Subsurface Flow and Transport

Remediation strategies have been developed for a variety of contaminants by integrating theory, experiment and numerical simulation prior to field-scale studies. Researchers can conduct experiments at various scales, and compare experimental and numerical results to address the nation's most challenging problems in the subsurface related to contaminant transport, carbon cycling, enhanced oil recovery and carbon dioxide sequestration.

Resources and Techniques

  • Users have access to all the tools—flow cells, simulation programs and analytical instruments from chromatographs to spectrometers—necessary for designing and conducting a subsurface flow and transport experiments.
  • Designing experiments—Simulators such as STOMP (Subsurface Transport Over Multiple Phases) are used to define the boundary and initial conditions of the experiment.
  • Conducting experiments—Micro- to intermediate-flow cells are used with analytical tools to generate data about how contaminants move through the soil.
  • A full suite of analytical tools are available to generate data about samples.

Capability Details

  • Intermediate-scale columns and flow cells
  • Pore-scale microfluidic and imaging capabilities
  • High-pressure/temperature cells for research at reservoir conditions
  • Dual energy gamma radiation system
  • Integrated hydraulic properties apparatus
  • Relative permeability apparatus
  • Analytical tools including ion, liquid and gas chromatographs, inductively coupled plasma-mass spectrometry and carbon analysis tools
EMSL's Subsurface Flow and Transport Experimental Laboratory offers several meter-scale flow cells and columns for research in saturated and...
Custodian(s): Tom Wietsma, Mart Oostrom
The Agilent 4500 Series inductively coupled plasma mass spectrometer (ICP-MS) is available for all research areas requiring analysis of trace metals...
Custodian(s): Tom Wietsma
This ion chromatography capability comprises two Dionex DX-500 modular chromatography systems that can be configured to conduct fully automated...
Custodian(s): Tom Wietsma
The Agilent 1100 Series liquid chromatography system is used for all research areas that require quantitative determination of nonvolatile and...
Custodian(s): Tom Wietsma
The pore-scale micromodel flow and transport lab is part of EMSL's Subsurface Flow and Transport Laboratory (SFTL) with a focus on coupled (...
Custodian(s): Mart Oostrom
Titanomagnetite (Fe3-xTixO4) nanoparticles were synthesized by room temperature aqueous precipitation, in which Ti(IV) replaces Fe(III) and is charge...
Long-term (> 4 months) column experiments were performed to investigate the kinetics of uranyl (U(VI)) desorption in sediments collected from...
Magnetic and density separation methods have been applied to composite sediment sample from the Hanford formation from sediment recovered during...
Aluminum is one of the most common components included in nuclear waste glasses. Therefore, Monte Carlo (MC) simulations were carried out to...
Adsorption at mineral surfaces is a critical factor controlling the mobility of uranium(VI) in aqueous environments. Therefore, molecular dynamics (...
Posted: July 11, 2014
The Science The physical and chemical processes that occur at the scale of individual soil particles dictate the way fluids flow underground over...
Posted: April 21, 2014
A multidisciplinary team of scientists at Pacific Northwest National Laboratory using EMSL resources developed a new approach to simulate water...
Posted: March 19, 2013
One of the most noteworthy concerns for the U.S. Department of Energy is controlling atmospheric carbon dioxide to mitigate its effects on global...
Posted: June 13, 2012
Using EMSL capabilities,  scientists at Pacific Northwest National Laboratory determined the wettability—the preference of a rock or other surface...

Remediation strategies have been developed for a variety of contaminants by integrating theory, experiment and numerical simulation prior to field-scale studies. Researchers can conduct experiments at various scales, and compare experimental and numerical results to address the nation's most challenging problems in the subsurface related to contaminant transport, carbon cycling, enhanced oil recovery and carbon dioxide sequestration.

Resources and Techniques

  • Users have access to all the tools—flow cells, simulation programs and analytical instruments from chromatographs to spectrometers—necessary for designing and conducting a subsurface flow and transport experiments.
  • Designing experiments—Simulators such as STOMP (Subsurface Transport Over Multiple Phases) are used to define the boundary and initial conditions of the experiment.
  • Conducting experiments—Micro- to intermediate-flow cells are used with analytical tools to generate data about how contaminants move through the soil.
  • A full suite of analytical tools are available to generate data about samples.

Current Understanding and Remaining Challenges in Modeling Long-Term Degradation of Borosilicate Nuclear Waste Glasses.

Abstract: 

Chemical durability is not a single material property that can be uniquely measured. Instead it is the response to a host of coupled material and environmental processes whose rates are estimated by a combination of theory, experiment, and modeling. High-level nuclear waste (HLW) glass is perhaps the most studied of any material yet there remain significant technical gaps regarding their chemical durability. The phenomena affecting the long-term performance of HLW glasses in their disposal environment include surface reactions, transport properties to and from the reacting glass surface, and ion exchange between the solid glass and the surrounding solution and alteration products. The rates of these processes are strongly influenced and are coupled through the solution chemistry, which is in turn influenced by the reacting glass and also by reaction with the near-field materials and precipitation of alteration products. Therefore, those processes must be understood sufficiently well to estimate or bound the performance of HLW glass in its disposal environment over geologic time-scales. This article summarizes the current state of understanding of surface reactions, transport properties, and ion exchange along with the near-field materials and alteration products influences on solution chemistry and glass reaction rates. Also summarized are the remaining technical gaps along with recommended approaches to fill those technical gaps.

Citation: 
Vienna JD, JV Ryan, S Gin, and Y Inagaki.2013."Current Understanding and Remaining Challenges in Modeling Long-Term Degradation of Borosilicate Nuclear Waste Glasses."International Journal of Applied Glass Science 4(4):283-294. doi:10.1111/ijag.12050
Authors: 
JD Vienna
JV Ryan
S Gin
Y Inagaki
Instruments: 
Volume: 
4
Issue: 
4
Pages: 
283-294
Publication year: 
2013

An international initiative on long-term behavior of high-level nuclear waste glass.

Abstract: 

Nations producing borosilicate glass as an immobilization material for radioactive wastes resulting from spent nuclear fuel reprocessing have reinforced scientific collaboration to obtain consensus on mechanisms controlling the long-term dissolution rate of glass. This goal is deemed to be crucial for the development of reliable performance assessment models for geological disposal. The collaborating laboratories all conduct fundamental and/or applied research with modern materials science techniques. The paper briefly reviews the radioactive waste vitrification programmes of the six participant nations and summarizes the state-of-the-art of glass corrosion science, emphasizing common scientific needs and justifications for on-going initiatives.

Citation: 
Gin S, A Abdelouas, LJ Criscenti, WL Ebert, K Ferrand, T Geisler, MT Harrison, Y Inagaki, S Mitsui, KT Mueller, JC Marra, CG Pantano, EM Pierce, JV Ryan, JM Schofield, CI Steefel, and JD Vienna.2013."An international initiative on long-term behavior of high-level nuclear waste glass."Materials Today 16(6):243-248. doi:10.1016/j.mattod.2013.06.008
Authors: 
S Gin
A Abdelouas
LJ Criscenti
WL Ebert
K Ferr
T Geisler
MT Harrison
Y Inagaki
S Mitsui
KT Mueller
JC Marra
CG Pantano
EM Pierce
JV Ryan
JM Schofield
CI Steefel
JD Vienna
Instruments: 
Volume: 
16
Issue: 
6
Pages: 
243-248
Publication year: 
2013

Monte Carlo Simulations of the Corrosion of Aluminoborosilicate Glasses.

Abstract: 

Aluminum is one of the most common components included in nuclear waste glasses. Therefore, Monte Carlo (MC) simulations were carried out to investigate the influence of aluminum on the rate and mechanism of dissolution of sodium borosilicate glasses in static conditions. The glasses studied were in the compositional range (70-2x)% SiO2 x% Al2O3 15% B2O3 (15+x)% Na2O, where 0 ≤ x ≤ 15%. The simulation results show that increasing amounts of aluminum in the pristine glasses slow down the initial rate of dissolution as determined from the rate of boron release. However, the extent of corrosion - as measured by the total amount of boron release - initially increases with addition of Al2O3, up to 5 Al2O3 mol%, but subsequently decreases with further Al2O3 addition. The MC simulations reveal that this behavior is due to the interplay between two opposing mechanisms: (1) aluminum slows down the kinetics of hydrolysis/condensation reactions that drive the reorganization of the glass surface and eventual formation of a blocking layer; and (2) aluminum strengthens the glass thereby increasing the lifetime of the upper part of its surface and allowing for more rapid formation of a blocking layer. Additional MC simulations were performed whereby a process representing the formation of a secondary aluminosilicate phase was included. Secondary phase formation draws dissolved glass components out of the aqueous solution, thereby diminishing the rate of condensation and delaying the formation of a blocking layer. As a result, the extent of corrosion is found to increase continuously with increasing Al2O3 content, as observed experimentally. For Al2O3 < 10 mol%, the MC simulations also indicate that, because the secondary phase solubility eventually controls the aluminum content in the part of the altered layer in contact with the bulk aqueous solution, the dissolved aluminum and silicon concentrations at steady state are not dependent on the Al2O3 content of the pristine aluminoborosilicate glass.

Citation: 
Kerisit SN, JV Ryan, and EM Pierce.2013."Monte Carlo Simulations of the Corrosion of Aluminoborosilicate Glasses."Journal of Non-crystalline Solids 378:273-281. doi:10.1016/j.jnoncrysol.2013.07.014
Authors: 
SN Kerisit
JV Ryan
EM Pierce
Instruments: 
Publication year: 
2013

Cold Crucible Induction Melter Studies for Making Glass Ceramic Waste Forms: A Feasibility Assessment.

Abstract: 

Glass ceramics are being developed to immobilize fission products, separated from used nuclear fuel by aqueous reprocessing, into a stable waste form suitable for disposal in a geological repository. This work documents the glass ceramic formulation at bench scale and for a scaled melter test performed in a pilot-scale (~1/4 scale) cold crucible induction meter (CCIM). Melt viscosity, electrical conductivity, and crystallization behavior upon cooling were measured on a small set of compositions to select a formulation for melter testing. Property measurements also identified a temperature range for melter operation and cooling profiles necessary to crystallize the targeted phases in the waste form. Bench scale and melter run results successfully demonstrate the processability of the glass ceramic using the CCIM melter technology.

Citation: 
Crum JV, V Maio, JS McCloy, C Scott, BJ Riley, B Benefiel, JD Vienna, K Archibald, CP Rodriguez, V Rutledge, Z Zhu, JV Ryan, and MJ Olszta.2014."Cold Crucible Induction Melter Studies for Making Glass Ceramic Waste Forms: A Feasibility Assessment."Journal of Nuclear Materials 444(1-3):481-492. doi:10.1016/j.jnucmat.2013.10.029
Authors: 
JV Crum
V Maio
JS McCloy
C Scott
BJ Riley
B Benefiel
JD Vienna
K Archibald
CP Rodriguez
V Rutledge
Z Zhu
JV Ryan
MJ Olszta
Instruments: 
Volume: 
444
Pages: 
481-492
Publication year: 
2014

Contribution of atom-probe tomography to a better understanding of glass alteration mechanisms: application to a nuclear glass

Abstract: 

We report and discuss results of atom probe tomography (APT) and energy-filtered transmission electron microscopy (EFTEM) applied to a borosilicate glass sample of nuclear interest altered for nearly 26 years at 90°C in a confined granitic medium in order to better understand the rate-limiting mechanisms under conditions representative of a deep geological repository for vitrified radioactive waste. The APT technique allows the 3D reconstruction of the elemental distribution at the reactive interphase with sub-nanometer precision. Profiles of the B distribution at pristine glass/hydrated glass interface obtained by different techniques are compared to show the challenge of accurate measurements of diffusion profiles at this buried interface on the nanometer length scale. Our results show that 1) Alkali from the glass and hydrogen from the solution exhibit anti-correlated 15 ± 3 nm wide gradients located between the pristine glass and the hydrated glass layer, 2) boron exhibits an unexpectedly sharp profile located just at the outside of the alkali/H interdiffusion layer; this sharp profile is more consistent with a dissolution front than a diffusion-controlled release of boron. The resulting apparent diffusion coefficients derived from the Li and H profiles are DLi = 1.5 × 10-22 m2.s-1 and DH = 6.8 × 10-23 m2.s-1. These values are around two orders of magnitude lower than those observed at the very beginning of the alteration process, which suggests that interdiffusion is slowed at high reaction progress by local conditions that could be related to the porous structure of the interphase. As a result, the accessibility of water to the pristine glass could be the rate-limiting step in these conditions. More generally, these findings strongly support the importance of interdiffusion coupled with hydrolysis reactions of the silicate network on the long-term dissolution rate, contrary to what has been suggested by recent interfacial dissolution-precipitation models for silicate minerals.

Citation: 
Gin S, JV Ryan, DK Schreiber, JJ Neeway, and M Cabie.2013."Contribution of atom-probe tomography to a better understanding of glass alteration mechanisms: application to a nuclear glass specimen altered 25 years in a granitic environment ."Chemical Geology 349-350:99-109.
Authors: 
S Gin
JV Ryan
DK Schreiber
JJ Neeway
M Cabie
Instruments: 
Publication year: 
2013

Solid-State NMR Examination of Alteration Layers on a Nuclear Waste Glasses.

Abstract: 

Solid-state NMR is a powerful tool for probing the role and significance of alteration layers in determining the kinetics for the corrosion of nuclear waste glass. NMR methods are used to probe the chemical structure of the alteration layers to elucidate information about their chemical complexity, leading to increased insight into the mechanism of altered layer formation. Two glass compositions were examined in this study: a glass preliminarily designed for nuclear waste immobilization (called AFCI) and a simplified version of this AFCI glass (which we call SA1R). Powdered glasses with controlled and known particles sizes were corroded at 90 °C for periods of one and five months with a surface-area to solution-volume ratio of 100,000 m-1. 1H-29Si CP-CPMG MAS NMR, 1H-27Al CP-MAS NMR, 1H-11B CP-MAS NMR, and 1H-23Na CP-MAS NMR experiments provide isolated structural information about the alteration layers, which differ in structure from that of the pristine glass. Both glasses studied here develop alteration layers composed primarily of [IV]Si species. Aluminum is also retained in the alteration layers, perhaps facilitated by the observed increase in coordination from [IV]Al to [VI]Al, which correlates with a loss of charge balancing cations. 1H-11B CP-MAS NMR observations indicated a retention of boron in hydrated glass layers, which has not been characterized by previous work. For the AFCI glass, secondary phase formation begins during the corrosion times considered here, and these neophases are detected within the alteration layers. We identify precursor phases as crystalline sodium metasilicates. An important finding is that layer thickness depends on the length of the initial alteration stages and varies only with respect to silicon species during the residual rate regime.

Citation: 
Murphy KA, NM Washton, JV Ryan, CG Pantano, and KT Mueller.2013."Solid-State NMR Examination of Alteration Layers on a Nuclear Waste Glasses."Journal of Non-crystalline Solids 369:44-54. doi:10.1016/j.jnoncrysol.2013.03.021
Authors: 
KA Murphy
NM Washton
JV Ryan
CG Pantano
KT Mueller
Instruments: 
Publication year: 
2013

Flagella-Mediated Differences in Deposition Dynamics for Azotobacter vinelandii in Porous Media.

Abstract: 

A multi-scale approach was designed to investigate deposition of flagellated and non-flagellated strains of Azotobacter vinelandii in porous media. In a radial stagnation point flow cell (RSPF), the deposition rate of the flagellated strain (DJ77) on quartz was higher than that of the non-flagellated (Fla-) strain. In contrast, deposition of the Fla- strain exceeded that of DJ77 in two-dimensional silicon microfluidic models (micromodels) and in columns packed with glass beads. Direct cell counts in micromodel experiments showed decreasing values of clean collector removal efficiencies over time, suggesting that approaching cells were blocked from deposition by cells already attached to the collector surface. Column breakthrough curves for both strains also showed a decrease in deposition rates with time. Modeling results showed that blocking becomes effective for DJ77 strain at lower ionic strengths (1mM and 10mM), while for Fla- strain blocking was similar at all ionic strengths. In later stages of micromodel experiments, a ripening effect was also observed, where cells preferentially attached to already attached cells. Ripening happened earlier with the Fla- strain, which suggested that flagella interfered with ripening. Different mechanisms dominate at different stages of bacteria transport in porous media.

Citation: 
Lu N, T Bevard, A Massoudieh, C Zhang, A Dohnalkova, JL Zilles, and TH Nguyen.2013."Flagella-Mediated Differences in Deposition Dynamics for Azotobacter vinelandii in Porous Media."Environmental Science & Technology 47(10):5162-5170. doi:10.1021/es3053398
Authors: 
Lu N
T Bevard
A Massoudieh
C Zhang
A Dohnalkova
JL Zilles
TH Nguyen
Volume: 
47
Issue: 
10
Pages: 
5162-5170
Publication year: 
2013

Role of collector alternating charged patches on transport of Cryptosporidium parvum oocyst in a patchwise charged heterogeneous

Abstract: 

The role of collector surface charge heterogeneity on transport of Cryptosporidium parvum oocyst and carboxylate microsphere in 2-dimensional micromodels was studied. The cylindrical silica collectors within the micromodels were coated with 0, 10, 20, 50 and 100% Fe2O3 patches. The experimental values of average single collector removal efficiencies (η) of the Fe2O3 patches and on the entire collectors were determined. In the presence of significant (>3500 kT) Derjaguin–Landau–Verwey–Overbeek (DLVO) energy barrier between the microspheres and the silica collectors at pH 5.8 and 8.1, the values of η determined for Fe2O3 patches were significantly less (p < 0.05, t-test) than that obtained for collectors coated entirely with Fe2O3. However, η on Fe2O3 patches for microspheres at pH 4.4 and for oocysts at pH 5.8 and 8.1, where the DLVO energy barrier was relatively small (ca. 200-360 kT), were significantly greater (p < 0.05, t-test) than that on the collectors coated entirely with Fe2O3. The dependence of η determined for Fe2O3 patches on the DLVO energy barrier indicated the importance of periodic favorable and unfavorable electrostatic interactions between colloids and collectors with alternating Fe2O3 and silica patches. Differences between experimentally determined η and that predicted by a patchwise geochemical heterogeneous model was observed, but can be explained by the model’s lack of consideration for the spatial distribution of charge heterogeneity on the collector surface and colloid migration on patchwise heterogeneous collectors.

Citation: 
Liu Y, C Zhang, D Hu, MS Kuhlenschmidt, TB Kuhlenschmidt, SE Mylon, R Kong, R Bhargava, and TH Nguyen.2013."Role of collector alternating charged patches on transport of Cryptosporidium parvum oocyst in a patchwise charged heterogeneous micromodel."Environmental Science & Technology 47(6):2670-2678. doi:10.1021/es304075j
Authors: 
Y Liu
C Zhang
D Hu
MS Kuhlenschmidt
TB Kuhlenschmidt
SE Mylon
R Kong
R Bhargava
TH Nguyen
Volume: 
47
Issue: 
6
Pages: 
2670-2678
Publication year: 
2013

Transport of Cryptosporidium parvum Oocysts in a Silicon Micromodel.

Abstract: 

Effective removal of Cryptosporidium parvum oocysts by granular filtration requires the knowledge of oocyst transport and deposition mechanisms, which can be obtained based on real time microscopic observation of oocyst transport in porous media. Attachment of oocysts to silica surface in a radial stagnation point flow (RSPF) cell and in a micromodel, which has 2-dimensional (2-D) microscopic pore structures consisting of an array of cylindrical collectors, was studied and compared. Real time transport of oocysts in the micromodel was recorded to determine the attached oocyst distributions in transversal and longitudinal directions. In the micromodel, oocysts attached to the forward portion of clean collectors, where the flow velocity was lowest. After initial attachment, oocysts attached onto already attached oocysts. As a result, the collectors ripened and the region available for flow was reduced. Results of attachment and detachment experiments suggest that surface charge heterogeneity allowed for oocyst attachment. In addition to experiments, Lattice-Boltzmann simulations helped understanding the slightly non-uniform flow field and explained differences in the removal efficiency in the transversal direction. However, the hydrodynamic modeling could not explain differences in attachment in the longitudinal direction.

Citation: 
Liu Y, C Zhang, M Hilpert, MS Kuhlenschmidt, TB Kuhlenschmidt, and TH Nguyen.2012."Transport of Cryptosporidium parvum Oocysts in a Silicon Micromodel."Environmental Science & Technology 46(3):1471-1479. doi:10.1021/es202567t
Authors: 
Y Liu
C Zhang
M Hilpert
MS Kuhlenschmidt
TB Kuhlenschmidt
TH Nguyen
Volume: 
46
Issue: 
3
Pages: 
1471-1479
Publication year: 
2012

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