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  • 1
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    A Review of the Stable Isotope Bio-geochemistry of the Global Silicon Cycle and Its Associated Trace Elements (2018)
    Frontiers
    In:  Frontiers in Earth Science, 5 (Article number 112).
    Details
    Publication Date: 2021-02-08
    Description: Silicon (Si) is the second most abundant element in the Earth’s crust and is an important nutrient in the ocean. The global Si cycle plays a critical role in regulating primary productivity and carbon cycling on the continents and in the oceans. Development of the analytical tools used to study the sources, sinks, and fluxes of the global Si cycle (e.g., elemental and stable isotope ratio data for Ge, Si, Zn, etc.) have recently led to major advances in our understanding of the mechanisms and processes that constrain the cycling of Si in the modern environment and in the past. Here, we provide background on the geochemical tools that are available for studying the Si cycle and highlight our current understanding of the marine, freshwater and terrestrial systems. We place emphasis on the geochemistry (e.g., Al/Si, Ge/Si, Zn/Si, δ13 C, δ15 N, δ18 O, δ30 Si) of dissolved and biogenic Si, present case studies, such as the Silicic Acid Leakage Hypothesis, and discuss challenges associated with the development of these environmental proxies for the global Si cycle. We also discuss how each system within the global Si cycle might change over time (i.e., sources, sinks, and processes) and the potential technical and conceptual limitations that need to be considered for future studies.
    Type: Article , PeerReviewed
    Format: text
    Format: text
    DOI: 10.3389/feart.2017.00112
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    OceanRep: Article in a Scientific Journal - peer-reviewed
  • 2
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    Constraints on Earth System Functioning at the Paleocene‐Eocene Thermal Maximum From the Marine Silicon Cycle (2020)
    AGU (American Geophysical Union) | Wiley
    Details
    Publication Date: 2023-02-08
    Description: The Paleocene‐Eocene Thermal Maximum (PETM, ca. 56 Ma) is marked by a negative carbon isotope excursion (CIE) and increased global temperatures. The CIE is thought to result from the release of 13C‐depleted carbon, although the source(s) of carbon and triggers for its release, its rate of release, and the mechanisms by which the Earth system recovered are all debated. Many of the proposed mechanisms for the onset and recovery phases of the PETM make testable predictions about the marine silica cycle, making silicon isotope records a promising tool to address open questions about the PETM. We analyzed silicon isotope ratios (δ30Si) in radiolarian tests and sponge spicules from the Western North Atlantic (ODP Site 1051) across the PETM. Radiolarian δ30Si decreases by 0.6‰ from a background of 1‰ coeval with the CIE, while sponge δ30Si remains consistent at 0.2‰. Using a box model to test the Si cycle response to various scenarios, we find the data are best explained by a weak silicate weathering feedback, implying the recovery was mostly driven by nondiatom organic carbon burial, the other major long‐term carbon sink. We find no resolvable evidence for a volcanic trigger for carbon release, or for a change in regional oceanography. Better understanding of radiolarian Si isotope fractionation and more Si isotope records spanning the PETM are needed to confirm the global validity of these conclusions, but they highlight how the coupling between the silica and carbon cycles can be exploited to yield insight into the functioning of the Earth system.
    Type: Article , PeerReviewed
    Format: text
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    OceanRep: Article in a Scientific Journal - peer-reviewed
  • 3
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    The biogeochemical impact of glacial meltwater from Southwest Greenland (2019)
    Elsevier
    In:  Progress in Oceanography, 176 . Art.Nr. 102126.
    Details
    Publication Date: 2022-01-31
    Description: Highlights • Novel multi-disciplinary approach to tracing freshwater and particle transport into boundary currents; • Significant glacial inputs reach coastal waters and are transported rapidly offshore; • Low surface water dissolved silicon concentrations maintained by diatom activity despite strong glacial and benthic supplies. Abstract Biogeochemical cycling in high-latitude regions has a disproportionate impact on global nutrient budgets. Here, we introduce a holistic, multi-disciplinary framework for elucidating the influence of glacial meltwaters, shelf currents, and biological production on biogeochemical cycling in high-latitude continental margins, with a focus on the silica cycle. Our findings highlight the impact of significant glacial discharge on nutrient supply to shelf and slope waters, as well as surface and benthic production in these regions, over a range of timescales from days to thousands of years. Whilst biological uptake in fjords and strong diatom activity in coastal waters maintains low dissolved silicon concentrations in surface waters, we find important but spatially heterogeneous additions of particulates into the system, which are transported rapidly away from the shore. We expect the glacially-derived particles – together with biogenic silica tests – to be cycled rapidly through shallow sediments, resulting in a strong benthic flux of dissolved silicon. Entrainment of this benthic silicon into boundary currents may supply an important source of this key nutrient into the Labrador Sea, and is also likely to recirculate back into the deep fjords inshore. This study illustrates how geochemical and oceanographic analyses can be used together to probe further into modern nutrient cycling in this region, as well as the palaeoclimatological approaches to investigating changes in glacial meltwater discharge through time, especially during periods of rapid climatic change in the Late Quaternary.
    Type: Article , PeerReviewed
    Format: text
    Format: text
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    DOI: 10.1016/j.pocean.2019.102126
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    OceanRep: Article in a Scientific Journal - peer-reviewed
  • 4
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    Deglacial diatom production in the tropical North Atlantic driven by enhanced silicic acid supply (2016)
    Elsevier
    Details
    Publication Date: 2023-08-01
    Description: Major shifts in ocean circulation are thought to be responsible for abrupt changes in temperature and atmospheric CO2 during the last deglaciation, linked to variability in meridional heat transport and deep ocean carbon storage. There is also widespread evidence for shifts in biological production during these times of deglacial CO2 rise, including enhanced diatom production in regions such as the tropical Atlantic. However, it remains unclear as to whether this diatom production was driven by enhanced wind-driven upwelling or density-driven vertical mixing, or by elevated thermocline concentrations of silicic acid supplied to the surface at a constant rate. Here, we demonstrate that silicic acid supply at depth in the NE Atlantic was enhanced during the abrupt climate events of the deglaciation. We use marine sediment archives to show that an increase in diatom production during abrupt climate shifts could only occur in regions of the NE Atlantic where the deep supply of silicic acid could reach the surface. The associated changes are indicative of enhanced regional wind-driven upwelling and/or weakened stratification due to circulation changes during phases of weakened Atlantic meridional overturning. Globally near-synchronous pulses of diatom production and enhanced thermocline concentrations of silicic acid suggest that widespread deglacial surface-driven breakdown of stratification, linked to changes in atmospheric circulation, had major consequences for biological productivity and carbon cycling.
    Type: Article , PeerReviewed
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    OceanRep: Article in a Scientific Journal - peer-reviewed
  • 5
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    Mg/Ca-Temperature Calibration of Polar Benthic foraminifera species for reconstruction of bottom water temperatures on the Antarctic shelf (2020)
    In:  EPIC3Geochimica et Cosmochimica Acta, 283, pp. 54-66, ISSN: 00167037
    Details
    Publication Date: 2020-07-15
    Description: Benthic foraminifera Mg/Ca is a well-established bottom water temperature (BWT) proxy used in paleoclimate studies. The relationship between Mg/Ca and BWT for numerous species has been determined using core-top and culturing studies. However, the scarcity of calcareous microfossils in Antarctic shelf sediments and poorly defined calibrations at low temperatures has limited the use of the foraminiferal Mg/Ca paleothermometer in ice proximal Antarctic sediments. Here we present paired ocean temperature and modern benthic foraminifera Mg/Ca data for three species, Trifarina angulosa, Bulimina aculeata, and Globocassidulina subglobosa, but with a particular focus on Trifarina angulosa. The core-top data from several Antarctic sectors span a BWT range of −1.7 to +1.2 °C and constrain the relationship between Mg/Ca and cold temperatures. We compare our results to published lower-latitude core-top data for species in the same or related genera, and in the case of Trifarina angulosa, produce a regional calibration. The resulting regional equation for Trifarina angulosa is Temperature (°C) = (Mg/Ca −1.14 ± 0.035)/0.069 ± 0.033). Addition of our Trifarina angulosa data to the previously published Uvigerina spp. dataset provides an alternative global calibration, although some data points appear to be offset from this relationship and are discussed. Mg-temperature relationships for Bulimina aculeata and Globocassidulina subglobosa are also combined with previously published data to produce calibration equations of Temperature (°C) = (Mg/Ca-1.04 ± 0.07)/0.099 ± 0.01 and Temperature (°C) = (Mg/Ca-0.99 ± 0.03)/0.087 ± 0.01, respectively. These refined calibrations highlight the potential utility of benthic foraminifera Mg/Ca-paleothermometry for reconstructing past BWT in Antarctic margin settings.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , isiRev
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  • 6
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    Changes in micronutrient supply to the surface Southern Ocean (Atlantic sector) across the glacial termination (2011)
    American Geophysical Union
    Details
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 12 (2011): Q09007, doi:10.1029/2011GC003691.
    Description: Major deepwater masses upwell and reach the surface in the Southern Ocean, forming an important conduit supplying nutrients and micronutrients to the surface and playing a key role in the regulation of global climate through ocean-atmosphere gas exchange. Here, we reconstruct changes in micronutrient distribution in this region in response to past changes in upwelling, oceanic mixing, and sea-ice seasonality. We present two downcore (Zn/Si)opal records from the Scotia Sea and Drake Passage region, which we interpret in the context of micronutrient distribution in the Atlantic sector of the Southern Ocean over the last glacial termination. Previous work shows that micronutrient availability in the surface waters in the South Atlantic appear to be controlled dominantly by upwelling and mixing of micronutrient rich deepwaters, which are additionally fuelled by the terrestrial sediment sources of the Scotia Arc and South Georgia. This is supported by our reconstructions, which show micronutrient availability to the west of the Scotia Arc and South Georgia are consistently lower than to the east over the last glacial termination due to downstream transport and mixing into surface waters of continentally derived material in the Antarctic Circumpolar Current. Micronutrient availability in this region was at a minimum from 20 to 25 ky BP, coinciding with maximum sea-ice coverage, and increased due to an expansion of the seasonal sea-ice zone and increased mixing of subsurface waters. Our findings are consistent with largely diminished upwelling of micronutrients during the maximum glacial extent, and reduced mixing due to the presence of persistent sea-ice. During the deglacial there was an increase in micronutrient availability, as well as other nutrients and inorganic carbon, within the Antarctic Circumpolar Current as a result of an increase in deep oceanic upwelling, mixing and strengthened zonal transport.
    Description: This work was funded by NERC/S/A/2004/12390 and the Antarctic Funding Initiative grant AFI4–02.
    Keywords: Deglaciation ; Diatom opal ; Westerlies ; Zinc
    Repository Name: Woods Hole Open Access Server
    Type: Article
    Format: application/pdf
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  • 7
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    Cadmium and phosphate in coastal Antarctic seawater : implications for Southern Ocean nutrient cycling (2011)
    Details
    Publication Date: 2022-05-25
    Description: Author Posting. © The Author(s), 2008. 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 112 (2008): 149-157, doi:10.1016/j.marchem.2008.09.004.
    Description: Cadmium is a biologically important trace metal that co-varies with phosphate (PO43- or Dissolved Inorganic Phosphate, DIP) in seawater. However, the exact nature of Cd uptake mechanisms and the relationship with phosphate and other nutrients in global oceans remains elusive. Here, we present a time series study of Cd and PO43- from coastal Antarctic seawater, showing that Cd co-varies with macronutrients during times of high biological activity even under nutrient and trace metal replete conditions. Our data imply that Cd/PO43- in coastal surface Antarctic seawater is higher than open ocean areas. Furthermore, the sinking of some proportion of this high Cd/PO43- water into Antarctic Bottom Water, followed by mixing into Circumpolar Deep Water, impacts Southern Ocean preformed nutrient and trace metal composition. A simple model of endmember water mass mixing with a particle fractionation of Cd/P (αCd-P) determined by the local environment can be used to account for the Cd/PO43- relationship in different parts of the ocean. The high Cd/PO43- of the coastal water is a consequence of two factors: the high input from terrestrial and continental shelf sediments and changes in biological fractionation with respect to P during uptake of Cd in regions of high Fe and Zn. This implies that the Cd/PO43- ratio of the Southern Ocean will vary on glacial-interglacial timescales as the proportion of deep water originating on the continental shelves of the Weddell Sea is reduced during glaciations because the ice shelf is pinned at the edge of the continental shelf. There could also be variations in biological fractionation of Cd/P in the surface waters of the Southern Ocean on these timescales as a result of changes in atmospheric inputs of trace metals. Further variations in the relationship between Cd and PO43- in seawater arise from changes in population structure and community requirements for macro- and micronutrients.
    Description: The work was funded as part of NERC Antarctic Funding Initiative AFI4-02. KRH is funded by NERC grant NER/S/A/2004/12390.
    Keywords: Cadmium ; Phosphate ; Coastal ; Nutrients ; Southern Ocean
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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  • 8
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    Controls on stable isotope and trace metal uptake in Neogloboquadrina pachyderma (sinistral) from an Antarctic sea-ice environment (2011)
    Details
    Publication Date: 2022-05-25
    Description: Author Posting. © The Author(s), 2008. 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 Earth and Planetary Science Letters 278 (2009): 67-77, doi:10.1016/j.epsl.2008.11.026.
    Description: The polar foraminifera Neogloboquadrina pachyderma (sinistral) dominates assemblages from the high latitude Southern Ocean, which is a key region for paleoclimate studies. Here, we use N. pachyderma (s.) harvested from sediment traps off the West Antarctic Peninsula to construct a seasonal time series for the calibration of calcite proxies in a high latitude seasonal sea-ice environment where temperature is decoupled from other environmental parameters. We have used a combination of δ18OCaCO3 and δ13CCaCO3 to decipher the calcification temperature and salinity, which reflect that N. pachyderma (s.) live in surface waters throughout the year, and at the ice-water interface in austral winter. Further, our results demonstrate that, during winter, the uptake of trace metals into N. pachyderma (s.) calcite is influenced by secondary environmental conditions in addition to temperature during periods of sea-ice. We suggest an elevated carbonate ion concentration at the ice-water interface resulting from biological utilisation CO2 could influence calcification in foraminifera. We demonstrate that for N. pachyderma (s.) Mg/Ca and Sr/Ca ratios are linear functions of calcification temperature and [CO32-]. N. pachyderma (s.) Mg/Ca ratios exhibit temperature sensitivity similar to previous studies (~ 10 % per °C) and a sensitivity to [CO32-] of ~ 1 % per μmol kg-1). Sr/Ca ratios are less sensitive to environmental parameters, exhibiting 〈 1% increase per °C and per 10 μmol kg-1. We show how a multi-proxy approach could be used to constrain past high latitude surface water temperature and [CO32-].
    Description: The work was funded as part of NERC Antarctic Funding Initiative AFI4-02. KRH is funded by NERC grant NER/S/A/2004/12390.
    Keywords: N. pachyderma ; Isotopes ; Trace metals ; Sea-ice ; Carbonate ion
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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  • 9
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    Evidence of silicic acid leakage to the tropical Atlantic via Antarctic Intermediate Water during Marine Isotope Stage 4 (2013)
    John Wiley & Sons
    Details
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2013. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 28 (2013): 307–318, doi:10.1002/palo.20030.
    Description: Antarctic Intermediate Water (AAIW) and Subantarctic Mode Water (SAMW) are the main conduits for the supply of dissolved silicon (silicic acid) from the deep Southern Ocean (SO) to the low-latitude surface ocean and therefore have an important control on low-latitude diatom productivity. Enhanced supply of silicic acid by AAIW (and SAMW) during glacial periods may have enabled tropical diatoms to outcompete carbonate-producing phytoplankton, decreasing the relative export of inorganic to organic carbon to the deep ocean and lowering atmospheric pCO2. This mechanism is known as the “silicic acid leakage hypothesis” (SALH). Here we present records of neodymium and silicon isotopes from the western tropical Atlantic that provide the first direct evidence of increased silicic acid leakage from the Southern Ocean to the tropical Atlantic within AAIW during glacial Marine Isotope Stage 4 (~60–70 ka). This leakage was approximately coeval with enhanced diatom export in the NW Atlantic and across the eastern equatorial Atlantic and provides support for the SALH as a contributor to CO2 drawdown during full glacial development.
    Description: The work is part of a wider project on the MIS 5/4 transition, supervised by S. B. and supported by NERC (UK) grant NE/F002734/1. K.R.H. is funded by National Science Foundation grant MCG-1029986. T.v.d.F. acknowledges funding from the European Commission (IRG 230828).
    Description: 2013-12-27
    Keywords: Silica leakage ; Diatom ; Carbon dioxide ; SAMW ; AAIW
    Repository Name: Woods Hole Open Access Server
    Type: Article
    Format: application/pdf
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  • 10
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    The role of sea ice formation in cycling of aluminium in northern Marguerite Bay, Antarctica (2010)
    Details
    Publication Date: 2022-05-25
    Description: Author Posting. © The Author(s), 2009. 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 Estuarine, Coastal and Shelf Science 87 (2010): 103-112, doi:10.1016/j.ecss.2009.12.017.
    Description: The use of dissolved Al as a tracer for oceanic water masses and atmospheric dust deposition of biologically important elements, such as iron, requires the quantitative assessment of its sources and sinks in seawater. Here, we address the relative importance of oceanic versus atmospheric inputs of Al, and the relationship with nutrient cycling, in a region of high biological productivity in coastal Antarctica. We investigate the concentrations of dissolved Al in seawater, sea ice, meteoric water and sediments collected from northern Marguerite Bay, off the West Antarctic Peninsula, from 2005-2006. Dissolved Al concentrations at 15 m water depth varied between 2 and 27 nM, showing a peak between two phytoplankton blooms. We find that, in this coastal setting, upwelling and incorporation of waters from below the surface mixed layer are responsible for this peak in dissolved Al as well as renewal of nutrients. This means that changes in the intensity and frequency of upwelling events may result in changes in biological production and carbon uptake. The waters below the mixed layer are most likely enriched in Al as a result of sea ice formation, either causing the injection of Al-rich brines or the resuspension of sediments and entrainment of pore fluids by brine cascades. Glacial, snow and sea ice melt contributes secondarily to the supply of Al to surface waters. Total particulate Al ranges from 93 to 2057 μg/g, and increases with meteoric water input towards the end of the summer, indicating glacial runoff is an important source of particulate Al. The (Al/Si)opal of sediment core top material is considerably higher than water column opal collected by sediment traps, indicative of a diagenetic overprint and incorporation of Al at the sediment-water interface. Opal that remains buried in the sediment could represent a significant sink of Al from seawater.
    Description: This project is part of AFI4‐02 and KRH was funded by NERC grant NER/S/A/2004/12390.
    Keywords: Biogeochemistry ; Nutrients (mineral) ; Trace metals ; Brines ; Antarctica
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
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