Skip to main content Accessibility help
×
Hostname: page-component-7c8c6479df-995ml Total loading time: 0 Render date: 2024-03-28T05:20:26.748Z Has data issue: false hasContentIssue false

The Chromium Isotope System as a Tracer of Ocean and Atmosphere Redox

Published online by Cambridge University Press:  26 January 2021

Kohen W. Bauer
Affiliation:
University of British Columbia, Vancouver
Noah J. Planavsky
Affiliation:
Yale University, Connecticut
Christopher T. Reinhard
Affiliation:
Georgia Institute of Technology
Devon B. Cole
Affiliation:
Georgia Institute of Technology

Summary

The stable chromium (Cr) isotope system has emerged over the past decade as a new tool to track changes in the amount of oxygen in earth's ocean-atmosphere system. Much of the initial foundation for using Cr isotopes (δ53Cr) as a paleoredox proxy has required recent revision. However, the basic idea behind using Cr isotopes as redox tracers is straightforward—the largest isotope fractionations are redox-dependent and occur during partial reduction of Cr(VI). As such, Cr isotopic signatures can provide novel insights into Cr redox cycling in both marine and terrestrial settings. Critically, the Cr isotope system—unlike many other trace metal proxies—can respond to short-term redox perturbations (e.g., on timescales characteristic of Pleistocene glacial-interglacial cycles). The Cr isotope system can also be used to probe the earth's long-term atmospheric oxygenation, pointing towards low but likely dynamic oxygen levels for the majority of Earth's history.
Get access
Type
Element
Information
Online ISBN: 9781108870443
Publisher: Cambridge University Press
Print publication: 25 February 2021

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Albut, G., Babechuk, M. G., Kleinhanns, I. C. et al., 2018, Modern rather than Mesoarchaean oxidative weathering responsible for the heavy stable Cr isotopic signatures of the 2.95 Ga old Ijzermijn iron formation (South Africa): Geochimica et Cosmochimica Acta, v. 228, pp. 157–89.Google Scholar
Aller, R. C., Mackin, J. E., and Cox, R. T., 1986, Diagenesis of Fe and S in Amazon Inner Shelf muds – apparent dominance of Fe reduction and implications for the genesis of ironstones: Continental Shelf Research, v. 6, no. 1–2, pp. 263–89.Google Scholar
Babechuk, M. G., Kleinhanns, I. C., Reitter, E., and Schoenberg, R., 2018, Kinetic stable Cr isotopic fractionation between aqueous Cr(III)-Cl-H2O complexes at 25 degrees C: Implications for Cr(III) mobility and isotopic variations in modern and ancient natural systems: Geochimica et Cosmochimica Acta, v. 222, pp. 383405.Google Scholar
Bartlett, R., and James, B., 1979, Behavior of chromium in soils: III. Oxidation: J. Environ. Qual., v. 8, no. 1, pp. 31–5.Google Scholar
Bauer, K. W., Cole, D. B., Asael, D. et al., 2019, Chromium isotopes in marine hydrothermal sediments: Chemical Geology, p. 119286.Google Scholar
Bauer, K. W., Gueguen, B., Cole, D. B. et al., 2018, Chromium isotope fractionation in ferruginous sediments: Geochimica et Cosmochimica Acta, v. 223, pp. 198215.Google Scholar
Bender, M. L., 1990, The δ18O of dissolved O2 in seawater: A unique tracer of circulation and respiration in the deep sea: Journal of Geophysical Research, v. 95, pp. 2224352.Google Scholar
Bonnand, P., James, R., Parkinson, I., Connelly, D., and Fairchild, I., 2013, The chromium isotopic composition of seawater and marine carbonates: Earth and Planetary Science Letters, v. 382, pp. 1020.Google Scholar
Brandes, J. A., and Devol, A. H., 1997, Isotopic fractionation of oxygen and nitrogen in coastal marine sediments: Geochimica et Cosmochimica Acta, v. 61, pp. 1793–801.Google Scholar
Bruggmann, S., Klaebe, R. M., Paulukat, C., and Frei, R., 2019a, Heterogeneity and incorporation of chromium isotopes in recent marine molluscs (Mytilus): Geobiology, v. 17, no. 4, pp. 417–35.Google Scholar
Bruggmann, S., Scholz, F., Klaebe, R., Canfield, D., and Frei, R., 2019b, Chromium isotope cycling in the water column and sediments of the Peruvian continental margin: Geochimica et Cosmochimica Acta, v. 257, pp. 224–242.Google Scholar
Brumsack, H. J., 1989, Geochemistry of recent TOC-rich sediments from the Gulf of California and the Black Sea: Geologische Rundschau, v. 78, pp. 851–82.CrossRefGoogle Scholar
Butterfield, N. J., 2009, Oxygen, animals and oceanic ventilation: An alternative view: Geobiology, v. 7, no. 1, pp. 17.Google Scholar
Canfield, D. E., Zhang, S. C., Frank, A. B. et al., 2018, Highly fractionated chromium isotopes in Mesoproterozoic-aged shales and atmospheric oxygen: Nature Communications, v. 9, pp. 1–11.Google Scholar
Clark, S. K., and Johnson, T. M., 2008, Effective isotopic fractionation factors for solute removal by reactive sediments: A laboratory microcosm and slurry study: Environmental Science & Technology, v. 42, pp. 7850–55.Google Scholar
Cole, D. B., Mills, D. B., Erwin, D. H. et al., 2020, On the co-evolution of surface oxygen levels and animals: Geobiology, v. 18, no. 3, pp. 260–81.Google Scholar
Cole, D. B., O’Connell, B., and Planavsky, N. J., 2018, Authigenic chromium enrichments in Proterozoic ironstones: Sedimentary Geology, v. 372, pp. 2543.Google Scholar
Cole, D. B., Reinhard, C. T., Wang, X. L. et al., 2016, A shale-hosted Cr isotope record of low atmospheric oxygen during the Proterozoic: Geology, v. 44, no. 7, pp. 555–8.Google Scholar
Colwyn, D. A., Sheldon, N. D., Maynard, J. B. et al., 2019, A paleosol record of the evolution of Cr redox cycling and evidence for an increase in atmospheric oxygen during the Neoproterozoic: Geobiology, v. 17, no. 6, pp. 57993.Google Scholar
Crowe, S. A., Dossing, L. N., Beukes, N. J. et al., 2013, Atmospheric oxygenation three billion years ago: Nature, v. 501, no. 7468, pp. 535–538.Google Scholar
D’Arcy, J., Babechuk, M. G., Dossing, L. N., Gaucher, C., and Frei, R., 2016, Processes controlling the chromium isotopic composition of river water: Constraints from basaltic river catchments: Geochimica et Cosmochimica Acta, v. 186, pp. 296315.Google Scholar
Daye, M., Klepac-Ceraj, V., Pajusalu, M. et al., 2019, Light-driven anaerobic microbial oxidation of manganese: Nature, v. 576, no. 7786, pp. 311–314.Google Scholar
Eary, L. E., and Rai, D., 1987, Kinetics of chromium(III) oxidation to chromium(VI) by reaction with manganese dioxide: Environmental Science & Technology, v. 21, no. 12, pp. 118793.Google Scholar
Eary, L. E., and Rai, D., 1989, Kinetics of chromate reduction by ferrous ions derived from hematite and biotite at 25 degrees C: American Journal of Science, v. 289, no. 2, pp. 180213.Google Scholar
Elderfield, H., and Schultz, A., 1996, Mid-ocean ridge hydrothermal fluxes and the chemical composition of the ocean: Annual Review of Earth and Planetary Sciences, v. 24, pp. 191224.Google Scholar
Ellis, A. S., Johnson, T. M., and Bullen, T. D., 2002, Chromium isotopes and the fate of hexavalent chromium in the environment: Science, v. 295, no. 5562, pp. 2060–62.Google Scholar
Ellis, A. S., Johnson, T. M., and Bullen, T. D., 2004, Using chromium stable isotope ratios to quantify Cr(VI) reduction: Lack of sorption effects: Environmental Science & Technology, v. 38, no. 13, pp. 3604–7.Google Scholar
Erwin, D. H., Laflamme, M., Tweedt, S. M. et al., 2011, The Cambrian conundrum: Early divergence and later ecological success in the early history of animals: Science, v. 334, no. 6059, pp. 1091–7.Google Scholar
Fandeur, D., Juillot, F., Morin, G. et al., 2009, Synchrotron-based speciation of chromium in an oxisol from New Caledonia: Importance of secondary Fe-oxyhydroxides: American Mineralogist, v. 94, no. 56, pp. 710–19.Google Scholar
Farkas, J., Fryda, J., Paulukat, C. et al., 2018, Chromium isotope fractionation between modern seawater and biogenic carbonates from the Great Barrier Reef, Australia: Implications for the paleo-seawater delta Cr-53 reconstruction: Earth and Planetary Science Letters, v. 498, pp. 140–51.Google Scholar
Fendorf, S. E., 1995, Surface reactions of chromium in soils and waters: Geoderma, v. 67, no. 1–2, pp. 5571.Google Scholar
Fralick, P., Planavsky, N., Burton, J.et al. R., 2017, Geochemistry of Paleoproterozoic gunflint formation carbonate: Implications for hydrosphere-atmosphere evolution: Precambrian Research, v. 290, pp. 126–46.Google Scholar
Frei, R., Crowe, S. A., Bau, M. et al., 2016, Oxidative elemental cycling under the low O-2 Eoarchean atmosphere: Scientific Reports, v. 6, pp. 210–58.Google Scholar
Frei, R., Gaucher, C., Poulton, S. W., and Canfield, D. E., 2009, Fluctuations in Precambrian atmospheric oxygenation recorded by chromium isotopes: Nature, v. 461, pp. 250−4.Google Scholar
German, C. R., Campbell, A. C., and Edmond, J. M., 1991, Hydrothermal scavenging at the Mid-Atlantic Ridge: Modification of trace element dissolved fluxes: Earth and Planetary Science Letters, v. 107, pp. 101–14.Google Scholar
Gilleaudeau, G. J., Frei, R., Kaufman, A. J. et al., 2016, Oxygenation of the mid-Proterozoic atmosphere: Clues from chromium isotopes in carbonates: Geochemical Perspectives Letters, v. 2, no. 2, pp. 178–187.Google Scholar
Goring-Harford, H. J., Klar, J. K., Pearce, C. R. et al., 2018, Behaviour of chromium isotopes in the eastern sub-tropical Atlantic Oxygen Minimum Zone: Geochimica et Cosmochimica Acta, v. 236, pp. 4159.Google Scholar
Gueguen, B., Reinhard, C. T., Algeo, T. J. et al., 2016, The chromium isotope composition of reducing and oxic marine sediments: Geochimica et Cosmochimica Acta, v. 184, pp. 119.Google Scholar
Holmden, C., Jacobson, A., Sageman, B., and Hurtgen, M., 2016a, Response of the Cr isotope proxy to Cretaceous Ocean Anoxic Event 2 in a pelagic carbonate succession from the Western Interior Seaway: Geochimica et Cosmochimica Acta, v. 186, pp. 27795.Google Scholar
Hood, A. V., Planavsky, N. J., Wallace, M. W., and Wang, X. L., 2018, The effects of diagenesis on geochemical paleoredox proxies in sedimentary carbonates: Geochimica et Cosmochimica Acta, v. 232, pp. 265–87.Google Scholar
Janssen, D. J., Rickli, J., Quay, P. D. et al., 2020, Biological control of chromium redox and stable isotope composition in the surface ocean: Global Biogeochemical Cycles, v. 34, no. 1. https://doi.org/10.1029/2019GB006397Google Scholar
Johnson, C. A., and Xyla, A. G., 1991, The oxidation of chromium(III) to chromium(VI) on the surface of manganite (γ-MnOOH): Geochimica et Cosmochimica Acta, v. 55, no. 10, pp. 28616.Google Scholar
Johnson, T. M., and Bullen, T. D., 2004, Mass-dependent fractionation of selenium and chromium isotopes in low-temperature environments: Reviews in Mineralogy and Geochemistry, v. 55, no. 1, pp. 289317.Google Scholar
Johnson, T. M., and DePaolo, D. J., 1994, Interpretation of isotopic data in groundwater-rock systems: Model development and application to Sr isotope data from Yucca Mountain: Water Resources Research, v. 30, pp. 1571–87.Google Scholar
Keeling, R. F., Kortzinger, A., and Gruber, N., 2010, Ocean deoxygenation in a warming world: Annual Review of Marine Science, v. 2, pp. 199229.CrossRefGoogle Scholar
Konhauser, K. O., Lalonde, S. V., Planavsky, N. J. et al., 2011, Aerobic bacterial pyrite oxidation and acid rock drainage during the Great Oxidation Event: Nature, v. 478, no. 7369, pp. 369–373.Google Scholar
Kump, L., 2008, The rise of atmospheric oxygen: Nature, v. 451, pp. 277–8.Google Scholar
Lyons, T. W., Reinhard, C. T., and Planavsky, N. J., 2014, The rise of oxygen in Earth’s early ocean and atmosphere: Nature, v. 506, no. 7488, pp. 30715.Google Scholar
Lyons, T. W., Werne, J. P., Hollander, D. J., and Murray, R. W., 2003, Contrasting sulfur geochemistry and Fe/Al and Mo/Al ratios across the last oxic-to-anoxic transition in the Cariaco Basin, Venezuela: Chemical Geology, v. 195, pp. 13157.Google Scholar
McClain, C. N., and Maher, K., 2016, Chromium fluxes and speciation in ultramafic catchments and global rivers: Chemical Geology, v. 426, pp. 135–57.Google Scholar
Moos, S. B., and Boyle, E. A., 2019, Determination of accurate and precise chromium isotope ratios in seawater samples by MC-ICP-MS illustrated by analysis of SAFe Station in the North Pacific Ocean: Chemical Geology, v. 511, pp. 481–93.Google Scholar
Moos, S. B., Boyle, E. A., Altabet, M. A., and Bourbonnais, A., 2020, Investigating the cycling of chromium in the oxygen deficient waters of the Eastern Tropical North Pacific Ocean and the Santa Barbara Basin using stable isotopes: Marine Chemistry, v. 221. https://doi.org/10.1016/j.marchem.2020.103756Google Scholar
Nasemann, P. H., Janssen, D. J., Rickli, J. et al., 2020, Chromium reduction and associated stable isotope fractionation restricted to anoxic shelf waters in the Peruvian Oxygen Minimum Zone: Geochimica et cosmochimica acta, v. 285, pp. 207–24.CrossRefGoogle Scholar
Oze, C., Bird, D. K., and Fendorf, S., 2007, Genesis of hexavalent chromium from natural sources in soil and groundwater: Proceedings of the National Academy of Sciences, v. 104, no. 16, pp. 65449.Google Scholar
Patterson, R. R., Fendorf, S., and Fendorf, M., 1997, Reduction of hexavalent chromium by amorphous iron sulfide: Environmental Science & Technology, v. 31, no. 7, pp. 203944.Google Scholar
Paulukat, C., Gilleaudeau, G. J., Chernyavskiy, P., and Frei, R., 2016, The Cr-isotope signature of surface seawater – A global perspective: Chemical Geology, v. 444, pp. 101–9.Google Scholar
Pereira, N. S., Vögelin, A. R., Paulukat, C. et al., 2015, Chromium isotope signatures in scleractinian corals from the Rocas Atoll, Tropical South Atlantic: Geobiology, v. 4, no. 1, p. 113.Google Scholar
Pereira, N. S., Voegelin, A. R., Paulukat, C. et al., 2016, Chromium-isotope signatures in scleractinian corals from the Rocas Atoll, Tropical South Atlantic: Geobiology, v. 14, no. 1, pp. 5467.Google Scholar
Planavsky, N. J., Cole, D.B., Isson, T.T. et al., 2018, A case for low atmospheric oxygen levels during Earth’s middle history: Emerging Topics in Life Sciences, p. ETLS20170161.Google Scholar
Planavsky, N. J., Reinhard, C. T., Wang, X. L. et al., 2014, Low Mid-Proterozoic atmospheric oxygen levels and the delayed rise of animals: Science, v. 346, no. 6209, pp. 635–8.Google Scholar
Reinhard, C. T., Planavsky, N. J., Robbins, L. J. et al., 2013, Proterozoic ocean redox and biogeochemical stasis: Proceedings of the National Academy of Sciences USA, v. 110, pp. 5357–62.Google Scholar
Reinhard, C. T., Planavsky, N. J., Wang, X. et al., 2014, The isotopic composition of authigenic chromium in anoxic marine sediments: A case study from the Cariaco Basin: Earth and Planetary Science Letters, v. 407, pp. 918.Google Scholar
Remmelzwaal, S. R. C., Sadekov, A. Y., Parkinson, I. J. et al., 2019, Post-depositional overprinting of chromium in foraminifera: Earth and Planetary Science Letters, v. 515, pp. 100–11.Google Scholar
Richard, F. C., and Bourg, A. C. M., 1991, Aqueous geochemistry of chromium: A review: Water Research, v. 25, no. 7, pp. 80716.Google Scholar
Rickli, J., Janssen, D. J., Hassler, C., Ellwood, M. J., and Jaccard, S. L., 2019, Chromium biogeochemistry and stable isotope distribution in the Southern Ocean: Geochimica Et Cosmochimica Acta, v. 262, pp. 188206.Google Scholar
Rodler, A. S., Frei, R., Gaucher, C., and Germs, G. J. B., 2016, Chromium isotope, REE and redox-sensitive trace element chemostratigraphy across the late Neoproterozoic Ghaub glaciation, Otavi Group, Namibia: Precambrian Research, v. 286, pp. 234–49.Google Scholar
Rudnick, R. L., and Gao, S., 2003, Composition of the continental crust: Treatise of Geochemistry, v. 3, pp. 164.Google Scholar
Saad, E. M., Wang, X. L., Planavsky, N. J., Reinhard, C. T., and Tang, Y. Z., 2017, Redox-independent chromium isotope fractionation induced by ligand-promoted dissolution: Nature Communications, v. 8, pp. 1–10.Google Scholar
Sander, S., and Koschinsky, A., 2000, Onboard-ship redox speciation of chromium in diffuse hydrothermal fluids from the North Fiji Basin: Marine Chemistry, v. 71, no. 1–2, pp. 83102.Google Scholar
Sander, S., Koschinsky, A., and Halbach, P., 2003, Redox speciation of chromium in the oceanic water column of the Lesser Antilles and offshore Otago Peninsula, New Zealand: Marine and Freshwater Research, v. 54, no. 6, pp. 74554.Google Scholar
Schauble, E., Rossman, G. R., and Taylor, H. P. Jr, 2004, Theoretical estimates of equilibrium chromium isotope fractionations: Chemical Geology, v. 205, no. 1–2, pp. 99114.Google Scholar
Scheiderich, K., Amini, M., Holmden, C., and Francois, R., 2015, Global variability of chromium isotopes in seawater demonstrated by Pacific, Atlantic, and Arctic Ocean samples: Earth and Planetary Science Letters, v. 423, pp. 8797.Google Scholar
Schoenberg, R., Zink, S., Staubwasser, M., and von Blanckenburg, F., 2008, The stable Cr isotope inventory of solid Earth reservoirs determined by double spike MC-ICP-MS: Chemical Geology, v. 249, no. 3–4, pp. 294306.Google Scholar
Scholz, F., Severmann, S., McManus, J. et al., 2014, On the isotope composition of reactive iron in marine sediments: Redox shuttle versus early diagenesis: Chemical Geology, v. 389, pp. 4859.Google Scholar
Shaw, T. J., Gieskes, J. M., and Jahnke, R. A., 1990, Early diagenesis in differing depositional environments: The response of transition metals in pore water: Geochimica et Cosmochimica Acta, v. 54, pp. 1233–46.Google Scholar
Sial, A. N., Campos, M. S., Gaucher, C. et al., 2015, Algoma-type Neoproterozoic BIFs and related marbles in the Serido Belt (NE Brazil): REE, C, O, Cr and Sr isotope evidence: Journal of South American Earth Sciences, v. 61, pp. 3352.Google Scholar
Sperling, E. A., Halverson, G. P., Knoll, A. H., Macdonald, F. A., and Johnston, D. T., 2013, A basin redox transect at the dawn of animal life: Earth and Planetary Science Letters, v. 371, pp. 143–55.Google Scholar
Sun, Z. Y., Wang, X. L., and Planavsky, N., 2019, Cr isotope systematics in the Connecticut River estuary: Chemical Geology, v. 506, pp. 2939.Google Scholar
Toma, J., Holmden, C., Shakotko, P., Pan, Y., and Ootes, L., 2019, Cr isotopic insights into ca. 1.9 Ga oxidative weathering of the continents using the Beaverlodge Lake paleosol, Northwest Territories, Canada: Geobiology, v. 17, no. 5, pp. 467–89.Google Scholar
Towe, K. M., 1970, Oxygen-collagen priority and early Metazoan fossil record: Proceedings of the National Academy of Sciences of the United States of America, v. 65, no. 4, pp. 781–788.Google Scholar
Wang, X. L., Glass, J. B., Reinhard, C. T., and Planavsky, N. J., 2019, Species-dependent chromium isotope fractionation across the Eastern Tropical North Pacific Oxygen Minimum Zone: Geochemistry Geophysics Geosystems, v. 20, no. 5, pp. 2499–514.Google Scholar
Wang, X. L., Planavsky, N. J., Hull, P. M. et al., 2017, Chromium isotopic composition of core-top planktonic foraminifera: Geobiology, v. 15, no. 1, pp. 5164.Google Scholar
Wang, X. L., Planavsky, N. J., Reinhard, C. T. et al., 2016a, Chromium isotope fractionation during subduction-related metamorphism, black shale weathering, and hydrothermal alteration: Chemical Geology, v. 423, pp. 1933.Google Scholar
Wang, X. L., Reinhard, C. T., Planavsky, N. J. et al., 2016b, Sedimentary chromium isotopic compositions across the Cretaceous OAE2 at Demerara Rise Site 1258: Chemical Geology, v. 429, pp. 8592.Google Scholar
Wei, W., Frei, R., Chen, T. Y. et al., 2018, Marine ferromanganese oxide: A potentially important sink of light chromium isotopes?: Chemical Geology, v. 495, pp. 90103.Google Scholar
Wu, W. H., Wang, X. L., Reinhard, C. T., and Planavsky, N. J., 2017, Chromium isotope systematics in the Connecticut River: Chemical Geology, v. 456, pp. 98111.Google Scholar
Zink, S., Schoenberg, R., and Staubwasser, M., 2010, Isotopic fractionation and reaction kinetics between Cr(III) and Cr(VI) in aqueous media: Geochimica Et Cosmochimica Acta, v. 74, no. 20, pp. 5729–45.Google Scholar

Save element to Kindle

To save this element to your Kindle, first ensure coreplatform@cambridge.org is added to your Approved Personal Document E-mail List under your Personal Document Settings on the Manage Your Content and Devices page of your Amazon account. Then enter the ‘name’ part of your Kindle email address below. Find out more about saving to your Kindle.

Note you can select to save to either the @free.kindle.com or @kindle.com variations. ‘@free.kindle.com’ emails are free but can only be saved to your device when it is connected to wi-fi. ‘@kindle.com’ emails can be delivered even when you are not connected to wi-fi, but note that service fees apply.

Find out more about the Kindle Personal Document Service.

The Chromium Isotope System as a Tracer of Ocean and Atmosphere Redox
Available formats
×

Save element to Dropbox

To save content items to your account, please confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your account. Find out more about saving content to Dropbox.

The Chromium Isotope System as a Tracer of Ocean and Atmosphere Redox
Available formats
×

Save element to Google Drive

To save content items to your account, please confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your account. Find out more about saving content to Google Drive.

The Chromium Isotope System as a Tracer of Ocean and Atmosphere Redox
Available formats
×