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Title: Contrasting Effects of Catecholate and Hydroxamate Siderophores on Molybdenite Dissolution

Journal Article · · Environmental Science and Technology

Molybdenum (Mo) is essential for many enzymes but is often sequestered within minerals, rendering it not readily bioavailable. Metallophores, metabolites secreted by microorganisms and plants, promote mineral dissolution to increase metal bioavailability. However, interactions between metallophores and Mo-bearing minerals remain unclear. Here, in this study, catecholate protochelin and hydroxamate desferrioxamine B (DFOB) were utilized to examine their effects on dissolution of the common Mo-bearing mineral, molybdenite (MoS2), under both oxic and anoxic conditions. Protochelin promoted molybdenite dissolution under oxic conditions with the formation of MoO3 on the surface and Mo-siderophore complexes in solution. This was attributed to air-oxidation of both molybdenite and protochelin, as evidenced by lack of dissolution under anoxic conditions but enhanced dissolution by either pre-oxidized protochelin or pre-oxidized molybdenite. Liquid chromatography-mass spectroscopy (LC-MS), X-ray photoelectron spectroscopy (XPS), and Time-of-flight secondary ion mass spectrometry (ToF-SIMS) analyses revealed degradation of protochelin and adsorptions of its byproducts on molybdenite surface to promote dissolution. Conversely, DFOB inhibited molybdenite dissolution under both oxic and anoxic conditions, likely attributed to surface adsorption of DFOB and its weak complexation with Mo(VI) at the circumneutral pH. This work highlights the need to consider the balance between promoting and inhibitory effects of different metallophores on Mo-mineral dissolution.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
2564582
Report Number(s):
PNNL-SA--206647
Journal Information:
Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 1 Vol. 59; ISSN 0013-936X
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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