Was There Really an Archean Phosphate Crisis?
Abstract
During the Archean, massive amounts of iron were deposited in the form of banded iron formations. It has been suggested that sedimenting particles of ferric oxyhydroxide may have stripped dissolved phosphate from the oceans, causing a reduction in phytoplankton productivity. However, that model does not take into account the high concentration of dissolved silica that was present in seawater at that time. We show experimentally that silica effectively competes with phosphate for sorption sites on ferrihydrite particles. Furthermore, coprecipitation of silica with ferrihydrite reduces particle reactivity toward phosphate. Hence, Archean oceans probably contained considerably more phosphate than previously predicted.
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Iron formation data have recently been linked to high dissolved silica concentrations rather than a phosphorus crisis; silica can outcompete phosphorus for binding sites on iron oxides.
“However, the iron formation data have recently been linked to high dissolved silica concentrations rather than a P crisis; silica can outcompete P for binding sites on iron oxides (Konhauser et al., 2007; Planavsky et al., 2010).”
From The Astrobiology Primer v2.0 (2016) · cites this paper as Konhauser et al., 2007
Iron formations have proven useful as paleomarine proxies because trace metal content in least metamorphosed units is almost entirely derived from seawater.
“As iron-and silica-rich chemical sedimentary deposits, IF have proven useful because the trace metal content in the least metamorphosed units are almost entirely derived from seawater (see Bjerrum and Canfield, 2002;Konhauser et al., 2007;2009;2015;Robbins et al., 2013).”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Konhauser et al., 2007
Because partitioning scenarios depend on matrix effects like varying Si levels and extra cations, they cannot be directly compared.
“As these partitioning scenarios are sensitive to matrix effects, such as different Si concentrations (e.g., Konhauser et al. (2007Konhauser et al. ( , 2009) ) and the presence of additional cations, (Jones et al. (2015), see also section 4.1), they cannot be directly equated.”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Konhauser et al. (2007
Konhauser et al. (2007) showed that high silica in seawater would reduce phosphate adsorption onto precipitating Fe oxyhydroxides, leaving P dissolved while still explaining low P/Fe in iron formations, which undermines the Archean P-crisis idea.
“Konhauser et al. (2007) demonstrated that a high silica ocean would have attenuated phosphate adsorption to precipitating Fe oxyhydroxides, thereby keeping P in solution while still accounting for low P/Fe ratios in IF (Fig. 4) -and casting doubt on the idea of an Archean P crisis.”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Konhauser et al. (2007)
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Phosphorus sources for phosphatic Cambrian carbonates
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“…rare earth elements—862 compete with phosphorus for adsorption sites on the surface of iron oxide particles (e.g., 863 Berner, 1973; Trocine and Trefry, 1988; Olivarez and Owen, 1989; Trefry and Metz, 864 1989; Feely et al., 1991; Feely et al., 1998; German et al., 1990; Konhauser et al., 2007).”
BackgroundHao, J., Knoll, A. H., Huang, F., Schieber, J., Hazen, R. M., & Daniel, I. (2020) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2020.04.005 · Cited by 81 · see citing works
Biogeochemical Transformations in the History of the Ocean
Lenton, T. M., & Daines, S. J. (2016) · Annual Review of Marine Science · doi:10.1146/annurev-marine-010816-060521 · Cited by 80 · see citing works
A <scp><scp>Zn</scp></scp> isotope perspective on the rise of continents
Pons, M. ‐., Fujii, T., Rosing, M., Quitté, G., Télouk, P., & Albarède, F. (2013) · Geobiology · doi:10.1111/gbi.12030 · Cited by 78 · see citing works
“Bjerrum & Canfield (2002) argued that scavenging by iron hydroxides further reduced the amount of phosphorus available in the Archean ocean, a suggestion challenged by Konhauser et al. (2007) who emphasized the mediating effect of dissolved silica.”
BackgroundKendall, B., Anbar, A. D., Kappler, A. A., & Konhauser, K. O. (2012) · Wiley eBooks · doi:10.1002/9781118280874.ch6 · Cited by 78 · see citing works
“Subsequently, experiments by Konhauser et al. (2007a) showed that photo-oxidation of Fe(II) in an anoxic Precambrian surface ocean was likely negligible in close proximity to hydrothermal plumes from shallow submarine volcanoes.”
BackgroundSelf-citationLimited oxygen production in the Mesoarchean ocean
Ossa, F. O., Hofmann, A., Spangenberg, J. E., Poulton, S. W., Stüeken, E. E., Schoenberg, R., Eickmann, B., Wille, M., Butler, M. J., & Bekker, A. (2019) · Proceedings of the National Academy of Sciences · doi:10.1073/pnas.1818762116 · Cited by 74 · see citing works
Zhang, J., Guo, L., & Fischer, C. J. (2009) · Aquatic Geochemistry · doi:10.1007/s10498-009-9081-4 · Cited by 77 · see citing works
Papineau, D., Purohit, R., Fogel, M. L., & Shields, G. (2013) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2012.11.050 · Cited by 70 · see citing works
Eickhoff, M., Obst, M., Schröder, C., Hitchcock, A. P., Tyliszczak, T., Martinez, R. E., Robbins, L. J., Konhauser, K. O., & Kappler, A. (2014) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2014.05.021 · Cited by 64 · see citing works
“negligible (Konhauser et al., 2007), which seems to be consistent with our findings.”
BackgroundMethodResultInfluentialSelf-citationSilicification and Si cycling in a silica-rich ocean during the Ediacaran-Cambrian transition
Gao, P., Li, S., Lash, G. G., He, Z., Xiao, X., Zhang, D., & Hao, Y. (2020) · Chemical Geology · doi:10.1016/j.chemgeo.2020.119787 · Cited by 63 · see citing works
Stable Fe isotope fractionations produced by aqueous Fe(II)-hematite surface interactions
Wu, L., Beard, B. L., Roden, E., Kennedy, C., & Johnson, C. M. (2010) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2010.04.060 · Cited by 62 · see citing works
Wu, L., Beard, B. L., Roden, E., & Johnson, C. M. (2009) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2009.06.026 · Cited by 62 · see citing works
“DIR are explored over a range in pH and dissolved ion contents to better approximate conditions that existed in ancient marine environments, particularly with regard to dissolved Si, which likely existed in Precambrian oceans at levels approaching saturation with amorphous Si (2.14 mM Si) at � 25 C( Maliva et al., 200…”
BackgroundInfluentialPapineau, D., Gregorio, B. T. D., Stroud, R. M., Steele, A., Ernesto Pecoits, A., Konhauser, K. O., Wang, J., & Fogel, M. L. (2010) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2010.07.002 · Cited by 61 · see citing works
“Accordingly, either the phosphate was initially associated with settling ferric oxyhydroxide particles (Bjerrum and Canfield, 2002) or it was incorporated within the biomass of lysed planktonic cells (Konhauser et al., 2002, 2007).”
BackgroundSelf-citationOxidative sulfide dissolution on the early Earth
Reinhard, C. T., Lalonde, S. V., & Lyons, T. W. (2013) · Chemical Geology · doi:10.1016/j.chemgeo.2013.10.006 · Cited by 60 · see citing works
“ocean ecology and nutrient limitation status (e.g., Bjerrum and Canfield, 2002; Konhauser et al., 2007; Planavsky et al., 2010b).”
BackgroundSelf-citationRare earth elements in Hamersley BIF minerals
Alibert, C. (2016) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2016.03.026 · Cited by 62 · see citing works
Vivianite formation in ferruginous sediments from Lake Towuti, Indonesia
Vuillemin, A., Friese, A., Wirth, R., Schuessler, J. A., Schleicher, A. M., Kemnitz, H., Lücke, A., Bauer, K. W., Nomosatryo, S., von Blanckenburg, F., et al. (2020) · Biogeosciences · doi:10.5194/bg-17-1955-2020 · Cited by 58 · see citing works
Halama, M., Swanner, E. D., Konhauser, K. O., & Kappler, A. (2016) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2016.06.032 · Cited by 55 · see citing works
“The Si-rich layers in BIFs originated from the chemical precipitation of amorphous silica since Precambrian oceans were quite likely enriched in Si up to 2.2 mM (Siever, 1992; Konhauser et al., 2007b).”
BackgroundInfluentialSelf-citationde Tombeur, F., Roux, P., & Cornelis, J. (2021) · Plant and Soil · doi:10.1007/s11104-021-05076-8 · Cited by 54 · see citing works
“…suggested competition between Si and phosphate ions (Smyth and Sanchez 1980; Kundu et al. 1988; Matychenkov and Ammosova 1996; Owino-Gerroh and Gascho 2004; Konhauser et al. 2007; Reithmaier et al. 2017; Hilbrandt et al. 2019; Hömberg et al. 2020; Klotzbücher et al. 2020; Schaller et al. 2020).”
BackgroundThompson, J. A., Poulton, S. W., Guilbaud, R., Doyle, K. A., Reid, S., & Krom, M. D. (2019) · Chemical Geology · doi:10.1016/j.chemgeo.2019.07.003 · Cited by 54 · see citing works
A review of the application of iron oxides for phosphorus removal and recovery from wastewater
Wang, S.-X., Huang, Y.-X., Wu, Q., Yao, W., Lu, Y., Huang, B., & Jin, R. (2023) · Critical Reviews in Environmental Science and Technology · doi:10.1080/10643389.2023.2242227 · Cited by 53 · see citing works
“Besides, silica was found to reduce the adsorption capacity of ferrihydrite for phosphate by competing for available adsorption sites (Konhauser et al., 2007).”
BackgroundThe effect of widespread early aerobic marine ecosystems on methane cycling and the Great Oxidation
Daines, S. J., & Lenton, T. M. (2015) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2015.11.021 · Cited by 53 · see citing works
“EP and hence [O2]s is approximately proportional to 238 nutrient level (Fig 2A) and nutrient levels are also uncertain (Konhauser et al., 2007), but even 239 nutrient levels as little as 10% of present provide sufficient productivity to support an aerobic 240 ecosystem ([O2]s ≈ 1 M) in upwelling…”
BackgroundDodd, M. S., Zhang, Z., Li, C., Algeo, T. J., Lyons, T. W., Hardisty, D. S., Loyd, S. J., Meyer, D. L., Gill, B. C., Shi, W., et al. (2021) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2021.02.038 · Cited by 54 · see citing works
Links Between Hydrothermal Environments, Pyrophosphate, Na+, and Early Evolution
Holm, N. G., & Baltscheffsky, H. (2011) · Origins of Life and Evolution of Biospheres · doi:10.1007/s11084-011-9235-4 · Cited by 52 · see citing works
“The concentration of phosphate in the Archean ocean was, however, probably much higher compared to the present ocean, since it is more scavenged in modern oceanic environments (Konhauser et al. 2007; Planavsky et al. 2010).”
BackgroundSwanner, E. D., Wu, W., Schoenberg, R., Byrne, J. M., Michel, F. M., Pan, Y., & Kappler, A. A. (2015) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2015.05.024 · Cited by 52 · see citing works
Phytoplankton contributions to the trace-element composition of Precambrian banded iron formations
Konhauser, K. O., Robbins, L. J., Alessi, D. S., Flynn, S. L., Gingras, M. K., Martinez, R. E., Kappler, A. A., Swanner, E. D., Li, Y., Crowe, S. A., et al. (2017) · Geological Society of America Bulletin · doi:10.1130/b31648.1 · Cited by 50 · see citing works
“…suggested that in the Precambrian oceans, those same minerals may not have been as reactive as previously believed because dissolved silica (e.g., Konhauser et al., 2007a, 2009; Jones et al., 2015) and organic carbon (Eickhoff et al., 2014) passivate the surface reactivity of ferrihydrite toward…”
BackgroundSelf-citationRaven, J. A., Giordano, M., & Beardall, J. (2008) · Physiologia Plantarum · doi:10.1111/j.1399-3054.2007.01024.x · Cited by 48 · see citing works
Habitability: from stars to cells
Javaux, E., & Dehant, V. (2010) · The Astronomy and Astrophysics Review · doi:10.1007/s00159-010-0030-4 · Cited by 46 · see citing works
“3), microbial filaments and cells are preserved as cast of iron oxides (Fernandez-Remolar and Knoll 2008), whereas in the Yellowstone hot springs, they are silicified by silica-rich fluids (Konhauser et al. 2007).”
BackgroundExploring the drivers of early biomineralization
Wood, R. A. (2018) · Emerging Topics in Life Sciences · doi:10.1042/etls20170164 · Cited by 45 · see citing works
“The earliest known skeletal macrobiota appeared in redox stratified oceans often characterised by a shallow and fluctuating oxic chemocline (5), high levels of silica (6), and a high Mg/Ca ratio”
BackgroundTAPHONOMY OF CAMBRIAN PHOSPHATIC SMALL SHELLY FOSSILS
Creveling, J. R., Knoll, A. H., & Johnston, D. T. (2014) · Palaios · doi:10.2110/palo.2014.002 · Cited by 43 · see citing works
Catalysts, autocatalysis and the origin of metabolism
Preiner, M., Xavier, J. C., Vieira, A. D. N., Kleinermanns, K., Allen, J. F., & Martin, W. F. (2019) · Interface Focus · doi:10.1098/rsfs.2019.0072 · Cited by 43 · see citing works
Lingam, M., & Loeb, A. (2018) · International Journal of Astrobiology · doi:10.1017/s1473550418000083 · Cited by 39 · see citing works
“On Earth, the intimately intertwined evolution of marine productivity and phosphorus availability during the Archean and Proterozoic aeons has been extensively investigated (Bjerrum and Canfield, 2002; Konhauser et al., 2007; Papineau, 2010; Laakso and Schrag, 2014; Kipp and Stüeken, 2017), especially in connection wi…”
BackgroundEvolution of the crustal phosphorus reservoir
Walton, C. R., Hao, J., Huang, F., Jenner, F. E., Williams, H. M., Zerkle, A. L., Lipp, A., Hazen, R. M., Peters, S. E., & Shorttle, O. (2023) · Science Advances · doi:10.1126/sciadv.ade6923 · Cited by 40 · see citing works
Mobility of nutrients and trace metals during weathering in the late Archean
Hao, J., Sverjensky, D. A., & Hazen, R. M. (2017) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2017.05.003 · Cited by 40 · see citing works
Using modern ferruginous habitats to interpret Precambrian banded iron formation deposition
Koeksoy, E., Halama, M., Konhauser, K. O., & Kappler, A. A. (2015) · International Journal of Astrobiology · doi:10.1017/s1473550415000373 · Cited by 40 · see citing works
“All five lakes exceed the upper estimate for Archean marine phosphate concentrations (5.3 ± 2.6 µM, Konhauser et al. 2007) (Table 1), with Lake Matano exhibiting the lowest phosphate concentration of 9 µM, followed by Lake Vechten (20 µM), Lake La Cruz (52.6 µM), Lake Pavin (340 µM) and Lake…”
BackgroundInfluentialSelf-citationMeishucun phosphorite succession (SW China) records redox changes of the early Cambrian ocean
Liu, Z.-R. R., & Zhou, M. (2017) · Geological Society of America Bulletin · doi:10.1130/b31612.1 · Cited by 39 · see citing works
Krissansen‐Totton, J., Kipp, M. A., & Catling, D. C. (2021) · Geobiology · doi:10.1111/gbi.12440 · Cited by 40 · see citing works
“While high Precambrian phosphorus levels have been proposed (Konhauser et al. 2007; Planavsky et al. 2010), limited availability of reductants (1) forg = (13)CBurial_carb − (13)Cinputs (13)CBurial_carb − (13)CBurial_org Key Points”
BackgroundThe Precambrian emergence of animal life: a geobiological perspective
Gaidos, E. J., DuBuc, T. Q., Dunford, M. D., MCANDREW, P., PADILLA‐GAMIÑO, J., STUDER, B., Weersing, K., & Stanley, S. M. (2007) · Geobiology · doi:10.1111/j.1472-4669.2007.00125.x · Cited by 38 · see citing works
“with elevated levels of silica (Konhauser et al., 2007).”
BackgroundTiming the evolution of phosphorus-cycling enzymes through geological time using phylogenomics
Boden, J. S., Zhong, J., Anderson, R. E., & Stüeken, E. E. (2024) · Nature Communications · doi:10.1038/s41467-024-47914-0 · Cited by 36 · see citing works
Geochemical Characterization of Two Ferruginous Meromictic Lakes in the Upper Midwest, USA
Lambrecht, N., Wittkop, C. A., Katsev, S., Fakhraee, M., & Swanner, E. D. (2018) · Journal of Geophysical Research Biogeosciences · doi:10.1029/2018jg004587 · Cited by 37 · see citing works
“Compilations of P/Fe ratios from marine iron formations, which can be used to calculate the phosphate concentration in coeval seawater (Konhauser et al., 2007), indicate that the phosphorus reservoir in the deep oceans in the Archean and early Proterozoic was up to four times larger than the modern reservoir (Planavsk…”
BackgroundInfluentialIs Struvite a Prebiotic Mineral?
Gull, M., & Pasek, M. A. (2013) · Life · doi:10.3390/life3020321 · Cited by 34 · see citing works
- Authors
- Konhauser, K. O., Lalonde, S. V., Amskold, L., & Holland, H. D.
- Affiliations
- Harvard University (US)
- Corresponding author
- Konhauser, Kurt O.
- Venue
- Science
- Published
- 2007-03-02
- Volume
- 315
- Issue
- 5816
- Pages
- 1234-1234
- ISSN
- 0036-8075 (ISSN-L)
- 1095-9203
- OpenAlex
- W2006491332
- Cited by
- 222
- References
- 7
- Citations by year
- 2026: 10 · 2025: 19 · 2024: 20 · 2023: 16 · 2022: 8 · 2021: 14 · 2020: 12 · 2019: 13 · 2018: 15 · 2017: 11 · 2016: 12 · 2015: 11 · 2014: 4 · 2013: 13 · 2012: 12
- FWCI
- 6.05
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Science (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Earth and Planetary Sciences › Paleontology › Paleontology and Stratigraphy of Fossils
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geochemistry and Elemental Analysis
- Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
- Keywords
- banded iron formations, ferrihydrite, dissolved silica, phosphate adsorption, co-precipitation, ferric oxyhydroxide, phytoplankton productivity, Archean ocean
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