{"id":{"repo_id":"soton","oai_identifier":"oai:eprints.soton.ac.uk:169045"},"canonical_url":"https://search.dev.ndltd.org/etd/soton/oai:eprints.soton.ac.uk:169045","repository":{"repo_id":"soton","name":"University of Southampton","base_url":"https://eprints.soton.ac.uk/cgi/oai2"},"display":{"title":"Iron inputs from sediments to the oceans","abstract":"This thesis explores the nature and ubiquity of iron (Fe) inputs from sediments to the<br/>oceans. In the last 10 years continental shelf sediments have become widely recognised<br/>as important vectors for dissolved Fe inputs to the oceans, where bacterial dissimilatory<br/>Fe-reduction (DIR) promotes the flux of Fe to the water column during the oxidation of<br/>sedimentary organic matter. Deep-sea and volcanogenic sediments however, are<br/>important reservoirs of Fe, which have not yet been investigated as sources of Fe to<br/>seawater. Furthermore knowledge of the nature of Fe phases involved in sediment, porefluid<br/>and seawater cycling is limited.<br/>The nature of Fe cycling was investigated in deep-sea volcaniclastic surface-sediments<br/>(0-20 cmbsf). Pore-fluid and sediment samples were collected from tephra-rich sites near<br/>the active volcanic island of Montserrat, Caribbean Sea, and mixed biosiliceous sites<br/>around the dormant Crozet Island archipelago, Southern Ocean. Analyses reveal both<br/>regions maintain high pore-fluid Fe concentrations close to the sediment surface (up to<br/>20 ?M 0-5 cmbsf), despite relatively low organic carbon supply and contrasting oxygen<br/>utilization pathways. The oxidation of young tephra is thought to maintain the steep<br/>oxygen gradient measured in Montserrat sediments, and is considered to be an important<br/>component of Fe, and in particular manganese (Mn), cycling with local bottom water.<br/>Unlike Montserrat dissolved Fe and Mn in Crozet pore-fluids are dominated by colloidal<br/>phases (0.02-0.2 ?m), and in both oxic and sub-oxic sediment layers. Thus mixed<br/>biosiliceous-volcaniclastic sediments are shown to host important colloidal-Fe generating<br/>reactions, which it is argued, promote the exchange of Fe with the overlying bottom<br/>waters. Re-cycling processes close to the seafloor are likely to determine the impact of<br/>this flux on seawater Fe budgets.<br/>Low-cost ex-situ incubation experiments were used to measure a benthic Fe flux on<br/>sediments from the river-dominated Californian margin (6.3 ± 5.9 ?mol Fe m-2 yr-1)<br/>consistent with previous studies. Fe and Mn fluxes from Montserrat tephra deposits were<br/>also assessed; Differences in oxidation kinetics are shown to prevent the accumulation of<br/>Fe, yet permit the accumulation of Mn (~27 ?mol m-2 yr-1) in Montserrat bottom waters.<br/>Studies indicate temporospatial variations to bioirrigation and sediment re-suspension are<br/>important aspects of sedimentary Fe inputs that are poorly represented by conventional<br/>sampling methods.<br/>In an effort to trace the biogeochemical processing of pore-fluid Fe in Crozet sediments,<br/>its isotopic composition was determined, representing the first measurements of their<br/>kind in deep-sea pore-fluids. Unique relative to previous studies of pore-fluid Fe isotopes,<br/>the near-crustal ?56Fe compositions, demonstrate that DIR does not impart the same light<br/>Fe-isotopic signature that characterises previous sub-oxic pore-fluids. Comparison of<br/>reactive Fe contents between Crozet and pacific margin sediments indicates pore-fluid Fe<br/>isotopes reflect the extent to which Fe is recycled by redox processes. This discovery<br/>brings to light the potential for Fe isotopes to trace the input of Fe from shelf sediments,<br/>where redox re-cycling of Fe is extensive. The mean oceanic Fe isotope composition<br/>(?56Fe) is predicted to be -0.1 to -3.2‰ depending on the balance of uncertainty in input<br/>terms. The predicted surface water Fe isotope composition in the Crozet region (-2.0 to -<br/>2.2‰) is shown to reflect the light composition of shelf-derived Fe for a Fe inventory<br/>already constrained for this region.","abstract_html":"This thesis explores the nature and ubiquity of iron (Fe) inputs from sediments to the&lt;br/&gt;oceans. In the last 10 years continental shelf sediments have become widely recognised&lt;br/&gt;as important vectors for dissolved Fe inputs to the oceans, where bacterial dissimilatory&lt;br/&gt;Fe-reduction (DIR) promotes the flux of Fe to the water column during the oxidation of&lt;br/&gt;sedimentary organic matter. Deep-sea and volcanogenic sediments however, are&lt;br/&gt;important reservoirs of Fe, which have not yet been investigated as sources of Fe to&lt;br/&gt;seawater. Furthermore knowledge of the nature of Fe phases involved in sediment, porefluid&lt;br/&gt;and seawater cycling is limited.&lt;br/&gt;The nature of Fe cycling was investigated in deep-sea volcaniclastic surface-sediments&lt;br/&gt;(0-20 cmbsf). Pore-fluid and sediment samples were collected from tephra-rich sites near&lt;br/&gt;the active volcanic island of Montserrat, Caribbean Sea, and mixed biosiliceous sites&lt;br/&gt;around the dormant Crozet Island archipelago, Southern Ocean. Analyses reveal both&lt;br/&gt;regions maintain high pore-fluid Fe concentrations close to the sediment surface (up to&lt;br/&gt;20 ?M 0-5 cmbsf), despite relatively low organic carbon supply and contrasting oxygen&lt;br/&gt;utilization pathways. The oxidation of young tephra is thought to maintain the steep&lt;br/&gt;oxygen gradient measured in Montserrat sediments, and is considered to be an important&lt;br/&gt;component of Fe, and in particular manganese (Mn), cycling with local bottom water.&lt;br/&gt;Unlike Montserrat dissolved Fe and Mn in Crozet pore-fluids are dominated by colloidal&lt;br/&gt;phases (0.02-0.2 ?m), and in both oxic and sub-oxic sediment layers. Thus mixed&lt;br/&gt;biosiliceous-volcaniclastic sediments are shown to host important colloidal-Fe generating&lt;br/&gt;reactions, which it is argued, promote the exchange of Fe with the overlying bottom&lt;br/&gt;waters. Re-cycling processes close to the seafloor are likely to determine the impact of&lt;br/&gt;this flux on seawater Fe budgets.&lt;br/&gt;Low-cost ex-situ incubation experiments were used to measure a benthic Fe flux on&lt;br/&gt;sediments from the river-dominated Californian margin (6.3 ± 5.9 ?mol Fe m-2 yr-1)&lt;br/&gt;consistent with previous studies. Fe and Mn fluxes from Montserrat tephra deposits were&lt;br/&gt;also assessed; Differences in oxidation kinetics are shown to prevent the accumulation of&lt;br/&gt;Fe, yet permit the accumulation of Mn (~27 ?mol m-2 yr-1) in Montserrat bottom waters.&lt;br/&gt;Studies indicate temporospatial variations to bioirrigation and sediment re-suspension are&lt;br/&gt;important aspects of sedimentary Fe inputs that are poorly represented by conventional&lt;br/&gt;sampling methods.&lt;br/&gt;In an effort to trace the biogeochemical processing of pore-fluid Fe in Crozet sediments,&lt;br/&gt;its isotopic composition was determined, representing the first measurements of their&lt;br/&gt;kind in deep-sea pore-fluids. Unique relative to previous studies of pore-fluid Fe isotopes,&lt;br/&gt;the near-crustal ?56Fe compositions, demonstrate that DIR does not impart the same light&lt;br/&gt;Fe-isotopic signature that characterises previous sub-oxic pore-fluids. Comparison of&lt;br/&gt;reactive Fe contents between Crozet and pacific margin sediments indicates pore-fluid Fe&lt;br/&gt;isotopes reflect the extent to which Fe is recycled by redox processes. This discovery&lt;br/&gt;brings to light the potential for Fe isotopes to trace the input of Fe from shelf sediments,&lt;br/&gt;where redox re-cycling of Fe is extensive. The mean oceanic Fe isotope composition&lt;br/&gt;(?56Fe) is predicted to be -0.1 to -3.2‰ depending on the balance of uncertainty in input&lt;br/&gt;terms. The predicted surface water Fe isotope composition in the Crozet region (-2.0 to -&lt;br/&gt;2.2‰) is shown to reflect the light composition of shelf-derived Fe for a Fe inventory&lt;br/&gt;already constrained for this region.","abstract_has_math":false,"creators":["Homoky, William Bela"],"institution":"University of Southampton","degree_name":"Ph.D.","degree_level":"doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2009,"date_issued":"2009-12","date_published":"2009-12","updated_at":"2026-07-24T04:36:17Z","subjects":[],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Homoky, William Bela"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2009-12"]},{"key":"dc:date.issued","label":"Date","values":["2009-12"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Ocean and Earth Science (pre 2011 reorg)","School of Ocean and Earth Science"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Southampton"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://eprints.soton.ac.uk/169045/"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["doctoral"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["Ph.D."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://eprints.soton.ac.uk/169045/1/Homoky_PhD_2010.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["This thesis explores the nature and ubiquity of iron (Fe) inputs from sediments to the<br/>oceans. In the last 10 years continental shelf sediments have become widely recognised<br/>as important vectors for dissolved Fe inputs to the oceans, where bacterial dissimilatory<br/>Fe-reduction (DIR) promotes the flux of Fe to the water column during the oxidation of<br/>sedimentary organic matter. Deep-sea and volcanogenic sediments however, are<br/>important reservoirs of Fe, which have not yet been investigated as sources of Fe to<br/>seawater. Furthermore knowledge of the nature of Fe phases involved in sediment, porefluid<br/>and seawater cycling is limited.<br/>The nature of Fe cycling was investigated in deep-sea volcaniclastic surface-sediments<br/>(0-20 cmbsf). Pore-fluid and sediment samples were collected from tephra-rich sites near<br/>the active volcanic island of Montserrat, Caribbean Sea, and mixed biosiliceous sites<br/>around the dormant Crozet Island archipelago, Southern Ocean. Analyses reveal both<br/>regions maintain high pore-fluid Fe concentrations close to the sediment surface (up to<br/>20 ?M 0-5 cmbsf), despite relatively low organic carbon supply and contrasting oxygen<br/>utilization pathways. The oxidation of young tephra is thought to maintain the steep<br/>oxygen gradient measured in Montserrat sediments, and is considered to be an important<br/>component of Fe, and in particular manganese (Mn), cycling with local bottom water.<br/>Unlike Montserrat dissolved Fe and Mn in Crozet pore-fluids are dominated by colloidal<br/>phases (0.02-0.2 ?m), and in both oxic and sub-oxic sediment layers. Thus mixed<br/>biosiliceous-volcaniclastic sediments are shown to host important colloidal-Fe generating<br/>reactions, which it is argued, promote the exchange of Fe with the overlying bottom<br/>waters. Re-cycling processes close to the seafloor are likely to determine the impact of<br/>this flux on seawater Fe budgets.<br/>Low-cost ex-situ incubation experiments were used to measure a benthic Fe flux on<br/>sediments from the river-dominated Californian margin (6.3 ± 5.9 ?mol Fe m-2 yr-1)<br/>consistent with previous studies. Fe and Mn fluxes from Montserrat tephra deposits were<br/>also assessed; Differences in oxidation kinetics are shown to prevent the accumulation of<br/>Fe, yet permit the accumulation of Mn (~27 ?mol m-2 yr-1) in Montserrat bottom waters.<br/>Studies indicate temporospatial variations to bioirrigation and sediment re-suspension are<br/>important aspects of sedimentary Fe inputs that are poorly represented by conventional<br/>sampling methods.<br/>In an effort to trace the biogeochemical processing of pore-fluid Fe in Crozet sediments,<br/>its isotopic composition was determined, representing the first measurements of their<br/>kind in deep-sea pore-fluids. Unique relative to previous studies of pore-fluid Fe isotopes,<br/>the near-crustal ?56Fe compositions, demonstrate that DIR does not impart the same light<br/>Fe-isotopic signature that characterises previous sub-oxic pore-fluids. Comparison of<br/>reactive Fe contents between Crozet and pacific margin sediments indicates pore-fluid Fe<br/>isotopes reflect the extent to which Fe is recycled by redox processes. This discovery<br/>brings to light the potential for Fe isotopes to trace the input of Fe from shelf sediments,<br/>where redox re-cycling of Fe is extensive. The mean oceanic Fe isotope composition<br/>(?56Fe) is predicted to be -0.1 to -3.2‰ depending on the balance of uncertainty in input<br/>terms. The predicted surface water Fe isotope composition in the Crozet region (-2.0 to -<br/>2.2‰) is shown to reflect the light composition of shelf-derived Fe for a Fe inventory<br/>already constrained for this region."]},{"key":"dc:format","label":"Dc Format","values":["text"]},{"key":"dc:title","label":"Title","values":["Iron inputs from sediments to the oceans"]}]}],"canonical_facts":{"dc:creator":["Homoky, William Bela"],"dc:date":["2009-12"],"dc:date.issued":["2009-12"],"dc:description.abstract":["This thesis explores the nature and ubiquity of iron (Fe) inputs from sediments to the<br/>oceans. In the last 10 years continental shelf sediments have become widely recognised<br/>as important vectors for dissolved Fe inputs to the oceans, where bacterial dissimilatory<br/>Fe-reduction (DIR) promotes the flux of Fe to the water column during the oxidation of<br/>sedimentary organic matter. Deep-sea and volcanogenic sediments however, are<br/>important reservoirs of Fe, which have not yet been investigated as sources of Fe to<br/>seawater. Furthermore knowledge of the nature of Fe phases involved in sediment, porefluid<br/>and seawater cycling is limited.<br/>The nature of Fe cycling was investigated in deep-sea volcaniclastic surface-sediments<br/>(0-20 cmbsf). Pore-fluid and sediment samples were collected from tephra-rich sites near<br/>the active volcanic island of Montserrat, Caribbean Sea, and mixed biosiliceous sites<br/>around the dormant Crozet Island archipelago, Southern Ocean. Analyses reveal both<br/>regions maintain high pore-fluid Fe concentrations close to the sediment surface (up to<br/>20 ?M 0-5 cmbsf), despite relatively low organic carbon supply and contrasting oxygen<br/>utilization pathways. The oxidation of young tephra is thought to maintain the steep<br/>oxygen gradient measured in Montserrat sediments, and is considered to be an important<br/>component of Fe, and in particular manganese (Mn), cycling with local bottom water.<br/>Unlike Montserrat dissolved Fe and Mn in Crozet pore-fluids are dominated by colloidal<br/>phases (0.02-0.2 ?m), and in both oxic and sub-oxic sediment layers. Thus mixed<br/>biosiliceous-volcaniclastic sediments are shown to host important colloidal-Fe generating<br/>reactions, which it is argued, promote the exchange of Fe with the overlying bottom<br/>waters. Re-cycling processes close to the seafloor are likely to determine the impact of<br/>this flux on seawater Fe budgets.<br/>Low-cost ex-situ incubation experiments were used to measure a benthic Fe flux on<br/>sediments from the river-dominated Californian margin (6.3 ± 5.9 ?mol Fe m-2 yr-1)<br/>consistent with previous studies. Fe and Mn fluxes from Montserrat tephra deposits were<br/>also assessed; Differences in oxidation kinetics are shown to prevent the accumulation of<br/>Fe, yet permit the accumulation of Mn (~27 ?mol m-2 yr-1) in Montserrat bottom waters.<br/>Studies indicate temporospatial variations to bioirrigation and sediment re-suspension are<br/>important aspects of sedimentary Fe inputs that are poorly represented by conventional<br/>sampling methods.<br/>In an effort to trace the biogeochemical processing of pore-fluid Fe in Crozet sediments,<br/>its isotopic composition was determined, representing the first measurements of their<br/>kind in deep-sea pore-fluids. Unique relative to previous studies of pore-fluid Fe isotopes,<br/>the near-crustal ?56Fe compositions, demonstrate that DIR does not impart the same light<br/>Fe-isotopic signature that characterises previous sub-oxic pore-fluids. Comparison of<br/>reactive Fe contents between Crozet and pacific margin sediments indicates pore-fluid Fe<br/>isotopes reflect the extent to which Fe is recycled by redox processes. This discovery<br/>brings to light the potential for Fe isotopes to trace the input of Fe from shelf sediments,<br/>where redox re-cycling of Fe is extensive. The mean oceanic Fe isotope composition<br/>(?56Fe) is predicted to be -0.1 to -3.2‰ depending on the balance of uncertainty in input<br/>terms. The predicted surface water Fe isotope composition in the Crozet region (-2.0 to -<br/>2.2‰) is shown to reflect the light composition of shelf-derived Fe for a Fe inventory<br/>already constrained for this region."],"dc:format":["text"],"dc:identifier.uri":["https://eprints.soton.ac.uk/169045/1/Homoky_PhD_2010.pdf"],"dc:publisher.department":["Ocean and Earth Science (pre 2011 reorg)","School of Ocean and Earth Science"],"dc:publisher.institution":["University of Southampton"],"dc:relation.isreferencedby":["https://eprints.soton.ac.uk/169045/"],"dc:title":["Iron inputs from sediments to the oceans"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["doctoral"],"dc:type.qualificationname":["Ph.D."]},"updated_at":"2026-07-24T04:36:17Z"}