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Mechanism of molybdenum removal from the sea and its concentration in black shales: EXAFS evidence

Helz, G.R., Miller, C.V., Charnock, J.M., Mosselmans, J.F.W., Pattrick, R.A.D., Garner, C.D., Vaughan, D.J.·1996·Geochimica et Cosmochimica Acta

DOI 10.1016/0016-7037(96)00195-0

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“…but is preferentially removed in strongly reducing environments through the formation of particle reactive thiomolybdate species such as MoOxS4-x and MoS42- (Adelson et al. 2001, Bertine and Turekian 1973, Calvert and Pedersen 1993, Erickson and Helz 2000, Helz et al. 1996, Neubert et al .”
Background
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“50–250 uM HS−) would facilitate conversion of molybdate (MoO4) to thiomolybdates (MoO4−xSx) that are subsequently scavenged by sedimentary particles (Helz et al., 1996; Zheng et al., 2000).”
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“…rates of phosphate mineral authigenesis on P tot at lower C org contents (Jilbert and Slomp, 2013), while the change in gradient may be related to the non-linear response of Mo uptake into sediments in response to increasing H 2 S concentrations (the so-called ‘sulfide-switch’, Helz et al., 1996).”
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“scavenged by pyrite (Bertine, 1972; Helz et al., 1996, Erickson and Helz, 2000).”
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“Profiles of sediment Mo are used as a proxy for anoxic and sulfidic bottom waters at the time of deposition [Helz et al., 1996; Lyons and Severmann, 2006].”
Background
Co-variation of nitrogen isotopes and redox states through glacial–interglacial cycles in the Black Sea
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“…is enriched under sulfidic (euxinic) conditions, but not under suboxic or anoxic conditions as high dissolved sulfide levels are necessary to form insoluble thiomolybdate species (Crusius et al., 1996; Helz et al., 1996; Algeo and Maynard, 2004; Algeo and Lyons, 2006; Tribovillard et al., 2006 ).”
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Centennial to millennial-scale changes in oxygenation and productivity in the Eastern Tropical South Pacific during the last 25,000 years
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“above a hydrogen sulfide concentration of ~50e250 mM HS ), Mo becomes activated facilitating the conversion of molybdate to thiomolybdates (MoOxS(2) 4 x, x 1⁄4 0e3) (Helz et al., 1996; Zheng et al., 2000; Algeo and Tribovillard, 2009).”
Background
Spatiotemporal redox heterogeneity and transient marine shelf oxygenation in the Mesoproterozoic ocean
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“…the more sulfidized species likely arises because thio-molybdates with two sulfur ligands (MoO 2 S 22 (cid:0) , MoOS 32 (cid:0) , and MoS 42 (cid:0) ) can be reduced to Mo(IV)-polysulfides by S 0 or other reductants (Dahl et al., 2013a; Dahl et al., 2010a; Helz et al., 1996; Vorlicek et al., 2004).”
Background
A possible capture of molybdenum during early diagenesis of dysoxic sediments
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Palaeoproterozoic oxygenated oceans following the Lomagundi–Jatuli Event
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Dissolved Mo and U in rivers and estuaries of India: Implication to geochemistry of redox sensitive elements and their marine budgets
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“Studies of Mo in estuaries are sparse (Colodner et al., 1993; Helz et al., 1996; Dalai et al., 2005; Audry”
Background
Evidence from molybdenum and iron isotopes and molybdenum–uranium covariation for sulphidic bottom waters during Eastern Mediterranean sapropel S1 formation
Azrieli-Tal, I., Matthews, A., Bar‐Matthews, M., Almogi‐Labin, A., Vance, D., Archer, C., & Teutsch, N. (2014) · Earth and Planetary Science Letters · doi:10.1016/j.epsl.2014.02.054 · Cited by 68
Anomalous molybdenum isotope trends in Upper Pennsylvanian euxinic facies: Significance for use of δ98Mo as a global marine redox proxy
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“9; Berrang and Grill, 1974; Helz et al., 1996; Zheng et al., 2000; Reitz et al., 2007).”
Background
Sedimentary molybdenum cycling in the aftermath of seawater inflow to the intermittently euxinic Gotland Deep, Central Baltic Sea
Scholz, F., Baum, M., Siebert, C., Eroglu, S., Dale, A. W., Naumann, M., & Sommer, S. (2018) · Chemical Geology · doi:10.1016/j.chemgeo.2018.04.031 · Cited by 65
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Molybdenum isotope, multiple sulfur isotope, and redox-sensitive element behavior in early Pleistocene Mediterranean sapropels
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Geochemical, metagenomic and metaproteomic insights into trace metal utilization by methane‐oxidizing microbial consortia in sulphidic marine sediments
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Pelagic molybdenum concentration anomalies and the impact of sediment resuspension on the molybdenum budget in two tidal systems of the North Sea
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Variations in the isotopic composition of molybdenum in freshwater lake systems
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“Presley et al., 1972; Helz et al., 1996; Adriano, 2001; Ivanochko and Pedersen, 2004).”
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Zhang, L., Audétat, A., & Dolejš, D. (2011) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2011.11.015 · Cited by 62
Dissolved sulfide distributions in the water column and sediment pore waters of the Santa Barbara Basin
Kuwabara, J. S., van Geen, A., McCorkle, D. C., & Bernhard, J. M. (1999) · Geochimica et Cosmochimica Acta · doi:10.1016/s0016-7037(99)00084-8 · Cited by 62
“The motivation for the present study of dissolved sulfides in the Santa Barbara Basin, one of the Southern California borderland basins, is that certain metals such as Cd and Mo precipitate in reducing sediment, most likely due to the formation of insoluble sulfide phases (Jacobs et al., 1985; Emerson and Huested, 199…”
Background
Mobility of trace elements in black shale assessed by leaching tests and sequential chemical extraction
Lavergren, U., Åström, M., Bergbäck, B., & Holmström, H. (2009) · Geochemistry Exploration Environment Analysis · doi:10.1144/1467-7873/08-188 · Cited by 62
“In black slates high Mo concentrations have been found to correlate with high carbon concentrations (Jeong 2006), and studies by Helz et al. (1996) and Erickson & Helz (2000) suggest that a major mechanism in the accumulation of Mo in euxinic sediments is formation of (non-reduced) thiomolybdates…”
Background
Geochemical stratigraphy, sedimentology, and Mo isotope systematics of the ca. 2.58–2.50 Ga-old Transvaal Supergroup carbonate platform, South Africa
Eroglu, S., Schoenberg, R., Wille, M., Beukes, N. J., & Taubald, H. (2015) · Precambrian Research · doi:10.1016/j.precamres.2015.04.014 · Cited by 64
Atypical Mo isotope signatures in eastern Mediterranean sediments
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Chemical Diversity of Metal Sulfide Minerals and Its Implications for the Origin of Life
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“Mo sulfide associated with Cretaceous deep-sea sediments and with other black shales is characterized by the molecular structure of the Mo center coordinated with sulfur and oxygen, as resolved by extended X-ray absorption fine structure spectroscopy [30].”
Background
Production and preservation of organic matter: The significance of iron
Meyers, S. (2007) · Paleoceanography · doi:10.1029/2006pa001332 · Cited by 61
“It has also been proposed that changes in the size of the local or global molybdenum inventory may impact the magnitude of molybdenum accumulation [Algeo, 2004; Algeo and Lyons, 2006], in addition to factors such the availability of scavenging substrates (organic matter and pyrite [ Helz et al., 1996 ]).”
Background
Recovery and purification of molybdenum from Ni–Mo ore by direct air oxidation in alkaline solution
Zhao, Z., Li, J., Cao, C., Huo, G., Zhang, G., & Li, H. (2010) · Hydrometallurgy · doi:10.1016/j.hydromet.2010.02.018 · Cited by 59
Organic matter accumulation of Late Ordovician sediments in North Guizhou Province, China: Sulfur isotope and trace element evidences
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The influence of thermal maturity on the stable isotope compositions and concentrations of molybdenum, zinc and cadmium in organic-rich marine mudrocks
Dickson, A. J., Idiz, E., Porcelli, D., & van den Boorn, S. H. J. M. (2019) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2019.11.001 · Cited by 60
Occurrence of molybdenum in British surface water and groundwater: Distributions, controls and implications for water supply
Smedley, P., Cooper, D., Ander, E., Milne, C., & Lapworth, D. (2014) · Applied Geochemistry · doi:10.1016/j.apgeochem.2013.03.014 · Cited by 60
Geochemical response on redox fluctuations in Holocene lake sediments, Lake Steisslingen, Southern Germany
Eusterhues, K., Heinrichs, H., & Schneider, J. (2005) · Chemical Geology · doi:10.1016/j.chemgeo.2005.06.006 · Cited by 59
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“Its concentrations are especially high in persistently anoxic and sulphidic environments because MoO4 2- reacts with HS - to create thiomolebdates, which are often bound to iron sulphides (Helz et al., 1996; Morford and Emerson, 1999; Tribovillard et al., 2006).”
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“Hence the potential for Mo sequestration based on the H 2 S concentration (Helz et al., 1996) is expected to be similar at all sites in August, and it is likely that contrasting Mo accumulation largely re ﬂ ects variable supply of Mo by Mn oxides.”
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“The entire core depth is not displayed. sediments ( Helz et al., 1996 ).”
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“The formation of thiomolybdates can potentially stabilize relatively high dissolved concentrations ofMo(VI) under sulfidic conditions in the absenceof reactive particles (H2SN11 μM;Helz et al., 1996; Ericksonand Helz, 2000; Zhenget al., 2000).”
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“Thus, molybdenum removal by anoxic or even euxinic sediments by sulphide–organic matter–Mo interactions presumably forms the ultimate process for Mo burial (Helz et al. 1996; McManus et al. 2002, 2006; Algeo 2006; Neubert et al. 2008).”
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“Molybdate (MoO4 2 ), for example, diffuses into sediments where, in the presence of >11 mmol H2S, it is rapidly converted to thiomolybdate (MoS4 2 ) and subsequently scavenged by Fe sulfides [Bertine, 1972; Helz et al., 1996; Erickson and Helz, 2000] leading to its enrichment.”
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“Thus, high Mo concentrations suggest sulfidic conditions at least to the sediment-water interface [ Helz et al., 1996 ] and, when combined with S-Fe-C systematics, indicate anoxic conditions commonly ex-Figure 6. Diagrams of d 13 C and d 18 O profiles across the inoceramid shell growth lines (GL1 to GL7).”
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“sediments in the presence of free H2S above a threshold concentration [Helz et al., 1996].”
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Marine redox conditions during deposition of Late Ordovician and Early Silurian organic-rich mudrocks in the Siljan ring district, central Sweden
Lu, X., Kendall, B., Stein, H. J., Li, C., Hannah, J. L., Gordon, G. W., & Ebbestad, J. O. R. (2017) · Chemical Geology · doi:10.1016/j.chemgeo.2017.03.015 · Cited by 49
“However, in an anoxic environment, Mo is removed into sediments, especially with the occurrence of hydrogen sulfide in bottom waters (e.g., Emerson and Huested, 1991; Helz et al., 1996; Erickson and Helz, 2000).”
Background
An experimental study of the behaviour of cerium/molybdenum ratios during subduction: Implications for tracing the slab component in the Lesser Antilles and Mariana Arc
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Mid-Proterozoic redox evolution and the possibility of transient oxygenation events
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Contrasting Mo–U enrichments of the basal Datangpo Formation in South China: Implications for the Cryogenian interglacial ocean redox
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Molybdenum speciation as a paleo-redox proxy: A case study from Late Cretaceous Western Interior Seaway black shales
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Influence of particulate versus diffusive molybdenum supply mechanisms on the molybdenum isotope composition of continental margin sediments
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Authors: Helz, G. R., Miller, C. V., Charnock, J. M., Mosselmans, J. F. W., Pattrick, R. A. D., Garner, C. D., & Vaughan, D. J.
Affiliations: University of Maryland, College Park (US)
Daresbury Laboratory (GB)
University of Manchester (GB)
ORCID: Helz, G.R.
Miller, C.V.
Mosselmans, J.F.W.
Pattrick, R.A.D.
Vaughan, D.J.
Venue: Geochimica et Cosmochimica Acta
Publisher: Elsevier BV
Published: 1996-10
Volume: 60
Issue: 19
Pages: 3631-3642
ISSN: 0016-7037 (ISSN-L)
DOI: 10.1016/0016-7037(96)00195-0
OpenAlex: W2042505381
Cited by: 921
References: 58
Citations by year: 2026: 28 · 2025: 46 · 2024: 46 · 2023: 65 · 2022: 52 · 2021: 69 · 2020: 54 · 2019: 48 · 2018: 45 · 2017: 56 · 2016: 43 · 2015: 50 · 2014: 29 · 2013: 41 · 2012: 29
FWCI: 5.39
Type: journal article
Language: en
Open access: closed
Licence: www.elsevier.com/tdm/userlicense/1.0/ (tdm)
Locations: Geochimica et Cosmochimica Acta (publishedVersion)
Research Explorer (The University of Manchester) (submittedVersion)
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 › Radiation › X-ray Spectroscopy and Fluorescence Analysis
Keywords: molybdenum removal, black shales, molybdenum speciation, MoS2, humic acid, sulfidic waters, hydrogen sulfide, molybdenum oxidation state

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Mechanism of molybdenum removal from the sea and its concentration in black shales: EXAFS evidence

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