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

Journal Article · · Environmental Science and Technology
ORCiD logo [1];  [2];  [1];  [3]; ORCiD logo [3]; ORCiD logo [4];  [1]
  1. Univ. of Texas at El Paso, TX (United States)
  2. Virginia Tech National Center for Earth and Environmental Nanotechnology (NanoEarth), Blacksburg, VA (United States)
  3. 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)
  4. 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 biogeochemistry of cobalt and in relevant remediation and resource recovery processes, are 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 So, and the presence/absence of sulfate-reducing bacteria. The initial abiogenic precipitates were composed exclusively of amorphous Co-sulfide nanoparticles (CoS·xH2O) that were stable in anoxic solution for two months, with estimated log K* of one to five orders of magnitude higher than that previously reported for Co-sulfides. The addition of So, in combination with acidic pH and elevated temperature (60°C), resulted in recrystallization of the amorphous precipitates into nanocrystalline jaipurite (hexagonal CoS) within one month. In the presence of Fe(II)aq, the abiogenic precipitates were composed of more crystalline Co-sulfides and/or Co-rich mackinawite, the exact phase dependent on the [Co]aq/[Fe]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. Furthermore, the revealed precipitation and transformation pathways of Co-(Fe-)sulfides in this study allows for a better constraint of Co biogeochemistry in various natural and engineered environments.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); USEPA; USDA
Grant/Contract Number:
AC05-76RL01830; FG02-06ER1578; DBI-1266377; 2016-67021-24985; EC-1449500; CHE-0840525; DBI-1429708; ECCS 1542100; FG02-06ER15786
OSTI ID:
1638020
Alternate ID(s):
OSTI ID: 1843553
Report Number(s):
PNNL-SA-148305; 1520-5851
Journal Information:
Environmental Science and Technology, Vol. 54, Issue 9; ISSN 0013-936X
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

References (62)

Elucidation of roles for vitamin B 12 in regulation of folate, ubiquinone, and methionine metabolism journal January 2017
Beyond catalysis: vitamin B 12 as a cofactor in gene regulation : B12 in gene regulation journal January 2014
Influence of Co and B12 on the growth and nitrogen fixation of Trichodesmium journal June 2015
COBALAMIN (COENZYME B 12 ): Synthesis and Biological Significance journal October 1996
Vitamin B12 transport from food to the body's cells—a sophisticated, multistep pathway journal May 2012
Cobalt and secondary poisoning in the terrestrial food chain: Data review and research gaps to support risk assessment journal August 2008
Effect of Nickel and Cobalt on Methanogenic Enrichment Cultures and Role of Biogenic Sulfide in Metal Toxicity Attenuation journal July 2017
Quantifying the recoverable resources of by-product metals: The case of cobalt journal November 2013
Co III EDTA - Reduction by Desulfovibrio vulgaris and Propagation of Reactions Involving Dissolved Sulfide and Polysulfides journal April 2001
Immobilization of Cobalt by Sulfate-Reducing Bacteria in Subsurface Sediments journal January 2003
Review of metal sulphide precipitation journal September 2010
Metal Sulfide Complexes and Clusters journal January 2006
Cobalt and marine redox evolution journal March 2014
Geological and Chemical Factors that Impacted the Biological Utilization of Cobalt in the Archean Eon journal March 2018
Influence of Structural Defects on Biomineralized ZnS Nanoparticle Dissolution: An in-Situ Electron Microscopy Study journal January 2018
Highly-defective nanocrystals of ZnS formed via dissimilatory bacterial sulfate reduction: A comparative study with their abiogenic analogues journal May 2016
Anaerobic, Nitrate-Dependent Oxidation of Pyrite Nanoparticles by Thiobacillus denitrificans journal January 2012
Influence of Size and Aggregation on the Reactivity of an Environmentally and Industrially Relevant Nanomaterial (PbS) journal November 2009
Effect of Reduced Sulfur Species on Chemolithoautotrophic Pyrite Oxidation with Nitrate journal November 2018
Phase, morphology, elemental composition, and formation mechanisms of biogenic and abiogenic Fe-Cu-sulfide nanoparticles: A comparative study on their occurrences under anoxic conditions journal May 2019
Nanoparticulate Nickel-Hosting Phases in Sulfidic Environments: Effects of Ferrous Iron and Bacterial Presence on Mineral Formation Mechanism and Solid-Phase Nickel Distribution journal June 2019
Reactions forming pyrite and marcasite from solution: II. Via FeS precursors below 100°C journal June 1991
Pyrite formation by reactions of iron monosulfides with dissolved inorganic and organic sulfur species journal November 1996
Nickel sulfide formation at low temperature: initial precipitates, solubility and transformation products journal January 2010
Performing elemental microanalysis with high accuracy and high precision by scanning electron microscopy/silicon drift detector energy-dispersive X-ray spectrometry (SEM/SDD-EDS) journal November 2014
The composition of nanoparticulate mackinawite, tetragonal iron(II) monosulfide journal December 2006
The composition of nanoparticulate nickel sulfide journal October 2010
Trapping of radiolytic hydrogen by amorphous cobalt oxysulfide journal December 2006
Amorphous Cobalt Oxysulfide as a Hydrogen Trap journal November 2006
“Amorphous Nickel Sulfide” Is Hydrated Nanocrystalline NiS with a Core−Shell Structure journal December 2009
Synthesis and Properties of Cobalt Sulfide Phases: CoS 2 and Co 9 S 8: Synthesis and Properties of Cobalt Sulfide Phases: CoS 2 and Co 9 S 8 journal February 2014
Highly Active Cobalt Sulfide/Carbon Nanotube Catalyst for Hydrogen Evolution at Soft Interfaces journal March 2016
Electrochemical characterization on cobalt sulfide for electrochemical supercapacitors journal June 2007
Synthesis of nickel and cobalt sulfide nanoparticles using a low cost sonochemical method journal March 2017
Electrodeposited Cobalt-Sulfide Catalyst for Electrochemical and Photoelectrochemical Hydrogen Generation from Water journal November 2013
Operando Spectroscopic Analysis of an Amorphous Cobalt Sulfide Hydrogen Evolution Electrocatalyst journal June 2015
Reactive transport codes for subsurface environmental simulation journal September 2014
Uptake of nickel by synthetic mackinawite journal June 2017
Greigite: a true intermediate on the polysulfide pathway to pyrite journal March 2007
Reaction pathways in the Fe–S system below 100°C journal June 2000
Nanoparticle Assembly Leads to Mackinawite Formation journal September 2018
Chemical influences on trace metal-sulfide interactions in anoxic sediments journal October 1999
Terrestrial sedimentary pyrites as a potential source of trace metal release to groundwater – A case study from the Emsland, Germany journal January 2017
Textures and compositions of cobalt pentlandite and cobaltian mackinawite from the Madan-Kudan copper deposit, Khetri Copper Belt, Rajasthan, India journal May 2018
Geochemistry of arsenic and metals in stored tailings of a Co–Ni arsenide-ore, Khovu-Aksy area, Russia journal November 2012
Transformation and mobilization of arsenic in the historic Cobalt mining camp, Ontario, Canada journal February 2007
Pitfalls in the Use of Solubility Limits for Radioactive Waste Disposal: The Case of Nickel in Sulfidic Groundwaters journal April 1999
Removal of trace metals by coprecipitation with Fe, Al and Mn from natural waters contaminated with acid mine drainage in the Ducktown Mining District, Tennessee journal May 2002
Groundwater and surface water contamination in the area of the Hitura nickel mine, Western Finland journal July 2002
Concentrations of arsenic and other elements in groundwater of Bangladesh and West Bengal, India: Potential cancer risk journal November 2015
Trace Elements in River Waters book January 2014
What Do We Really Know about the Role of Microorganisms in Iron Sulfide Mineral Formation? journal June 2016
Sulfate-reducing bacteria influence the nucleation and growth of mackinawite and greigite journal January 2018
Formation of Covellite (CuS) Under Biological Sulfate-Reducing Conditions journal December 2006
Formation of Fe-sulfides in cultures of sulfate-reducing bacteria journal March 2010
Extracellular Proteins Limit the Dispersal of Biogenic Nanoparticles journal June 2007
Metal adsorption onto bacterial surfaces: development of a predictive approach journal December 2001
Uptake and retention of metals by cell walls of Bacillus subtilis. journal January 1976
When nanoparticles meet biofilms—interactions guiding the environmental fate and accumulation of nanoparticles journal June 2015
The transformation of mackinawite into greigite studied by Raman spectroscopy journal March 2011
Mackinawite and greigite in ancient alkaline hydrothermal chimneys: Identifying potential key catalysts for emergent life journal November 2015
Fabrication and characterization of nanocrystalline cobalt oxide thin films journal January 2001