as early as 1981, and we compare the 2014 data with these older data,
some of which are reported here for the first time. Lead concentrations were
highest in subsurface Mediterranean Water (MW) near the coast of Portugal,
which agrees well with other recent observations by the US GEOTRACES program
(Noble et al., 2015). The recently formed Labrador Sea Water (LSW) between
Greenland and Nova Scotia is much lower in Pb concentration than the older
LSW found in the West European Basin due to decreases in Pb
emissions into the atmosphere during the past 20 years. Comparison of North
Atlantic data from 1989 to 2014 shows decreasing Pb concentrations consistent
with decreased anthropogenic inputs, active scavenging, and
advection/convection. Although the isotopic composition of northern North
Atlantic seawater appears more homogenous compared to previous decades, a
clear spatiotemporal trend in isotope ratios is evident over the past
15 years and implies that small changes to atmospheric Pb emissions continue.
Emissions data indicate that the relative proportions of US and European Pb
sources to the ocean have been relatively uniform during the past 2 decades,
while aerosol data may suggest a greater relative proportion of natural
mineral Pb. Using our measurements in conjunction with emissions inventories,
we support the findings of previous atmospheric analyses that a significant
portion of the Pb deposited to the ocean in 2014 was natural, although it is
obscured by the much greater solubility of anthropogenic aerosols over
natural ones.
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