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Mechanism of molybdenum removal from the sea and its concentration in black shales: EXAFS evidence
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“in the presence of abundant (10 -3 -10 -4 M) free hydrogen sulfide, Mo is converted to a series of particle-reactive thiomolybdates and is efficiently removed from seawater (the so-called Mo”
From Trace elements at the intersection of marine biological and geochemical evolution (2016) · cites this paper as Helz et al., 1996
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“Changes in the sedimentary Fe and Mo contents can provide insight into past bottom water redox conditions (e.g. Helz et al., 1996; Lyons and Severmann, 2006; Scott and Lyons, 2012).”
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“the particle surfaces of Mn and Fe oxyhydroxides as well as organic matter, resulting in strong Mo enrichment in sediments deposited under euxinic conditions (Helz et al., 1996).”
BackgroundLi, L., Wang, X., Ren, Y., Su, H., Hu, L., Yang, G., Li, Z., Bosin, A. A., Астахов, А. С., Chen, J., et al. (2021) · Journal of Geophysical Research Oceans · doi:10.1029/2020jc016960 · Cited by 19
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“…and black shales typically occurs due to their removal from seawater or porewater at the transition from dysoxic to anoxic conditions, above the sulphate reduction zone (V, U) or under anoxic to euxinic conditions (U, Mo) (Helz et al ., 1996, 2011; Tribovillard et al ., 2006; Algeo & Li, 2020).”
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Just like the universe the emergence of life had high enthalpy and low entropy beginnings
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“In fact, there is evidence that it does not form over geologic time periods unless host rocks are subject to elevated temperatures through metamorphism or hydrothermal alteration (Helz et al. 1996).”
BackgroundPang, Q., Zhang, X.-H., Chen, C., Gao, Z.-L., Shan, S., Chen, Y., You, J., Hu, C.-W., & Hu, G.-H. (2021) · Journal of Petroleum Science and Engineering · doi:10.1016/j.petrol.2021.110058 · Cited by 15
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“Vanadium (V) and uranium (U) are redox-sensitive elements and are considered as redox-sensitive indicators (Algeo & Maynard, 2004; Calvert & Pedersen, 1993; Crusius, Calvert, Pedersen, & Sage, 1996; Dean, Gardner, & Piper, 1997; Helz et al., 1996; Tribovillard, Algeo, Lyons, & Riboulleau, 2006).”
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“Studies on the chemistry of molybdenum, sulfur, and oxygen (Prasilova and Burclova, 1972; Helz et al. , 1996) have shown that MoS 3 and MoS 2 are either too soluble or kinetically too unfavorable to be candidates for molybdenum sediment accumulation.”
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“S, forming a solid solution with iron sulfides (Helz et al., 1996).”
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“In early studies, concentrations of RSTE, especially molybdenum (Mo) and uranium (U), in marine shale may reflect benthic redox conditions: higher concentrations were interpreted to be caused by the more reducing environment (e.g., Helz et al., 1996; Dean et al., 1999; Vorlicek and Helz, 2002).”
BackgroundZhao, K., Zhu, G.-Y., Zheng, W., Sun, G.-Y., Li, T., & Zhang, Z.-Y. (2023) · Global and Planetary Change · doi:10.1016/j.gloplacha.2023.104214 · Cited by 16
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“Mo may be moderately enriched under reducing conditions but becomes significantly enriched in the presence of free sulfide and is “activated” at a critical HS − activity to form thiomolyb-dates (MoO x S 2 − 4-x ) ( 92 ).”
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“When sulfide is present in pore or bottom waters, molybdate ions are converted into particle reactive thiomolybdates (MoSxO 2− x − 4), enabling sequestration and burial of Mo (Helz et al. 1996; Tribovillard et al. 2006, and references therein).”
BackgroundCalculation of the UV-visible spectra and the stability of Mo and Re oxysulfides in aqueous solution
Tossell, J. A. (2005) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2004.12.004 · Cited by 16
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“suboxic conditions which may be the Fe (II)–Fe (III) redox boundary, whereas Mo enrichment requires an euxinic conditions (Helz et al., 1996; McManus et al., 2005; Morford & Emerson, 1999; Zheng et al., 2002).”
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“In addition, to DOP, other elemental ratios, notably Fetot/Altot and FeHR/Fetot [Berner, 1980; Lyons et al., 2009; Raiswell et al., 1994], Mo/Al [Jacobs et al., 1987] and Mo abundances [Helz et al., 1996; Tribovillard et al., 2006; Xu et al., 2012] are also used as indicators of oxygenation.”
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16 Good Golly, Why Moly? THE STABLE ISOTOPE GEOCHEMISTRY OF MOLYBDENUM
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“Although conversion to thiomolybdates is catalyzed by mineral surfaces (Helz et al. 1996), Crusius et al.”
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“The release of Mo during the reduction of Mn-oxides also results in the scavenging of Mo by Fe sulfides and organic matter (Huerta Diaz and Morse, 1992; Helz et al., 1996; Vorlicek et al., 2004).”
BackgroundNwaila, G. T., & Frimmel, H. E. (2019) · Mineralogy and Petrology · doi:10.1007/s00710-018-0650-3 · Cited by 14
“The higher concentrations of Au and PGE in black shales are thought to be due to organic complexation of Au and PGE from seawater in anoxic organic-rich mud which is eventually incorporated into diagenetic sulphide minerals (Helz et al. 1996).”
BackgroundGibson, T. M., Kunzmann, M., Poirier, A., Schumann, D., Tosca, N. J., & Halverson, G. P. (2020) · Geochimica et Cosmochimica Acta · doi:10.1016/j.gca.2020.04.013 · Cited by 14
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Ivanochko, T., Calvert, S. E., Southon, J. R., Enkin, R. J., Baker, J., Dallimore, A., & Pedersen, T. F. (2008) · Canadian Journal of Earth Sciences · doi:10.1139/e08-030 · Cited by 14
“In anoxic sedimentary environments, Mo (VI) is reduced to Mo (IV), which precipitates as Mosulfide (Adelson et al. 2001; Helz et al. 1996) or as complexed Mo–Fe-sulphides (Zheng et al.”
BackgroundAlam, M., Tripti, M., Gurumurthy, G. P., Sohrin, Y., Tsujisaka, M., Singh, A. D., Takano, S., & Verma, K. K. (2021) · Palaeogeography Palaeoclimatology Palaeoecology · doi:10.1016/j.palaeo.2021.110790 · Cited by 13
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Metal stable isotopes in the marine realm
Little, S., de Souza, G. F., & Xie, R. C. (2024) · Elsevier eBooks · doi:10.1016/b978-0-323-99762-1.00019-x · Cited by 16
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“Similarly, Mo can be scavenged at or below the sea floor but requires the presence of H 2 S (Helz et al., 1996, 2011).”
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Fundamental Aspects and Applications of X-Ray Absorption Spectroscopy in Clay and Soil Sciences
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“Under anoxic/euxinic conditions, Mo is efficiently scavenged from the water column in the form of thiomolybdate complexes leading to an accumulation of Mo in the sediment (Helz et al. 1996).”
Metadata
- 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)
- Venue
- Geochimica et Cosmochimica Acta
- Publisher
- Elsevier BV
- Published
- 1996-10
- Volume
- 60
- Issue
- 19
- Pages
- 3631-3642
- ISSN
- 0016-7037 (ISSN-L)
- 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
- 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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