_version_ 1867170927224029184
author Kraal, Peter
Slomp, Caroline P
Forster, Astrid
Kuypers, Marcel MM
Sluijs, Appy
author_facet Kraal, Peter
Slomp, Caroline P
Forster, Astrid
Kuypers, Marcel MM
Sluijs, Appy
collection Datos científicos de ciencias marinas y ambientales
contents We investigated the phosphorus (P) and iron (Fe) fractionation in four cores with anoxic sediments, deposited during the mid-Cretaceous oceanic anoxic event 2 (~94 Ma) and the Paleocene-Eocene thermal maximum (?55 Ma), that were exposed to oxygen after core recovery. Surprisingly, P associated with iron oxyhydroxides (Fe-bound P) was a major P phase in these laminated sediments deposited under euxinic conditions. A significant fraction of total Fe was present as (poorly) crystalline ferric Fe. This fraction increased with increasing storage time of the investigated cores. In carbonate-poor samples, Fe-bound P accounted for up to 99% of total P and its abundance correlated with pyrite contents. In samples with higher CaCO3 contents (>5 wt% in the investigated samples), P was mostly present in authigenic Ca-P minerals, irrespective of pyrite contents. We conclude that the P fractionation in anoxic, carbonate-poor, sediments is strongly affected by pyrite oxidation that occurs when these sediments are exposed to oxygen. Pyrite oxidation produces sulfuric acid and iron oxyhydroxides. The abundance of poorly crystalline Fe oxyhydroxides provides further evidence that these were indeed formed through recent (post-recovery) oxidation rather than in situ tens of millions of years ago. The acid dissolves apatite and the released phosphate is subsequently bound in the freshly formed iron oxyhydroxides. Pyrite oxidation thus leads to a conversion of authigenic Ca-P to Fe-bound P. In more calcareous samples, CaCO3 can act as an effective buffer against acidic dissolution of Ca-P minerals. The results indicate that shielding of sediments from atmospheric oxygen is vital to preserve the in situ P fractionation and to enable a valid reconstruction of marine phosphorus cycling based on sediment records.
format Dataset Open Access
id pangaea_https___doi_org_10_1594_PANGAEA_783338
institution PANGAEA
language en
publishDate 2009
publisher PANGAEA
record_format pangaea
spellingShingle Geochemistry and P and Fe fractionation in anoxic sediments
Kraal, Peter
Slomp, Caroline P
Forster, Astrid
Kuypers, Marcel MM
Sluijs, Appy
207-1260; 302-M0004A; 41-367; 93-603B; ACEX-M4A; Arctic Coring Expedition, ACEX; Arctic Ocean; Calcium carbonate; CCGS Captain Molly Kool (Vidar Viking); COMPCORE; Composite Core; Deep Sea Drilling Project; DEPTH, sediment/rock; DRILL; Drilling/drill rig; DSDP; Event label; Exp302; Glomar Challenger; Integrated Ocean Drilling Program / International Ocean Discovery Program; IODP; Iron; Iron/Sulfur ratio; Joides Resolution; Leg207; Leg41; Leg93; North Atlantic/BASIN; North Atlantic Ocean; Ocean Drilling Program; ODP; Phosphorus, authigenic; Phosphorus, exchangeable; Phosphorus, iron-bound; Phosphorus, total; Pyrite, FeS2; Ratio
We investigated the phosphorus (P) and iron (Fe) fractionation in four cores with anoxic sediments, deposited during the mid-Cretaceous oceanic anoxic event 2 (~94 Ma) and the Paleocene-Eocene thermal maximum (?55 Ma), that were exposed to oxygen after core recovery. Surprisingly, P associated with iron oxyhydroxides (Fe-bound P) was a major P phase in these laminated sediments deposited under euxinic conditions. A significant fraction of total Fe was present as (poorly) crystalline ferric Fe. This fraction increased with increasing storage time of the investigated cores. In carbonate-poor samples, Fe-bound P accounted for up to 99% of total P and its abundance correlated with pyrite contents. In samples with higher CaCO3 contents (>5 wt% in the investigated samples), P was mostly present in authigenic Ca-P minerals, irrespective of pyrite contents. We conclude that the P fractionation in anoxic, carbonate-poor, sediments is strongly affected by pyrite oxidation that occurs when these sediments are exposed to oxygen. Pyrite oxidation produces sulfuric acid and iron oxyhydroxides. The abundance of poorly crystalline Fe oxyhydroxides provides further evidence that these were indeed formed through recent (post-recovery) oxidation rather than in situ tens of millions of years ago. The acid dissolves apatite and the released phosphate is subsequently bound in the freshly formed iron oxyhydroxides. Pyrite oxidation thus leads to a conversion of authigenic Ca-P to Fe-bound P. In more calcareous samples, CaCO3 can act as an effective buffer against acidic dissolution of Ca-P minerals. The results indicate that shielding of sediments from atmospheric oxygen is vital to preserve the in situ P fractionation and to enable a valid reconstruction of marine phosphorus cycling based on sediment records.
title Geochemistry and P and Fe fractionation in anoxic sediments
topic 207-1260; 302-M0004A; 41-367; 93-603B; ACEX-M4A; Arctic Coring Expedition, ACEX; Arctic Ocean; Calcium carbonate; CCGS Captain Molly Kool (Vidar Viking); COMPCORE; Composite Core; Deep Sea Drilling Project; DEPTH, sediment/rock; DRILL; Drilling/drill rig; DSDP; Event label; Exp302; Glomar Challenger; Integrated Ocean Drilling Program / International Ocean Discovery Program; IODP; Iron; Iron/Sulfur ratio; Joides Resolution; Leg207; Leg41; Leg93; North Atlantic/BASIN; North Atlantic Ocean; Ocean Drilling Program; ODP; Phosphorus, authigenic; Phosphorus, exchangeable; Phosphorus, iron-bound; Phosphorus, total; Pyrite, FeS2; Ratio
url https://doi.org/10.1594/PANGAEA.783338