Insights into the Biogeochemical Cycling of Cobalt: Precipitation and Transformation of Cobalt Sulfide Nanoparticles under Low-Temperature Aqueous Conditions

Mansor, Muammar; Cantando, Elizabeth; Wang, Yi; Hernandez-Viezcas, Jose A.; Gardea-Torresdey, Jorge L.; Hochella, Michael F.; Xu, Jie

doi:10.1021/acs.est.0c01363

Insights into the Biogeochemical Cycling of Cobalt: Precipitation and Transformation of Cobalt Sulfide Nanoparticles under Low-Temperature Aqueous Conditions

Journal Article · Fri Apr 03 00:00:00 EDT 2020 · Environmental Science and Technology

DOI:https://doi.org/10.1021/acs.est.0c01363· OSTI ID:1638020

^[1]; Cantando, Elizabeth ^[2]; Wang, Yi ^[1]; Hernandez-Viezcas, Jose A. ^[3]; ^[3]; ^[4]; Xu, Jie ^[1]

Univ. of Texas at El Paso, TX (United States)
Virginia Tech National Center for Earth and Environmental Nanotechnology (NanoEarth), Blacksburg, VA (United States)
Univ. of Texas at El Paso, TX (United States); Univ. of California Center for Environmental Implications of Nanotechnology (UC CEIN), Univ. of Texas at El Paso, TX (United States)
Virginia Tech National Center for Earth and Environmental Nanotechnology (NanoEarth), Blacksburg, VA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Cobalt sulfide precipitates, key phases in the natural biogeochemical cycling of cobalt and in relevant remediation and resource recovery processes, remain poorly defined under low-temperature aqueous conditions. Here, we systematically studied the Co-(Fe) sulfides precipitated and aged in environmentally relevant solutions, defined by different combinations of pH, initial cobalt-to-iron ratios ([Co]_aq/[Fe]_aq), with/without S⁰, and the presence/absence of sulfate-reducing bacteria. The initial abiogenic precipitates without Fe_aq were composed exclusively of amorphous Co-sulfide hydrates (CoS· x H₂O), whose estimated log K* was three orders of magnitude higher than that previously reported for crystalline Co-sulfides. The addition of S⁰, in combination with acidic pH and elevated temperature (60°C), resulted in the recrystallization of the amorphous precipitates into nanocrystalline jaipurite (hexagonal CoS) within one month (which otherwise remained stable for up to two months). In the presence of Fe(II)_aq, the abiogenic precipitates were composed of more crystalline Co-sulfide hydrates and/or Co-rich mackinawite, the exact phase being dependent on the specific [Co]_aq/[Fe(II)]_aq. The biogenic precipitates displayed higher crystallinity for Co sulfides (up to the formation of nanocrystalline cobalt pentlandite, Co₉S₈) and lower crystallinity for Co-rich mackinawite, suggestive of mineral-specific bacterial interaction. The revealed precipitation and transformation pathways of Co-(Fe-)sulfides in this study allows for predicting the prevalent Co-bearing phases in various natural and engineered environments.

View Accepted Manuscript (DOE)

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); NSF; EPA; USDA

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1638020

Alternate ID(s):: OSTI ID: 1843553

Report Number(s):: PNNL-SA--148305

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 9 Vol. 54; ISSN 1520-5851; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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58 GEOSCIENCES
Sulfides
cobalt
cobalt sulfides
cobalt-pentlandite
jaipurite
mackinawite
metals
nanoparticles
physical and chemical processes
sulfate-reducing bacteria
sulfidic environments

Insights into the Biogeochemical Cycling of Cobalt: Precipitation and Transformation of Cobalt Sulfide Nanoparticles under Low-Temperature Aqueous Conditions

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