The marine biogeochemistry of chromium isotopes

In the ocean, chromium (Cr) is a redox-sensitive trace metal. The reduction of Cr(VI) to Cr(III) occurs in oxygen deficient zones (ODZs), and Cr reduction in general has been identified as a significant Cr isotope fractionation mechanism. This thesis presents the first Cr isotope variations (653 Cr) in ODZs of the ocean and adds to the sparse Cr isotope data published for modern seawater. I developed a precise and accurate Cr isotope method for seawater samples. Seawater acidification converts total Cr to Cr(III) which is preconcentrated by Mg(OH) 2 coprecipitation. A three-column anion exchange chromatography scheme separates Cr from isobaric and polyatomic interferences present in the seawater and reagent matrixes. Isotope analysis is performed on a MC-ICP-MS IsoProbe. The addition of a 50Cr-54Cr double spike allows for accurate correction of procedural and instrumental Cr mass fractionations. The first Cr isotope ratio data for a full water column profile in the Pacific Ocean is presented. This station serves as a fully oxic counterpart to stations located within the ODZ of the Eastern Tropical North Pacific. At one station, Cr concentrations are lower and [delta]53Cr values are heavier within the ODZ. This is consistent with Cr reduction resulting in isotopically lighter, particle-reactive Cr(III), which is scavenged and exported from the water column. A strong correlation of [delta]53Cr and [delta]15 NNo3- at this station suggests that Cr reduction may be microbially mediated instead of simply being a product of thermodynamic equilibrium. Alternatively, Cr may be reduced by Fe(II). In the anoxic bottom waters of the Santa Barbara Basin a strong Cr reduction signal (lower [Cr], heavier [delta]53Cr) is observed, which may result from the same aforementioned Cr reduction mechanisms. A shift to the heaviest seawater Cr isotope signatures yet observed was detected in the oxic bottom waters of the shallow Arctic Chukchi shelf, while Cr concentrations decreased. This extreme isotope signal may result from Cr reduction by a reduced species (e.g. Fe(II)), which was released from the underlying anoxic shelf sediments. Cr in the Atlantic layer and in the bottom water of a central Arctic station appears to be shaped by a novel, unidentified process.

Department dc:contributor.department

Joint Program in Oceanography/Applied Ocean Science and Engineering

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2018

Author dc:creator

• Moos, Simone Beatrice

Advisor dc:contributor.advisor

• Edward A. Boyle.

• Joint Program in Oceanography/Applied Ocean Science and Engineering.
• Earth, Atmospheric, and Planetary Sciences.
• Woods Hole Oceanographic Institution.

Statement dc:rights

• MIT theses are protected by copyright. They may be viewed, downloaded, or printed from this source but further reproduction or distribution in any format is prohibited without written permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/115788

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/115788