Award Abstract # 1056480
CAREER: Nanoscale Mineral Transformations During Biogeochemical Cycling and the Fate of Trace Elements and Nutrients

NSF Org: EAR
Division Of Earth Sciences
Recipient: WASHINGTON UNIVERSITY, THE
Initial Amendment Date: March 9, 2011
Latest Amendment Date: March 9, 2011
Award Number: 1056480
Award Instrument: Standard Grant
Program Manager: Enriqueta Barrera
EAR
 Division Of Earth Sciences
GEO
 Directorate for Geosciences
Start Date: March 15, 2011
End Date: February 28, 2017 (Estimated)
Total Intended Award Amount: $460,000.00
Total Awarded Amount to Date: $460,000.00
Funds Obligated to Date: FY 2011 = $460,000.00
History of Investigator:
  • Jeffrey Catalano (Principal Investigator)
    catalano@wustl.edu
Recipient Sponsored Research Office: Washington University
1 BROOKINGS DR
SAINT LOUIS
MO  US  63130-4862
(314)747-4134
Sponsor Congressional District: 01
Primary Place of Performance: Washington University
1 BROOKINGS DR
SAINT LOUIS
MO  US  63130-4862
Primary Place of Performance
Congressional District:
01
Unique Entity Identifier (UEI): L6NFUM28LQM5
Parent UEI:
NSF Program(s): EDUCATION AND HUMAN RESOURCES,
Geobiology & Low-Temp Geochem
Primary Program Source: 01001112DB NSF RESEARCH & RELATED ACTIVIT
Program Reference Code(s): 1045, 1187
Program Element Code(s): 157500, 729500
Award Agency Code: 4900
Fund Agency Code: 4900
Assistance Listing Number(s): 47.050

ABSTRACT

The availability and speciation of phosphate and trace elements in sediments, soils, and aquatic systems are strongly affected by biogeochemical cycling involving iron and manganese oxide minerals. These phases are commonly thought to affect the fate of such elements through passive means such as adsorption and coprecipitation. While mineral structural transformations during biogeochemical cycling and their impact on trace element and nutrient fate are well studied for the iron oxides, analogous studies are generally lacking for the Mn system. Similar to iron, environments where active biogeochemical Mn cycling is occurring often contain coexisting aqueous Mn(II) and solid Mn(III/IV) oxides. However, the lamellar structure and complex composition of these manganese minerals and the ability of Mn to undergo complex reactions, suggest that interfacial atom exchange and electron transfer reactions will be more involved for Mn oxides than for Fe oxides and likely lead to bulk structural transformations. Such chemical and structural modification of Mn oxides may have a substantial impact on the fate of trace elements and phosphate in biogeochemical systems. The primary research objective of this proposal is to expand our understanding of how atom exchange and electron transfer reactions drive nanoscale mineral transformations and affect trace element and nutrient fate. The PI?s objectives will be accomplished through a series of systematic studies that combine laboratory-based wet chemistry with advanced chemical and structural characterization of the solid bulk and surface structures and the speciation of associated trace elements and phosphate. The proposed research activities will demonstrate the operation of a new class of mineral transformations and trace element and nutrient reactions during biogeochemical cycling. This work will improve our understanding of how Fe and Mn cycling in sediments, soils, and aquatic systems affect phosphate and micronutrient availability and the fate of contaminants.

The proposed research will provide potential societal benefits in the form of identifying new processes affecting contaminant fate and transport, suggesting new remediation approaches, and serving as inspiration for novel synthesis routes for battery materials. More importantly, the research described in this CAREER proposal will be leveraged to enhance a number of educational activities. These activities are organized around a theme of inquiry-based learning at the undergraduate and high school level. The proposed research activities will be actively used as learning activities for both undergraduate and high school students. These research-based educational activities will be improved and optimized in the PI?s research group, department, and for a local program providing research opportunities to high school students through the development and implementation of assessment plans. A new undergraduate course on Geology and Human Health that incorporates inquiry-based learning and inquiry-based learning modules for an aqueous geochemistry course will be developed. Course materials, pedagogical approaches, and research results will be widely disseminated through websites, blogs, and publication in scientific and education journals.

PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH

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Hinkle M.A.G., Catalano J.G. "Effect of phosphate and sulfate on Ni repartitioning during Fe(II)-catalyzed Fe(III) oxide mineral recrystallization" Geochimica et Cosmochimica Acta , v.165 , 2015 , p.62
Hinkle M.A.G.Catalano J.G. "Effect of phosphate and sulfate on Ni repartitioning during Fe(II)-catalyzed Fe(III) oxide mineral recrystallization" Geochimica et Cosmochimica Acta , v.165 , 2015 , p.62 10.1016/j.gca.2015.05.032
Hinkle M.A.G., Dye K.G., Catalano J.G. "Impact of Mn(II)-manganese oxide reactions on trace element fate" Environmental Science & Technology , v.51 , 2017 , p.3187
Hinkle M.A.G., Flynn E.D., Catalano J.G. "Structural response of phyllomanganates to wet aging and aqueous Mn(II)" Geochimica et Cosmochimica Acta , v.192 , 2016 , p.220
Hinkle M.A.G., Wang Z., Giammar D.E., Catalano J.G. "Interaction of Fe(II) with phosphate and sulfate on iron oxide surfaces" Geochimica et Cosmochimica Acta , v.158 , 2015 , p.130
Hinkle M.A.G.Wang Z.Giammar D.E.Catalano J.G. "Interaction of Fe(II) with phosphate and sulfate on iron oxide surfaces" Geochimica et Cosmochimica Acta , v.158 , 2015 , p.130 10.1016/j.gca.2015.02.030
Hinkle, Margaret A. and Dye, Katherine G. and Catalano, Jeffrey G. "Impact of Mn(II)-Manganese Oxide Reactions on Ni and Zn Speciation" Environmental Science & Technology , v.51 , 2017 10.1021/acs.est.6b04347 Citation Details
Hinkle, Margaret A.G. and Flynn, Elaine D. and Catalano, Jeffrey G. "Structural response of phyllomanganates to wet aging and aqueous Mn(II)" Geochimica et Cosmochimica Acta , v.192 , 2016 10.1016/j.gca.2016.07.035 Citation Details
Lee S.S., Li W., Cho M., Catalano J.G., Lafferty B.J., Decuzzi P., Fortner J.D. "Engineered manganese oxide nanocrystals for enhanced uranyl sorption and separation" Environmental Science: Nano , v.2 , 2015 , p.500
Lee S.S.Li W.Cho M.Catalano J.G.Lafferty B.J.Decuzzi P.Fortner J.D. "Engineered manganese oxide nanocrystals for enhanced uranyl sorption and separation" Environmental Science: Nano , v.2 , 2015 , p.500

PROJECT OUTCOMES REPORT

Disclaimer

This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.

This project revealed ways in which unexpected and surprising transformations of iron and manganese oxide minerals affect the fate and availability of metal contaminants and micronutrients. Dissolved reduced (ferrous) iron had previously been shown to cause iron oxide minerals to simultaneously dissolve and regrow, in the process redistributing metals that can be both toxins and also nutrients. This project demonstrated that common dissolved compounds in soils, rivers, and groundwater, both inorganic and organic, modify these mineral transformations. Compounds like phosphate inhibit this process and preserve metals in the mineral phase, reduced their concentrations in water. In contrast, organic compounds produced by plant root and during organic matter decomposition enhance iron oxide mineral transformations, releasing metals to water. Inorganic and organic compounds thus have distinct effects on contaminant fate and micronutrient availability. Our work has further shown that dissolved reduced manganese can induce structural changes in manganese oxides that are analogous to what occurs with reduced iron and iron oxide minerals, but with important differences. In the case of manganese oxides the mineral undergoes subtle structural changes that alters, and in fact decreases, the ability of the mineral to bind metals. This involves a complex series of chemical processes involving electron transfer. The interaction of organic compounds common in nature with manganese oxide minerals was also studied and found to have a similar effect on the mineral structure and metal binding as dissolved reduced manganese. However, the reactions with organic compounds can occur under aerobic conditions, such as in soils, and are likely more widespread than the processes caused by reduced manganese, which can only occur in the subsurface in the absence of oxygen. Together, this work has identified previously-unknown natural processes that control soil and sediment mineralogy, contaminant fate, and micronutrient availability. This project has also strengthened the STEM workforce by supporting the training of two female Ph.D. students, one female Master’s students, and five female undergraduate students. It also supported the development of a graduate professional development seminar, the design and assessment of new geochemical modeling course modules, and the development of a new freshman course on geology and human health with substantial active-learning components.


Last Modified: 05/22/2017
Modified by: Jeffrey G Catalano

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