A sequential extraction procedure for particulate manganese and its application to coastal marine sediments

Wytze Lenstra; Robin Klomp; Ferike Molema; Thilo Behrends; Caroline Slomp

doi:10.1016/j.chemgeo.2021.120538

A sequential extraction procedure for particulate manganese and its application to coastal marine sediments

Wytze Lenstra^*, Robin Klomp, Ferike Molema, Thilo Behrends, Caroline Slomp

^*Corresponding author for this work

Utrecht University

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

An existing sequential extraction scheme for particulate iron (Fe) is evaluated for manganese (Mn) using a range of Mn standards. The scheme consists of 5 steps and quantifies 5 operationally defined Mn pools (1) poorly ordered Mn oxides and Mn phosphates (ascorbic acid extractable); (2) Mn carbonates and Mn sulfides (1 M HCl extractable), (3 and 4) crystalline Mn oxides (citrate buffered dithionite and ammonium oxalate extractable, respectively) and (5) Mn associated with pyrite (concentrated HNO₃ extractable). Application of the extraction scheme to coastal sediments from six locations (Black Sea, Baltic Sea, Bothnian Sea, Gulf of Mexico and Chesapeake Bay) highlights the dependency of sediment Mn partitioning on bottom water redox conditions. In sediments deposited in anoxic and sulfidic (euxinic) bottom waters, Mn is mostly present in Mn carbonates, pyrite and in non-reactive Mn forms, in approximately equal amounts. We find that in sediments deposited in periodically euxinic and hypoxic (oxygen <63 μmol L⁻¹) waters, Mn carbonates dominate over the two other fractions, and small amounts of Mn oxides are observed. In sediments deposited in oxygenated bottom waters, Mn oxides, Mn-rich vivianite-type minerals and Mn carbonates dominate and no pyrite-bound Mn is observed. A large advantage of the extraction scheme is that it quantifies sediment forms of Mn and Fe simultaneously. Given the role of Mn as a bottom water redox proxy, the separation of poorly ordered Mn oxides, carbonates and pyrite is of specific relevance.

Original language	English
Article number	120538
Pages (from-to)	1-10
Journal	Chemical Geology
Volume	584
DOIs	https://doi.org/10.1016/j.chemgeo.2021.120538
Publication status	Published - 5 Dec 2021

Bibliographical note

Funding Information:
We thank C. Mulder, H. de Waard, N. van Helmond and A. van Leeuwen-Tolboom for analytical assistance. This research was funded by the Netherlands Organisation for Scientific Research (NWO-Vici grant 865.13.005), Netherlands Earth System Science Centre (NESSC Gravitation grant 024.002.001) and ERC (ERC synergy MARIX grant 854088).

Funding Information:
We thank C. Mulder, H. de Waard, N. van Helmond and A. van Leeuwen-Tolboom for analytical assistance. This research was funded by the Netherlands Organisation for Scientific Research ( NWO -Vici grant 865.13.005 ), Netherlands Earth System Science Centre (NESSC Gravitation grant 024.002.001 ) and ERC (ERC synergy MARIX grant 854088 ).

Publisher Copyright:
© 2021

Keywords

Manganese
Manganese standards
Sediment
Sequential extraction

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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Cite this

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title = "A sequential extraction procedure for particulate manganese and its application to coastal marine sediments",

abstract = "An existing sequential extraction scheme for particulate iron (Fe) is evaluated for manganese (Mn) using a range of Mn standards. The scheme consists of 5 steps and quantifies 5 operationally defined Mn pools (1) poorly ordered Mn oxides and Mn phosphates (ascorbic acid extractable); (2) Mn carbonates and Mn sulfides (1 M HCl extractable), (3 and 4) crystalline Mn oxides (citrate buffered dithionite and ammonium oxalate extractable, respectively) and (5) Mn associated with pyrite (concentrated HNO3 extractable). Application of the extraction scheme to coastal sediments from six locations (Black Sea, Baltic Sea, Bothnian Sea, Gulf of Mexico and Chesapeake Bay) highlights the dependency of sediment Mn partitioning on bottom water redox conditions. In sediments deposited in anoxic and sulfidic (euxinic) bottom waters, Mn is mostly present in Mn carbonates, pyrite and in non-reactive Mn forms, in approximately equal amounts. We find that in sediments deposited in periodically euxinic and hypoxic (oxygen <63 μmol L−1) waters, Mn carbonates dominate over the two other fractions, and small amounts of Mn oxides are observed. In sediments deposited in oxygenated bottom waters, Mn oxides, Mn-rich vivianite-type minerals and Mn carbonates dominate and no pyrite-bound Mn is observed. A large advantage of the extraction scheme is that it quantifies sediment forms of Mn and Fe simultaneously. Given the role of Mn as a bottom water redox proxy, the separation of poorly ordered Mn oxides, carbonates and pyrite is of specific relevance.",

keywords = "Manganese, Manganese standards, Sediment, Sequential extraction",

author = "Wytze Lenstra and Robin Klomp and Ferike Molema and Thilo Behrends and Caroline Slomp",

note = "Funding Information: We thank C. Mulder, H. de Waard, N. van Helmond and A. van Leeuwen-Tolboom for analytical assistance. This research was funded by the Netherlands Organisation for Scientific Research (NWO-Vici grant 865.13.005), Netherlands Earth System Science Centre (NESSC Gravitation grant 024.002.001) and ERC (ERC synergy MARIX grant 854088). Funding Information: We thank C. Mulder, H. de Waard, N. van Helmond and A. van Leeuwen-Tolboom for analytical assistance. This research was funded by the Netherlands Organisation for Scientific Research ( NWO -Vici grant 865.13.005 ), Netherlands Earth System Science Centre (NESSC Gravitation grant 024.002.001 ) and ERC (ERC synergy MARIX grant 854088 ). Publisher Copyright: {\textcopyright} 2021",

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doi = "10.1016/j.chemgeo.2021.120538",

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AU - Lenstra, Wytze

AU - Klomp, Robin

AU - Molema, Ferike

AU - Behrends, Thilo

AU - Slomp, Caroline

N1 - Funding Information: We thank C. Mulder, H. de Waard, N. van Helmond and A. van Leeuwen-Tolboom for analytical assistance. This research was funded by the Netherlands Organisation for Scientific Research (NWO-Vici grant 865.13.005), Netherlands Earth System Science Centre (NESSC Gravitation grant 024.002.001) and ERC (ERC synergy MARIX grant 854088). Funding Information: We thank C. Mulder, H. de Waard, N. van Helmond and A. van Leeuwen-Tolboom for analytical assistance. This research was funded by the Netherlands Organisation for Scientific Research ( NWO -Vici grant 865.13.005 ), Netherlands Earth System Science Centre (NESSC Gravitation grant 024.002.001 ) and ERC (ERC synergy MARIX grant 854088 ). Publisher Copyright: © 2021

PY - 2021/12/5

Y1 - 2021/12/5

N2 - An existing sequential extraction scheme for particulate iron (Fe) is evaluated for manganese (Mn) using a range of Mn standards. The scheme consists of 5 steps and quantifies 5 operationally defined Mn pools (1) poorly ordered Mn oxides and Mn phosphates (ascorbic acid extractable); (2) Mn carbonates and Mn sulfides (1 M HCl extractable), (3 and 4) crystalline Mn oxides (citrate buffered dithionite and ammonium oxalate extractable, respectively) and (5) Mn associated with pyrite (concentrated HNO3 extractable). Application of the extraction scheme to coastal sediments from six locations (Black Sea, Baltic Sea, Bothnian Sea, Gulf of Mexico and Chesapeake Bay) highlights the dependency of sediment Mn partitioning on bottom water redox conditions. In sediments deposited in anoxic and sulfidic (euxinic) bottom waters, Mn is mostly present in Mn carbonates, pyrite and in non-reactive Mn forms, in approximately equal amounts. We find that in sediments deposited in periodically euxinic and hypoxic (oxygen <63 μmol L−1) waters, Mn carbonates dominate over the two other fractions, and small amounts of Mn oxides are observed. In sediments deposited in oxygenated bottom waters, Mn oxides, Mn-rich vivianite-type minerals and Mn carbonates dominate and no pyrite-bound Mn is observed. A large advantage of the extraction scheme is that it quantifies sediment forms of Mn and Fe simultaneously. Given the role of Mn as a bottom water redox proxy, the separation of poorly ordered Mn oxides, carbonates and pyrite is of specific relevance.

AB - An existing sequential extraction scheme for particulate iron (Fe) is evaluated for manganese (Mn) using a range of Mn standards. The scheme consists of 5 steps and quantifies 5 operationally defined Mn pools (1) poorly ordered Mn oxides and Mn phosphates (ascorbic acid extractable); (2) Mn carbonates and Mn sulfides (1 M HCl extractable), (3 and 4) crystalline Mn oxides (citrate buffered dithionite and ammonium oxalate extractable, respectively) and (5) Mn associated with pyrite (concentrated HNO3 extractable). Application of the extraction scheme to coastal sediments from six locations (Black Sea, Baltic Sea, Bothnian Sea, Gulf of Mexico and Chesapeake Bay) highlights the dependency of sediment Mn partitioning on bottom water redox conditions. In sediments deposited in anoxic and sulfidic (euxinic) bottom waters, Mn is mostly present in Mn carbonates, pyrite and in non-reactive Mn forms, in approximately equal amounts. We find that in sediments deposited in periodically euxinic and hypoxic (oxygen <63 μmol L−1) waters, Mn carbonates dominate over the two other fractions, and small amounts of Mn oxides are observed. In sediments deposited in oxygenated bottom waters, Mn oxides, Mn-rich vivianite-type minerals and Mn carbonates dominate and no pyrite-bound Mn is observed. A large advantage of the extraction scheme is that it quantifies sediment forms of Mn and Fe simultaneously. Given the role of Mn as a bottom water redox proxy, the separation of poorly ordered Mn oxides, carbonates and pyrite is of specific relevance.

KW - Manganese

KW - Manganese standards

KW - Sediment

KW - Sequential extraction

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U2 - 10.1016/j.chemgeo.2021.120538

DO - 10.1016/j.chemgeo.2021.120538

M3 - Article

SN - 0009-2541

VL - 584

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JO - Chemical Geology

JF - Chemical Geology

M1 - 120538

ER -

A sequential extraction procedure for particulate manganese and its application to coastal marine sediments

Abstract

Bibliographical note

Keywords

UN SDGs

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