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  • 1
    Publication Date: 2021-03-19
    Description: The Rare Earth Elements (REEs) have been widely used to investigate marine biogeochemical processes as well as the sources and mixing of water masses. However, there are still important uncertainties about the global aqueous REE cycle with respect to the contributions of highly reactive basaltic minerals originating from volcanic islands and the role of Submarine Groundwater Discharge (SGD). Here we present dissolved REE concentrations obtained from waters at the island-ocean interface (including SGD, river, lagoon and coastal waters) from the island of Tahiti and from three detailed open ocean profiles on the Manihiki Plateau (including neodymium (Nd) isotope compositions), which are located in ocean currents downstream of Tahiti. Tahitian fresh waters have highly variable REE concentrations that likely result from variable water–rock interaction and removal by secondary minerals. In contrast to studies on other islands, the SGD samples do not exhibit elevated REE concentrations but have distinctive REE distributions and Y/Ho ratios. The basaltic Tahitian rocks impart a REE pattern to the waters characterized by a middle REE enrichment, with a peak at europium similar to groundwaters and coastal waters of other volcanic islands in the Pacific. However, the basaltic island REE characteristics (with the exception of elevated Y/Ho ratios) are lost during transport to the Manihiki Plateau within surface waters that also exhibit highly radiogenic Nd isotope signatures. Our new data demonstrate that REE concentrations are enriched in Tahitian coastal water, but without multidimensional sampling, basaltic island Nd flux estimates range over orders of magnitude from relatively small to globally significant. Antarctic Intermediate Water (AAIW) loses its characteristic Nd isotopic signature (-6 to-9) around the Manihiki Plateau as a consequence of mixing with South Equatorial Pacific Intermediate Water (SEqPIW), which shows more positive values (-1 to -2). However, an additional Nd input/exchange along the pathway of AAIW, eventually originating from the volcanic Society, Tuamotu and Tubuai Islands (including Tahiti), is indicated by an offset from the mixing array of AAIW and SEqPIW to more radiogenic Nd isotope compositions.
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  • 2
    Publication Date: 2021-02-08
    Description: Seawater rare earth element (REE) concentrations are increasingly applied to reconstruct water mass histories by exploiting relative changes in the distinctive normalised patterns. However, the mechanisms by which water masses gain their patterns are yet to be fully explained. To examine this, we collected water samples along the Extended Ellett Line (EEL), an oceanographic transect between Iceland and Scotland, and measured dissolved REE by offline automated chromatography (SeaFAST) and ICP-MS. The proximity to two continental boundaries, the incipient spring bloom coincident with the timing of the cruise, and the importance of deep water circulation in this climatically sensitive gateway region make it an ideal location to investigate sources of REE to seawater and the effects of vertical cycling and lateral advection on their distribution. The deep waters have REE concentrations closest to typical North Atlantic seawater and are dominated by lateral advection. Comparison to published seawater REE concentrations of the same water masses in other locations provides a first measure of the temporal and spatial stability of the seawater REE signal. We demonstrate the REE pattern is replicated for Iceland-Scotland Overflow Water (ISOW) in the Iceland Basin from adjacent stations sampled 16 years previously. A recently published Labrador Sea Water (LSW) dissolved REE signal is reproduced in the Rockall Trough but shows greater light and mid REE alteration in the Iceland Basin, possibly due to the dominant effect of ISOW and/or continental inputs. An obvious concentration gradient from seafloor sediments to the overlying water column in the Rockall Trough, but not the Iceland Basin, highlights release of light and mid REE from resuspended sediments and pore waters, possibly a seasonal effect associated with the timing of the spring bloom in each basin. The EEL dissolved oxygen minimum at the permanent pycnocline corresponds to positive heavy REE enrichment, indicating maximum rates of organic matter remineralisation and associated REE release. We tentatively suggest a bacterial role to account for the observed heavy REE deviations. This study highlights the need for fully constrained REE sources and sinks, including the temporary nature of some sources, to achieve a balanced budget of seawater REE.
    Type: Article , PeerReviewed , info:eu-repo/semantics/article
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  • 3
    Publication Date: 2023-02-08
    Description: The Asian summer monsoon affects the lives of billions of people. With the aim of identifying geochemical tracers for the monsoon-related freshwater input from the major rivers draining into the Bay of Bengal (BoB) and the Andaman Sea (AnS), we have analyzed the yttrium and rare earth element (YREE) concentration of surface seawater samples from various locations spanning the Andaman Islands in 2011 to 2013. In some locations, samples have been taken in March, July, and November 2011, thus spanning the seasonal cycle and including different monsoon phases. Generally, the YREE patterns are similar to those reported for offshore samples from the BoB and AnS in January 1997, with seawater-normalized patterns of most samples characterized by middle REE enrichments. An enhancement of these middle REE bulges accompanies large increases in dissolved REE concentrations from streams and sediment-rich areas such as mangrove environments. Conversely, some samples, in particular those taken 1–2 days after heavy rainfall in March 2011, show pronounced REE scavenging accompanied by the preferential removal of dissolved light REEs (LREEs) and by higher Y/Ho ratios. The Nd isotope signature of the remaining dissolved REE phase of these low YREE samples is more radiogenic than local rocks and sediments. The time series at a location away from local input sources show remarkably similar REE patterns and concentrations in March and July. Then in October–November, following the peak in monsoon-induced river discharge, the dissolved REE concentrations increase by almost a factor of two, whereas Nd isotopes become less radiogenic by 1.5 εNd units. These unradiogenic values are found at the same site in the winter dry season of the following year, demonstrating the decoupling of sea surface salinity (SSS) and Nd. The large sub-annual variability of YREE concentrations and Nd isotopes encountered was likely caused by the conversion of YREE from the dissolved (probably colloidal) pool to the labile particulate fraction. The comparison of unfiltered and filtered sample concentrations reveals the existence of a large labile particulate pool in the BoB and AnS that most likely originates from the massive river sediment fluxes and is instrumental in the seasonal changes observed.
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  • 4
    Publication Date: 2024-02-07
    Description: Coralline algae play important ecological roles throughout the photic zone of the world’s oceans. Recent studies have shown that attached-living coralline algae can contain records of past climate variability. So far, algal-based paleo-reconstructions are mainly available from mid- to high-latitudes, while in low latitude and temperate regions only few examples exist. Here, we investigate samples from the attached-living encrusting coralline algal species Neogoniolithon hauckii (Rothpletz) R.A Townsend & Huisman [= Neogoniolithon mamillosum (Hauck) Setchell & L.R. Mason, nom illeg.] from a temperate site in the Mediterranean Sea to assess its potential as an environmental recorder. The specimens were collected at different water depths (20 and 40 m) in the Columbretes Islands (Spain). Sclerochronological analysis of sectioned samples revealed seasonal growth patterns. Mg/Ca, Li/Ca, and Ba/Ca ratios were measured in the algal skeletons using laser ablation inductively coupled mass spectrometry (LA-ICP-MS) in ultra-high resolution. We report a mean vertical extension rate of 1.1 to 1.2 mm/year (based on analysis of Mg/Ca cycles in 40 m and 20 m samples), representing the first growth rate measurement for this species. In addition, subannual banding patterns were mapped, measured, and could be linked to high frequency variability in laser-analyzed Mg/Ca ratios. Elemental ratios analyzed in Neogoniolithon hauckii were compared to in situ water temperatures measured at the water depth of sample collection. Our results show significant positive relationships between algal Mg/Ca (R=0.55) as well as Li/Ca ratios (R=0.46) and in situ measured temperature data (40 m specimen). Ba/Ca ratios show no significant correlation to temperature and may be influenced by other factors. These data suggest potential of this species for climate reconstructions in warm-temperate regions as Neogoniolithon hauckii is not only widely distributed in the Mediterranean, but also one of the few species that may be used as a temperature archive for mesophotic coralligenous assemblages that are strongly affected by the recent anthropogenic temperature rise. Further calibration studies are needed to test the element-temperature relationships on samples with longer growth records and in different settings and water depths.
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