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Title: Computational Studies in Molecular Geochemistry and Biogeochemistry

Abstract

The ability to predict the transport and transformations of contaminants within the subsurface is critical for decisions on virtually every waste disposal option facing the Department of Energy (DOE), from remediation technologies such as in situ bioremediation to evaluations of the safety of nuclear waste repositories. With this fact in mind, the DOE has recently sponsored a series of workshops on the development of a Strategic Simulation Plan on applications of high perform-ance computing to national problems of significance to the DOE. One of the areas selected for application was in the area of subsurface transport and environmental chemistry. Within the SSP on subsurface transport and environmental chemistry several areas were identified where applications of high performance computing could potentially significantly advance our knowledge of contaminant fate and transport. Within each of these areas molecular level simulations were specifically identified as a key capability necessary for the development of a fundamental mechanistic understanding of complex biogeochemical processes. This effort consists of a series of specific molecular level simulations and program development in four key areas of geochemistry/biogeochemistry (i.e., aqueous hydrolysis, redox chemistry, mineral surface interactions, and microbial surface properties). By addressing these four differ-ent, but computationally related, areas it becomesmore » possible to assemble a team of investigators with the necessary expertise in high performance computing, molecular simulation, and geochemistry/biogeochemistry to make significant progress in each area. The specific targeted geochemical/biogeochemical issues include: Microbial surface mediated processes: the effects of lipopolysacchardies present on gram-negative bacteria. Environmental redox chemistry: Dechlorination pathways of carbon tetrachloride and other polychlorinated compounds in the subsurface. Mineral surface interactions: Describing surfaces at multiple scales with realistic surface functional groups Aqueous Hydrolysis Reactions and Solvation of Highly Charged Species: Understanding the formation of polymerized species and ore formation under extreme (Hanford Vadose Zone and geothermo) conditions. By understanding on a fundamental basis these key issues, it is anticipated that the impacts of this research will be extendable to a wide range of biogeochemical issues. Taken in total such an effort truly represents a “Grand Challenge” in molecular geochemistry and biogeochemistry.« less

Authors:
; ; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
881689
Report Number(s):
PNNL-15462
1835; 1835a; KP1704020; TRN: US0603017
DOE Contract Number:
AC05-76RL01830
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE WASTES, AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; BACTERIA; BIOGEOCHEMISTRY; BIOREMEDIATION; CARBON TETRACHLORIDE; CHEMISTRY; DECHLORINATION; FUNCTIONALS; GEOCHEMISTRY; HYDROLYSIS; RADIOACTIVE WASTES; SAFETY; SOLVATION; TRANSFORMATIONS; TRANSPORT; WASTE DISPOSAL; Environmental Molecular Sciences Laboratory

Citation Formats

Felmy, Andrew R., Bylaska, Eric J., Dixon, David A., Dupuis, Michel, Halley, James W., Kawai, R., Rosso, Kevin M., Rustad, James R., Smith, Paul E., Straatsma, TP, Voth, Gregory A., Weare, John H., and Yuen, David A.. Computational Studies in Molecular Geochemistry and Biogeochemistry. United States: N. p., 2006. Web. doi:10.2172/881689.
Felmy, Andrew R., Bylaska, Eric J., Dixon, David A., Dupuis, Michel, Halley, James W., Kawai, R., Rosso, Kevin M., Rustad, James R., Smith, Paul E., Straatsma, TP, Voth, Gregory A., Weare, John H., & Yuen, David A.. Computational Studies in Molecular Geochemistry and Biogeochemistry. United States. doi:10.2172/881689.
Felmy, Andrew R., Bylaska, Eric J., Dixon, David A., Dupuis, Michel, Halley, James W., Kawai, R., Rosso, Kevin M., Rustad, James R., Smith, Paul E., Straatsma, TP, Voth, Gregory A., Weare, John H., and Yuen, David A.. Tue . "Computational Studies in Molecular Geochemistry and Biogeochemistry". United States. doi:10.2172/881689. https://www.osti.gov/servlets/purl/881689.
@article{osti_881689,
title = {Computational Studies in Molecular Geochemistry and Biogeochemistry},
author = {Felmy, Andrew R. and Bylaska, Eric J. and Dixon, David A. and Dupuis, Michel and Halley, James W. and Kawai, R. and Rosso, Kevin M. and Rustad, James R. and Smith, Paul E. and Straatsma, TP and Voth, Gregory A. and Weare, John H. and Yuen, David A.},
abstractNote = {The ability to predict the transport and transformations of contaminants within the subsurface is critical for decisions on virtually every waste disposal option facing the Department of Energy (DOE), from remediation technologies such as in situ bioremediation to evaluations of the safety of nuclear waste repositories. With this fact in mind, the DOE has recently sponsored a series of workshops on the development of a Strategic Simulation Plan on applications of high perform-ance computing to national problems of significance to the DOE. One of the areas selected for application was in the area of subsurface transport and environmental chemistry. Within the SSP on subsurface transport and environmental chemistry several areas were identified where applications of high performance computing could potentially significantly advance our knowledge of contaminant fate and transport. Within each of these areas molecular level simulations were specifically identified as a key capability necessary for the development of a fundamental mechanistic understanding of complex biogeochemical processes. This effort consists of a series of specific molecular level simulations and program development in four key areas of geochemistry/biogeochemistry (i.e., aqueous hydrolysis, redox chemistry, mineral surface interactions, and microbial surface properties). By addressing these four differ-ent, but computationally related, areas it becomes possible to assemble a team of investigators with the necessary expertise in high performance computing, molecular simulation, and geochemistry/biogeochemistry to make significant progress in each area. The specific targeted geochemical/biogeochemical issues include: Microbial surface mediated processes: the effects of lipopolysacchardies present on gram-negative bacteria. Environmental redox chemistry: Dechlorination pathways of carbon tetrachloride and other polychlorinated compounds in the subsurface. Mineral surface interactions: Describing surfaces at multiple scales with realistic surface functional groups Aqueous Hydrolysis Reactions and Solvation of Highly Charged Species: Understanding the formation of polymerized species and ore formation under extreme (Hanford Vadose Zone and geothermo) conditions. By understanding on a fundamental basis these key issues, it is anticipated that the impacts of this research will be extendable to a wide range of biogeochemical issues. Taken in total such an effort truly represents a “Grand Challenge” in molecular geochemistry and biogeochemistry.},
doi = {10.2172/881689},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Tue Apr 18 00:00:00 EDT 2006},
month = {Tue Apr 18 00:00:00 EDT 2006}
}

Technical Report:

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  • This report covers the topics of discussion and the recommendations of the panel members. On December 8 and 9, 2010, the Geochemistry, Biogeochemistry, and Subsurface Science (GBSS) Science Theme Advisory Panel (STAP) convened for a more in-depth exploration of the five Science Theme focus areas developed at a similar meeting held in 2009. The goal for the fiscal year (FY) 2011 meeting was to identify potential topical areas for science campaigns, necessary experimental development needs, and scientific members for potential research teams. After a review of the current science in each of the five focus areas, the 2010 STAP discussionsmore » successfully led to the identification of one well focused campaign idea in pore-scale modeling and five longer-term potential research campaign ideas that would likely require additional workshops to identify specific research thrusts. These five campaign areas can be grouped into two categories: (1) the application of advanced high-resolution, high mass accuracy experimental techniques to elucidate the interplay between geochemistry and microbial communities in terrestrial ecosystems and (2) coupled computation/experimental investigations of the electron transfer reactions either between mineral surfaces and outer membranes of microbial cells or between the outer and inner membranes of microbial cells.« less
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  • Arsenic contamination was studied in the Clinch River/Watts Bar Reservoir (CR/WBR) system downstream from the US Department of Energy`s Oak Ridge Reservation (ORR). Arsenic is of particular interest and concern because (1) it occurs commonly in coal-bearing rock and waste products such as fly ash associated with the burning of coal, (2) it is classified as a Class A carcinogen by the US Environmental Protection Agency, and (3) disposal of fly ash, both on and off the ORR, may have contaminated surface water and sediments in the Clinch River and Watts Bar Reservoir. The present study dffers from previous reportsmore » on arsenic concentrations in the CR/WBR system in the use of much more sensitive and precise processing and analytical techniques to measure arsenic species (arsenate, arsenite, and organic arsenic) at levels well below the ecological and human health risk screening criteria. The absolute detection limits using these techniques are approximately 20 to 40 pmol/L or 0.0015 to 0.003 {mu}g/L.« less
  • Arsenic contamination was studied in the Clinch River/Watts Bar Reservoir (CR/WBR) system downstream from the U.S. Department of Energy's Oak Ridge Reservation (ORR). Arsenic is of particular interest and concern because (1) it occurs commonly in coal-bearing rock and waste products such as fly ash associated with the burning of coal, (2) it is classified as a Class A carcinogen by the U. S. Environmental Protection Agency, and (3) disposal of fly ash, both on and off the ORR, may have contaminated surface water and sediments in the Clinch River and Watts Bar Reservoir. The present study differs from previousmore » reports on arsenic concentrations in the CR/WBR system in the use of much more sensitive and precise processing and analytical techniques to measure arsenic species (arsenate, arsenite, and organic arsenic) at levels well below the ecological and human health risk screening criteria. The absolute detection limits using these techniques are approximately 20 to 40 pmol/L, or 0.0015 to 0.003 {micro}g/L. Four main sites were sampled quarterly over a 3-year period (1990 through 1992). Sites investigated included Lower Watts Bar Reservoir near the Watts Bar Dam (Tennessee River kilometer 849.6), the Kingston area (Clinch River kilometer 1.6), Poplar Creek (Poplar Creek kilometer 1.6), and the McCoy Branch Embayment (McCoy Branch kilometer 0.3). Additional sites were investigated in the vicinity of these main stations to determine the distribution of contamination and to identify possible alternative or additional sources of arsenic. Detection limits that were a factor of 20 below the minimum risk screening criteria were achieved for 100% of arsenic speciation data. However, 118 samples for inductively coupled plasma metals analysis were not preserved to analytical specifications, and the analytical holding times for 180 ion chromatography samples were not met. More rigorous preservative testing protocols and more tightly defined analytical statements of work will prevent these problems in the future. Introduction, background, materials and methods, results, discussion, and conclusions are presented in Volume 1. The Quality Assurance/Quality Control Summary Report; the listing of water quality and surface water arsenic speciation data by source and site; and the listing of pore water arsenic speciation and particle-to-water distribution coefficients for As, Fe, and Mn by source, site, and season are presented in Volume 2. The Clinch River Environmental Restoration Program is currently completing the second phase of the Clinch River Remedial Investigation, with the intent of performing a baseline risk assessment on collected data. The data collected for this report will contribute to the baseline risk assessment for the Clinch River. Many of the goals of the Clinch River Remedial Investigation were refined using the results of this study.« less
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