Science.gov

Sample records for 1d reactive transport

  1. Column Testing and 1D Reactive Transport Modeling to Evaluate Uranium Plume Persistence Processes

    SciTech Connect

    Johnson, Raymond H.; Morrison, Stan; Morris, Sarah; Tigar, Aaron; Dam, William; Dayvault, Jalena

    2016-04-26

    Motivation for Study: Natural flushing of contaminants at various U.S. Department of Energy Office of Legacy Management sites is not proceeding as quickly as predicted (plume persistence) Objectives: Help determine natural flushing rates using column tests. Use 1D reactive transport modeling to better understand the major processes that are creating plume persistence Approach: Core samples from under a former mill tailings area Tailings have been removed. Column leaching using lab-prepared water similar to nearby Gunnison River water. 1D reactive transport modeling to evaluate processes

  2. A 1D plug flow reactor as validation tool for reactive transport simulations

    NASA Astrophysics Data System (ADS)

    Battaïa, G.; Garcia, D.

    2012-04-01

    Predictions in CO2 geological sequestration involve a broad range of earth sciences linked in complex models. Amongst the processes commonly described, fluid-rock interactions are both a central issue and a source of discomfort for modelers since it has to deal with 1) kinetics data obtained through experimental procedures that dramatically differ from natural systems and 2) reactive surface model that are very diverse and often empirical. This study presents a new type of plug flow reactor developed to provide an experimental validation of reactive transport simulations. This is a 1D pressurized packed-bed plug-flow reactor containing a granular mixture as a porous medium. This mixture is composed of a reactive solids and unreactive quartz used to set an adequate ratio between fluid and reactive mineral to control the front velocity. A seven sampling valve unit allows concentration profiles of the reacting fluid to be captured at any time. One the one side, a low reaction rate (diopside, HNO3, pH 2) produces linear profile resulting from a constant dissolution rate along the reactor length. But on the other side, when performing the reaction of CO2 saturated solutions (5 bar) at 40°C with dolomite it gives rise to dissolution fronts migrating downstream. A proper projection of experimental data reveals a dynamic steady state of front shape is reached. Texture of the mineral recovered at the end of the experiment is quantified by Hg-porosimetry and these results are linked to SEM observations. Altogether, this provides a robust way for the parameterization of a reactive surface area model.

  3. Column Testing and 1D Reactive Transport Modeling to Evaluate Uranium Plume Persistence Processes

    NASA Astrophysics Data System (ADS)

    Johnson, R. H.; Morrison, S.; Morris, S.; Tigar, A.; Dam, W. L.; Dayvault, J.

    2015-12-01

    At many U.S. Department of Energy Office of Legacy Management sites, 100 year natural flushing was selected as a remedial option for groundwater uranium plumes. However, current data indicate that natural flushing is not occurring as quickly as expected and solid-phase and aqueous uranium concentrations are persistent. At the Grand Junction, Colorado office site, column testing was completed on core collected below an area where uranium mill tailings have been removed. The total uranium concentration in this core was 13.2 mg/kg and the column was flushed with laboratory-created water with no uranium and chemistry similar to the nearby Gunnison River. The core was flushed for a total of 91 pore volumes producing a maximum effluent uranium concentration of 6,110 μg/L at 2.1 pore volumes and a minimum uranium concentration of 36.2 μg/L at the final pore volume. These results indicate complex geochemical reactions at small pore volumes and a long tailing affect at greater pore volumes. Stop flow data indicate the occurrence of non-equilibrium processes that create uranium concentration rebound. These data confirm the potential for plume persistence, which is occurring at the field scale. 1D reactive transport modeling was completed using PHREEQC (geochemical model) and calibrated to the column test data manually and using PEST (inverse modeling calibration routine). Processes of sorption, dual porosity with diffusion, mineral dissolution, dispersion, and cation exchange were evaluated separately and in combination. The calibration results indicate that sorption and dual porosity are major processes in explaining the column test data. These processes are also supported by fission track photographs that show solid-phase uranium residing in less mobile pore spaces. These procedures provide valuable information on plume persistence and secondary source processes that may be used to better inform and evaluate remedial strategies, including natural flushing.

  4. Reactive Transport Modeling of Microbially-Mediated Chromate Reduction in 1-D Soil Columns

    NASA Astrophysics Data System (ADS)

    Qiu, H.; Viamajala, S.; Alam, M. M.; Peyton, B. M.; Petersen, J. N.; Yonge, D. R.

    2002-12-01

    Cr(VI) reduction tests were performed with the well known metal reducing bacterium Shewanella oneidensis MR-1 in liquid phase batch reactors and continuous flow soil columns under anaerobic conditions. In the batch tests, the cultures were grown with fumarate as the terminal electron acceptor and lactate as the electron donor in a simulated groundwater medium to determine yield coefficients and specific growth rates. The bench-scale soil column experiments were carried out with MR-1 to test the hypothesis that the kinetic parameters obtained in batch studies, combined with microbial attachment /detachment processes, will accurately predict reactive transport of Cr(VI) during bacterial Cr(VI) reduction in a soil matrix. Cr(VI)-free simulated groundwater media containing fumarate as the limiting substrate and lactate was supplied to a 2.1cm (ID) x 15 cm soil column inoculated with MR-1 for a duration of 9 residence times to allow for biomass to build-up in the column. Thereafter the column was supplied with both Cr(VI) and substrate. The concentrations of effluent substrate, biomass and Cr(VI) were monitored on a periodic basis and attached biomass in the column was measured in the termination of each column test. A reactive transport model was developed in which 6 governing equations deal with Cr(VI) bioreaction, fumarate (as electron donor) consumption, aqueous biomass growth and transport, solid biomass detachment and attachment kinetics, aqueous and solid phase enzyme reaction and transport, respectively. The model incorporating the enzyme reaction kinetics for Cr(VI) reduction, Monod kinetic expressions for substrate depletion, nonlinear attachment and detachment kinetics for aqueous and solid phase microorganism concentration, was solved by a fully implicit, finite-difference procedure using RT3D (A Modular Computer Code for Reactive Multi-species Transport in 3-Dimensional Groundwater Systems) platform in one dimension. Cr(VI)-free column data was used to

  5. 1D Thermal-Hydraulic-Chemical (THC) Reactive transport modeling for deep geothermal systems: A case study of Groß Schönebeck reservoir, Germany

    NASA Astrophysics Data System (ADS)

    Driba, D. L.; De Lucia, M.; Peiffer, S.

    2014-12-01

    Fluid-rock interactions in geothermal reservoirs are driven by the state of disequilibrium that persists among solid and solutes due to changing temperature and pressure. During operation of enhanced geothermal systems, injection of cooled water back into the reservoir disturbs the initial thermodynamic equilibrium between the reservoir and its geothermal fluid, which may induce modifications in permeability through changes in porosity and pore space geometry, consequently bringing about several impairments to the overall system.Modeling of fluid-rock interactions induced by injection of cold brine into Groß Schönebeck geothermal reservoir system situated in the Rotliegend sandstone at 4200m depth have been done by coupling geochemical modeling Code Phreeqc with OpenGeoSys. Through batch modeling the re-evaluation of the measured hydrochemical composition of the brine has been done using Quintessa databases, the results from the calculation indicate that a mineral phases comprising of K-feldspar, hematite, Barite, Calcite and Dolomite was found to match the hypothesis of equilibrium with the formation fluid, Reducing conditions are presumed in the model (pe = -3.5) in order to match the amount of observed dissolved Fe and thus considered as initial state for the reactive transport modeling. based on a measured composition of formation fluids and the predominant mineralogical assemblage of the host rock, a preliminary 1D Reactive transport modeling (RTM) was run with total time set to 30 years; results obtained for the initial simulation revealed that during this period, no significant change is evident for K-feldspar. Furthermore, the precipitation of calcite along the flow path in the brine results in a drop of pH from 6.2 to a value of 5.2 noticed over the simulated period. The circulation of cooled fluid in the reservoir is predicted to affect the temperature of the reservoir within the first 100 -150m from the injection well. Examination of porosity change in

  6. Reactive transport modeling

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This special section in the Vadose Zone Journal focusing on reactive transport modeling was developed from a special symposium jointly sponsored by the Soil Physics and Soil Chemistry Divisions of the Soil Science Society of America at the 2010 annual meetings held in Long Beach, CA. It contains eig...

  7. Interaction of environmental contaminants with zebrafish organic anion transporting polypeptide, Oatp1d1 (Slco1d1)

    SciTech Connect

    Popovic, Marta; Zaja, Roko; Fent, Karl; Smital, Tvrtko

    2014-10-01

    Polyspecific transporters from the organic anion transporting polypeptide (OATP/Oatp) superfamily mediate the uptake of a wide range of compounds. In zebrafish, Oatp1d1 transports conjugated steroid hormones and cortisol. It is predominantly expressed in the liver, brain and testes. In this study we have characterized the transport of xenobiotics by the zebrafish Oatp1d1 transporter. We developed a novel assay for assessing Oatp1d1 interactors using the fluorescent probe Lucifer yellow and transient transfection in HEK293 cells. Our data showed that numerous environmental contaminants interact with zebrafish Oatp1d1. Oatp1d1 mediated the transport of diclofenac with very high affinity, followed by high affinity towards perfluorooctanesulfonic acid (PFOS), nonylphenol, gemfibrozil and 17α-ethinylestradiol; moderate affinity towards carbaryl, diazinon and caffeine; and low affinity towards metolachlor. Importantly, many environmental chemicals acted as strong inhibitors of Oatp1d1. A strong inhibition of Oatp1d1 transport activity was found by perfluorooctanoic acid (PFOA), chlorpyrifos-methyl, estrone (E1) and 17β-estradiol (E2), followed by moderate to low inhibition by diethyl phthalate, bisphenol A, 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4 tetrahydronapthalene and clofibrate. In this study we identified Oatp1d1 as a first Solute Carrier (SLC) transporter involved in the transport of a wide range of xenobiotics in fish. Considering that Oatps in zebrafish have not been characterized before, our work on zebrafish Oatp1d1 offers important new insights on the understanding of uptake processes of environmental contaminants, and contributes to the better characterization of zebrafish as a model species. - Highlights: • We optimized a novel assay for determination of Oatp1d1 interactors • Oatp1d1 is the first SLC characterized fish xenobiotic transporter • PFOS, nonylphenol, diclofenac, EE2, caffeine are high affinity Oatp1d1substrates • PFOA, chlorpyrifos

  8. Validation of 1-D transport and sawtooth models for ITER

    SciTech Connect

    Connor, J.W.; Turner, M.F.; Attenberger, S.E.; Houlberg, W.A.

    1996-12-31

    In this paper the authors describe progress on validating a number of local transport models by comparing their predictions with relevant experimental data from a range of tokamaks in the ITER profile database. This database, the testing procedure and results are discussed. In addition a model for sawtooth oscillations is used to investigate their effect in an ITER plasma with alpha-particles.

  9. Morphodynamics and sediment tracers in 1-D (MAST-1D): 1-D sediment transport that includes exchange with an off-channel sediment reservoir

    NASA Astrophysics Data System (ADS)

    Lauer, J. Wesley; Viparelli, Enrica; Piégay, Hervé

    2016-07-01

    Bed material transported in geomorphically active gravel bed rivers often has a local source at nearby eroding banks and ends up sequestered in bars not far downstream. However, most 1-D numerical models for gravel transport assume that gravel originates from and deposits on the channel bed. In this paper, we present a 1-D framework for simulating morphodynamic evolution of bed elevation and size distribution in a gravel-bed river that actively exchanges sediment with its floodplain, which is represented as an off-channel sediment reservoir. The model is based on the idea that sediment enters the channel at eroding banks whose elevation depends on total floodplain sediment storage and on the average elevation of the floodplain relative to the channel bed. Lateral erosion of these banks occurs at a specified rate that can represent either net channel migration or channel widening. Transfer of material out of the channel depends on a typical bar thickness and a specified lateral exchange rate due either to net channel migration or narrowing. The model is implemented using an object oriented framework that allows users to explore relationships between bank supply, bed structure, and lateral change rates. It is applied to a ∼50-km reach of the Ain River, France, that experienced significant reduction in sediment supply due to dam construction during the 20th century. Results are strongly sensitive to lateral exchange rates, showing that in this reach, the supply of sand and gravel at eroding banks and the sequestration of gravel in point bars can have strong influence on overall reach-scale sediment budgets.

  10. Potential energy surface intersections in the C(1D)H2 reactive system.

    PubMed

    Liu, Xiaojun; Bian, Wensheng; Zhao, Xian; Tao, Xutang

    2006-08-21

    Potential energy surface (PES) intersection seams of two or more electronic states from the 1 1A', 2 1A', 3 1A', 1 1A", and 2 1A" states in the C(1D)H2 reactive system are investigated using the internally contracted multireference configuration interaction method and the aug-cc-pVQZ basis set. Intersection seams with energies less than 20 kcal/mol relative to the C(1D) + H2 asymptote are searched systematically, and finally several seam lines (at the linear H-C-H, linear C-H-H, and C(2v), geometries, respectively) and a seam surface (at Cs geometries) are discovered and determined. The minimum energy crossing points on these seams are reported and the influences of the PES intersections, in particular, conical intersections, on the CH2 spectroscopy and the C(1D) + H2 reaction dynamics are discussed. In addition, geometries and energies of the 1 1A2 and 1 1B2 states of methylene biradical CH2 are reported in detail for the first time.

  11. MULTICOMPONENT GEOCHEMICAL TRANSPORT MODELING USING HYDRUS-1D AND HP1

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The transport of reactive contaminants in the subsurface is generally affected by a large number of nonlinear and often interactive physical, chemical, and biological processes. Simulating these processes requires a comprehensive reactive transport code that couples the physical processes of water f...

  12. XCHEM-1D: A Heat Transfer/Chemical Kinetics Computer Program for multilayered reactive materials

    SciTech Connect

    Gross, R.J.; Baer, M.R.; Hobbs, M.L.

    1993-10-01

    An eXplosive CHEMical kinetics code, XCHEM, has been developed to solve the reactive diffusion equations associated with thermal ignition of energetic materials. This method-of-lines code uses stiff numerical methods and adaptive meshing to resolve relevant combustion physics. Solution accuracy is maintained between multilayered materials consisting of blends of reactive components and/or inert materials. Phase change and variable properties are included in one-dimensional slab, cylindrical and spherical geometries. Temperature-dependent thermal properties have been incorporated and the modification of thermal conductivities to include decomposition effects are estimated using solid/gas volume fractions determined by species fractions. Gas transport properties, including high pressure corrections, have also been included. Time varying temperature, heat flux, convective and thermal radiation boundary conditions, and layer to layer contact resistances have also been implemented.

  13. A New 2D-Transport, 1D-Diffusion Approximation of the Boltzmann Transport equation

    SciTech Connect

    Larsen, Edward

    2013-06-17

    The work performed in this project consisted of the derivation, implementation, and testing of a new, computationally advantageous approximation to the 3D Boltz- mann transport equation. The solution of the Boltzmann equation is the neutron flux in nuclear reactor cores and shields, but solving this equation is difficult and costly. The new “2D/1D” approximation takes advantage of a special geometric feature of typical 3D reactors to approximate the neutron transport physics in a specific (ax- ial) direction, but not in the other two (radial) directions. The resulting equation is much less expensive to solve computationally, and its solutions are expected to be sufficiently accurate for many practical problems. In this project we formulated the new equation, discretized it using standard methods, developed a stable itera- tion scheme for solving the equation, implemented the new numerical scheme in the MPACT code, and tested the method on several realistic problems. All the hoped- for features of this new approximation were seen. For large, difficult problems, the resulting 2D/1D solution is highly accurate, and is calculated about 100 times faster than a 3D discrete ordinates simulation.

  14. TCTEX1D2 mutations underlie Jeune asphyxiating thoracic dystrophy with impaired retrograde intraflagellar transport

    PubMed Central

    Schmidts, Miriam; Hou, Yuqing; Cortés, Claudio R.; Mans, Dorus A.; Huber, Celine; Boldt, Karsten; Patel, Mitali; van Reeuwijk, Jeroen; Plaza, Jean-Marc; van Beersum, Sylvia E. C.; Yap, Zhi Min; Letteboer, Stef J. F.; Taylor, S. Paige; Herridge, Warren; Johnson, Colin A.; Scambler, Peter J.; Ueffing, Marius; Kayserili, Hulya; Krakow, Deborah; King, Stephen M.; Beales, Philip L.; Al-Gazali, Lihadh; Wicking, Carol; Cormier-Daire, Valerie; Roepman, Ronald; Mitchison, Hannah M.; Witman, George B.; Al-Turki, Saeed; Anderson, Carl; Anney, Richard; Antony, Dinu; Asimit, Jennifer; Ayub, Mohammad; Barrett, Jeff; Barroso, Inês; Bentham, Jamie; Bhattacharya, Shoumo; Blackwood, Douglas; Bobrow, Martin; Bochukova, Elena; Bolton, Patrick; Boustred, Chris; Breen, Gerome; Brion, Marie-Jo; Brown, Andrew; Calissano, Mattia; Carss, Keren; Chatterjee, Krishna; Chen, Lu; Cirak, Sebhattin; Clapham, Peter; Clement, Gail; Coates, Guy; Collier, David; Cosgrove, Catherine; Cox, Tony; Craddock, Nick; Crooks, Lucy; Curran, Sarah; Daly, Allan; Danecek, Petr; Smith, George Davey; Day-Williams, Aaron; Day, Ian; Durbin, Richard; Edkins, Sarah; Ellis, Peter; Evans, David; Farooqi, I. Sadaf; Fatemifar, Ghazaleh; Fitzpatrick, David; Flicek, Paul; Floyd, Jamie; Foley, A. Reghan; Franklin, Chris; Futema, Marta; Gallagher, Louise; Gaunt, Tom; Geschwind, Daniel; Greenwood, Celia; Grozeva, Detelina; Guo, Xiaosen; Gurling, Hugh; Hart, Deborah; Hendricks, Audrey; Holmans, Peter; Huang, Jie; Humphries, Steve E.; Hurles, Matt; Hysi, Pirro; Jackson, David; Jamshidi, Yalda; Jewell, David; Chris, Joyce; Kaye, Jane; Keane, Thomas; Kemp, John; Kennedy, Karen; Kent, Alastair; Kolb-Kokocinski, Anja; Lachance, Genevieve; Langford, Cordelia; Lee, Irene; Li, Rui; Li, Yingrui; Ryan, Liu; Lönnqvist, Jouko; Lopes, Margarida; MacArthur, Daniel G.; Massimo, Mangino; Marchini, Jonathan; Maslen, John; McCarthy, Shane; McGuffin, Peter; McIntosh, Andrew; McKechanie, Andrew; McQuillin, Andrew; Memari, Yasin; Metrustry, Sarah; Min, Josine; Moayyeri, Alireza; Morris, James; Muddyman, Dawn; Muntoni, Francesco; Northstone, Kate; O'Donovan, Michael; O'Rahilly, Stephen; Onoufriadis, Alexandros; Oualkacha, Karim; Owen, Michael; Palotie, Aarno; Panoutsopoulou, Kalliope; Parker, Victoria; Parr, Jeremy; Paternoster, Lavinia; Paunio, Tiina; Payne, Felicity; Perry, John; Pietilainen, Olli; Plagnol, Vincent; Quail, Michael A.; Quaye, Lydia; Raymond, Lucy; Rehnström, Karola; Brent Richards, J.; Ring, Sue; Ritchie, Graham R S; Savage, David B.; Schoenmakers, Nadia; Semple, Robert K.; Serra, Eva; Shihab, Hashem; Shin, So-Youn; Skuse, David; Small, Kerrin; Smee, Carol; Soler, Artigas María; Soranzo, Nicole; Southam, Lorraine; Spector, Tim; St Pourcain, Beate; St. Clair, David; Stalker, Jim; Surdulescu, Gabriela; Suvisaari, Jaana; Tachmazidou, Ioanna; Tian, Jing; Timpson, Nic; Tobin, Martin; Valdes, Ana; van Kogelenberg, Margriet; Vijayarangakannan, Parthiban; Wain, Louise; Walter, Klaudia; Wang, Jun; Ward, Kirsten; Wheeler, Ellie; Whittall, Ros; Williams, Hywel; Williamson, Kathy; Wilson, Scott G.; Wong, Kim; Whyte, Tamieka; ChangJiang, Xu; Zeggini, Eleftheria; Zhang, Feng; Zheng, Hou-Feng

    2015-01-01

    The analysis of individuals with ciliary chondrodysplasias can shed light on sensitive mechanisms controlling ciliogenesis and cell signalling that are essential to embryonic development and survival. Here we identify TCTEX1D2 mutations causing Jeune asphyxiating thoracic dystrophy with partially penetrant inheritance. Loss of TCTEX1D2 impairs retrograde intraflagellar transport (IFT) in humans and the protist Chlamydomonas, accompanied by destabilization of the retrograde IFT dynein motor. We thus define TCTEX1D2 as an integral component of the evolutionarily conserved retrograde IFT machinery. In complex with several IFT dynein light chains, it is required for correct vertebrate skeletal formation but may be functionally redundant under certain conditions. PMID:26044572

  15. Significance of flow clustering and sequencing on sediment transport: 1D sediment transport modelling

    NASA Astrophysics Data System (ADS)

    Hassan, Kazi; Allen, Deonie; Haynes, Heather

    2016-04-01

    This paper considers 1D hydraulic model data on the effect of high flow clusters and sequencing on sediment transport. Using observed flow gauge data from the River Caldew, England, a novel stochastic modelling approach was developed in order to create alternative 50 year flow sequences. Whilst the observed probability density of gauge data was preserved in all sequences, the order in which those flows occurred was varied using the output from a Hidden Markov Model (HMM) with generalised Pareto distribution (GP). In total, one hundred 50 year synthetic flow series were generated and used as the inflow boundary conditions for individual flow series model runs using the 1D sediment transport model HEC-RAS. The model routed graded sediment through the case study river reach to define the long-term morphological changes. Comparison of individual simulations provided a detailed understanding of the sensitivity of channel capacity to flow sequence. Specifically, each 50 year synthetic flow sequence was analysed using a 3-month, 6-month or 12-month rolling window approach and classified for clusters in peak discharge. As a cluster is described as a temporal grouping of flow events above a specified threshold, the threshold condition used herein is considered as a morphologically active channel forming discharge event. Thus, clusters were identified for peak discharges in excess of 10%, 20%, 50%, 100% and 150% of the 1 year Return Period (RP) event. The window of above-peak flows also required cluster definition and was tested for timeframes 1, 2, 10 and 30 days. Subsequently, clusters could be described in terms of the number of events, maximum peak flow discharge, cumulative flow discharge and skewness (i.e. a description of the flow sequence). The model output for each cluster was analysed for the cumulative flow volume and cumulative sediment transport (mass). This was then compared to the total sediment transport of a single flow event of equivalent flow volume

  16. Epitaxial 1D electron transport layers for high-performance perovskite solar cells.

    PubMed

    Han, Gill Sang; Chung, Hyun Suk; Kim, Dong Hoe; Kim, Byeong Jo; Lee, Jin-Wook; Park, Nam-Gyu; Cho, In Sun; Lee, Jung-Kun; Lee, Sangwook; Jung, Hyun Suk

    2015-10-07

    We demonstrate high-performance perovskite solar cells with excellent electron transport properties using a one-dimensional (1D) electron transport layer (ETL). The 1D array-based ETL is comprised of 1D SnO2 nanowires (NWs) array grown on a F:SnO2 transparent conducting oxide substrate and rutile TiO2 nanoshells epitaxially grown on the surface of the 1D SnO2 NWs. The optimized devices show more than 95% internal quantum yield at 750 nm, and a power conversion efficiency (PCE) of 14.2%. The high quantum yield is attributed to dramatically enhanced electron transport in the epitaxial TiO2 layer, compared to that in conventional nanoparticle-based mesoporous TiO2 (mp-TiO2) layers. In addition, the open space in the 1D array-based ETL increases the prevalence of uniform TiO2/perovskite junctions, leading to reproducible device performance with a high fill factor. This work offers a method to achieve reproducible, high-efficiency perovskite solar cells with high-speed electron transport.

  17. Epitaxial 1D electron transport layers for high-performance perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Han, Gill Sang; Chung, Hyun Suk; Kim, Dong Hoe; Kim, Byeong Jo; Lee, Jin-Wook; Park, Nam-Gyu; Cho, In Sun; Lee, Jung-Kun; Lee, Sangwook; Jung, Hyun Suk

    2015-09-01

    We demonstrate high-performance perovskite solar cells with excellent electron transport properties using a one-dimensional (1D) electron transport layer (ETL). The 1D array-based ETL is comprised of 1D SnO2 nanowires (NWs) array grown on a F:SnO2 transparent conducting oxide substrate and rutile TiO2 nanoshells epitaxially grown on the surface of the 1D SnO2 NWs. The optimized devices show more than 95% internal quantum yield at 750 nm, and a power conversion efficiency (PCE) of 14.2%. The high quantum yield is attributed to dramatically enhanced electron transport in the epitaxial TiO2 layer, compared to that in conventional nanoparticle-based mesoporous TiO2 (mp-TiO2) layers. In addition, the open space in the 1D array-based ETL increases the prevalence of uniform TiO2/perovskite junctions, leading to reproducible device performance with a high fill factor. This work offers a method to achieve reproducible, high-efficiency perovskite solar cells with high-speed electron transport.We demonstrate high-performance perovskite solar cells with excellent electron transport properties using a one-dimensional (1D) electron transport layer (ETL). The 1D array-based ETL is comprised of 1D SnO2 nanowires (NWs) array grown on a F:SnO2 transparent conducting oxide substrate and rutile TiO2 nanoshells epitaxially grown on the surface of the 1D SnO2 NWs. The optimized devices show more than 95% internal quantum yield at 750 nm, and a power conversion efficiency (PCE) of 14.2%. The high quantum yield is attributed to dramatically enhanced electron transport in the epitaxial TiO2 layer, compared to that in conventional nanoparticle-based mesoporous TiO2 (mp-TiO2) layers. In addition, the open space in the 1D array-based ETL increases the prevalence of uniform TiO2/perovskite junctions, leading to reproducible device performance with a high fill factor. This work offers a method to achieve reproducible, high-efficiency perovskite solar cells with high-speed electron transport

  18. The organic anion transport polypeptide 1d1 (Oatp1d1) mediates hepatocellular uptake of phalloidin and microcystin into skate liver

    SciTech Connect

    Meier-Abt, F.; Hammann-Haenni, A.; Stieger, B.; Ballatori, N.; Boyer, J.L. . E-mail: james.boyer@yale.edu

    2007-02-01

    Organic anion transporting polypeptides (rodent Oatp; human OATP) mediate cellular uptake of numerous organic compounds including xenobiotic toxins into mammalian hepatocytes. In the little skate Leucoraja erinacea a liver-specific Oatp (Oatp1d1, also called sOatp) has been identified and suggested to represent an evolutionarily ancient precursor of the mammalian liver OATP1B1 (human), Oatp1b2 (rat), and OATP1B3 (human). The present study tested whether Oatp1d1 shares functional transport activity of the xenobiotic oligopeptide toxins phalloidin and microcystin with the mammalian liver Oatps/OATPs. The phalloidin analogue [{sup 3}H]-demethylphalloin was taken up into skate hepatocytes with high affinity (Km {approx} 0.4 {mu}M), and uptake could be inhibited by phalloidin and a variety of typical Oatp/OATP substrates such as bromosulfophthalein, bile salts, estrone-3-sulfate, cyclosporine A and high concentrations of microcystin-LR (Ki {approx} 150 {mu}M). When expressed in Xenopus laevis oocytes Oatp1d1 increased uptake of demethylphalloin (Km {approx} 2.2 {mu}M) and microcystin-LR (Km {approx} 27 {mu}M) 2- to 3-fold over water-injected oocytes, whereas the alternative skate liver organic anion transporter, the dimeric Ost{alpha}/{beta}, exhibited no phalloidin and only minor microcystin-LR transport. Also, the closest mammalian Oatp1d1 orthologue, the human brain and testis OATP1C1, did not show any phalloidin transport activity. These results demonstrate that the evolutionarily ancient Oatp1d1 is able to mediate uptake of cyclic oligopeptide toxins into skate liver. The findings support the notion that Oatp1d1 is a precursor of the liver-specific mammalian Oatps/OATPs and that its transport properties are closely associated with certain forms of toxic liver injury such as for example protein phosphatase inhibition by the water-borne toxin microcystin.

  19. Benchmarks and models for 1-D radiation transport in stochastic participating media

    SciTech Connect

    Miller, David Scott

    2000-08-01

    Benchmark calculations for radiation transport coupled to a material temperature equation in a 1-D slab and 1-D spherical geometry binary random media are presented. The mixing statistics are taken to be homogeneous Markov statistics in the 1-D slab but only approximately Markov statistics in the 1-D sphere. The material chunk sizes are described by Poisson distribution functions. The material opacities are first taken to be constant and then allowed to vary as a strong function of material temperature. Benchmark values and variances for time evolution of the ensemble average of material temperature energy density and radiation transmission are computed via a Monte Carlo type method. These benchmarks are used as a basis for comparison with three other approximate methods of solution. One of these approximate methods is simple atomic mix. The second approximate model is an adaptation of what is commonly called the Levermore-Pomraning model and which is referred to here as the standard model. It is shown that recasting the temperature coupling as a type of effective scattering can be useful in formulating the third approximate model, an adaptation of a model due to Su and Pomraning which attempts to account for the effects of scattering in a stochastic context. This last adaptation shows consistent improvement over both the atomic mix and standard models when used in the 1-D slab geometry but shows limited improvement in the 1-D spherical geometry. Benchmark values are also computed for radiation transmission from the 1-D sphere without material heating present. This is to evaluate the performance of the standard model on this geometry--something which has never been done before. All of the various tests demonstrate the importance of stochastic structure on the solution. Also demonstrated are the range of usefulness and limitations of a simple atomic mix formulation.

  20. Benchmarks and models for 1-D radiation transport in stochastic participating media

    NASA Astrophysics Data System (ADS)

    Miller, David Scott

    Benchmark calculations for radiation transport coupled to a material temperature equation in a 1-D slab and 1-D spherical geometry binary random media are presented. The mixing statistics are taken to be homogeneous Markov statistics in the 1-D slab but only approximately Markov statistics in the 1-D sphere. The material chunk sizes are described by Poisson distribution functions. The material opacities are first taken to be constant and then allowed to vary as a strong function of material temperature. Benchmark values and variances for time evolution of the ensemble average of material temperature energy density and radiation transmission are computed via a Monte Carlo type method. These benchmarks are used as a basis for comparison with three other approximate methods of solution. One of these approximate methods is simple atomic mix. The second approximate model is an adaptation of what is commonly called the Levermore-Pomraning model and which is referred to here as the standard model. It is shown that recasting the temperature coupling as a type of effective scattering can be useful in formulating the third approximate model, an adaptation of a model due to Su and Pomraning which attempts to account for the effects of scattering in a stochastic context. This last adaptation shows consistent improvement over both the atomic mix and standard models when used in the 1-D slab geometry but shows limited improvement in the 1-D spherical geometry. Benchmark values are also computed for radiation transmission from the 1-D sphere without material heating present. This is to evaluate the performance of the standard model on this geometry-something which has never been done before. All of the various tests demonstrate the importance of stochastic structure on the solution. Also demonstrated are the range of usefulness and limitations of a simple atomic mix formulation.

  1. Discontinuous Galerkin finite element method applied to the 1-D spherical neutron transport equation

    SciTech Connect

    Machorro, Eric . E-mail: machorro@amath.washington.edu

    2007-04-10

    Discontinuous Galerkin finite element methods are used to estimate solutions to the non-scattering 1-D spherical neutron transport equation. Various trial and test spaces are compared in the context of a few sample problems whose exact solution is known. Certain trial spaces avoid unphysical behaviors that seem to plague other methods. Comparisons with diamond differencing and simple corner-balancing are presented to highlight these improvements.

  2. quantifying and Predicting Reactive Transport

    SciTech Connect

    Peter C. Burns, Department of Civil Engineering and Geological Sciences, University of Notre Dame

    2009-12-04

    This project was led by Dr. Jiamin Wan at Lawrence Berkeley National Laboratory. Peter Burns provided expertise in uranium mineralogy and in identification of uranium minerals in test materials. Dr. Wan conducted column tests regarding uranium transport at LBNL, and samples of the resulting columns were sent to Dr. Burns for analysis. Samples were analyzed for uranium mineralogy by X-ray powder diffraction and by scanning electron microscopy, and results were provided to Dr. Wan for inclusion in the modeling effort. Full details of the project can be found in Dr. Wan's final reports for the associated effort at LBNL.

  3. Long distance transport of ultracold atoms using a 1D optical lattice

    NASA Astrophysics Data System (ADS)

    Schmid, Stefan; Thalhammer, Gregor; Winkler, Klaus; Lang, Florian; Hecker Denschlag, Johannes

    2006-08-01

    We study the horizontal transport of ultracold atoms over macroscopic distances of up to 20 cm with a moving 1D optical lattice. By using an optical Bessel beam to form the optical lattice, we can achieve nearly homogeneous trapping conditions over the full transport length, which is crucial in order to hold the atoms against gravity for such a wide range. Fast transport velocities of up to 6 m s-1 (corresponding to about 1100 photon recoils) and accelerations of up to 2600 m s-2 are reached. Even at high velocities the momentum of the atoms is precisely defined with an uncertainty of less than one photon recoil. This allows for construction of an atom catapult with high kinetic energy resolution, which might have applications in novel collision experiments.

  4. Transport of a Bose gas in 1D disordered lattices at the fluid-insulator transition.

    PubMed

    Tanzi, Luca; Lucioni, Eleonora; Chaudhuri, Saptarishi; Gori, Lorenzo; Kumar, Avinash; D'Errico, Chiara; Inguscio, Massimo; Modugno, Giovanni

    2013-09-13

    We investigate the momentum-dependent transport of 1D quasicondensates in quasiperiodic optical lattices. We observe a sharp crossover from a weakly dissipative regime to a strongly unstable one at a disorder-dependent critical momentum. In the limit of nondisordered lattices the observations suggest a contribution of quantum phase slips to the dissipation. We identify a set of critical disorder and interaction strengths for which such critical momentum vanishes, separating a fluid regime from an insulating one. We relate our observation to the predicted zero-temperature superfluid-Bose glass transition.

  5. The missing dimension: effects of lateral variation on 1-D calculations of fluvial bedload transport

    NASA Astrophysics Data System (ADS)

    Ferguson, R. I.

    2003-11-01

    Most calculations of bedload transport in rivers, including those in numerical models of aggradation and degradation, are 1-D: all hydraulic and transport-rate calculations are averaged over the channel width. Because bedload transport laws are nonlinear, width-averaged calculations will underestimate the true bedload flux if there is any local spatial variation in either the bed or the flow. This paper analyses the effects on bedload transport capacity of spatial variation in applied ( τ) and critical ( τc) shear stress, separately and in combination. A simple but versatile statistical model is used to represent variability in τ, with allowance for differences between sand- and gravel-bed rivers and for below-bankfull flow. Bedload flux is shown to increase greatly with the variance of τ, especially in gravel-bed rivers. Variability in τc through bed patchiness may increase, reduce, or make little difference to bedload flux depending on the correlation between τ and τc. Simple width averaging leads to severe underestimation of bedload transport in most conditions; some alternatives are considered. The findings have implications for sediment routing models (SRMs), but further research is needed to explore the issue fully.

  6. Evaluation of the Transport of Natural Radioactive Materials in Large Lysimeters Using Hydrus-1D

    NASA Astrophysics Data System (ADS)

    Pontedeiro, E.; Cipriani, M.; van Genuchten, M.; Simunek, J.

    2007-12-01

    The mining industry in Brazil often uses raw materials that contain relatively high concentrations of naturally occurring radioactive materials (referred to as NORM). Ores of relatively low grade typically are used to produce refined metals of high purity (e.g., Nb, Ta, Sn, and Au) using pyrometallurgic processes. The final waste is a slag rich in natural radioactive contaminants (the U and Th decay series), which are then usually deposited in industrial landfills. To study the long-term fate and transport of radionuclides leached from the NORM wastes, several large (3 m deep) lysimeters were constructed at the Pocos de Caldas Laboratory of the Brazilian Nuclear Energy Commision (CNEN). The lysimeters were packed with surface soils and slags from one of the mining sites in South East Brazil. Main purpose of our lysimeter experiments was to follow the dissolution and transport of radionuclides from the slags under natural climatic conditions. Leaching rates and radionuclide concentrations of the effluent were observed during a three-year time period. A variety of physical and chemical properties of the soils and slags (including laboratory batch equilibrium sorption values) were also determined. The data were analyzed using several computer software packages, including the STANMOD code for analytical modeling of decay chain transport during steady flow, the HYDRUS-1D code for variably-saturated flow and the transport of multiple solutes, and the HP1 code for a more comprehensive analysis of the geochemistry involved. In this presentation we describe the experimental setup and provide preliminary results of the theoretical analyses, especially those using HYDRUS-1D.

  7. Review of existing reactive transport software

    SciTech Connect

    Glassley, W., LLNL

    1998-02-03

    Simulations of thermal and hydrological evolution following the potential emplacement of a subterranean nuclear waste repository at Yucca Mountain, NV provide data that suggest the inevitability of dependent, simultaneous chemical evolution in this system. These chemical changes will modify significantly both the magnitude and structure of local porosity and permeability; hence, they will have a dynamic feedback effect on the evolving thermal and hydrological regime. Yet, despite this intimate interdependence of transport and chemical processes, a rigorous quantitative analysis of the post- emplacement environment that incorporates this critical feedback mechanism has not been completed to date. As an initial step in this direction, the present document outlines the fundamental chemical and transport processes that must be accounted for in such an analysis, and reviews the inventory of existing software that encodes these processed in explicitly coupled form. A companion report describes the prioritization of specific capabilities that are needed for modeling post-emplacement reactive transport at Yucca Mountain.

  8. On a 1D nonlocal transport equation with nonlocal velocity and subcritical or supercritical diffusion

    NASA Astrophysics Data System (ADS)

    Lazar, Omar

    2016-11-01

    We study a 1D transport equation with nonlocal velocity with subcritical or supercritical dissipation. For all data in the weighted Sobolev space Hk (wλ,κ) ∩L∞, where k = max ⁡ (0 , 3 / 2 - α) and wλ,κ is a given family of Muckenhoupt weights, we prove a global existence result in the subcritical case α ∈ (1 , 2). We also prove a local existence theorem for large data in H2 (wλ,κ) ∩L∞ in the supercritical case α ∈ (0 , 1). The proofs are based on the use of the weighted Littlewood-Paley theory, interpolation along with some new commutator estimates.

  9. Mesoscopic Modeling of Reactive Transport Processes

    NASA Astrophysics Data System (ADS)

    Kang, Q.; Chen, L.; Deng, H.

    2012-12-01

    Reactive transport processes involving precipitation and/or dissolution are pervasive in geochemical, biological and engineered systems. Typical examples include self-assembled patterns such as Liesegang rings or bands, cones of stalactites in limestones caves, biofilm growth in aqueous environment, formation of mineral deposits in boilers and heat exchangers, uptake of toxic metal ions from polluted water by calcium carbonate, and mineral trapping of CO2. Compared to experimental studies, a numerical approach enables a systematic study of the reaction kinetics, mass transport, and mechanisms of nucleation and crystal growth, and hence provides a detailed description of reactive transport processes. In this study, we enhance a previously developed lattice Boltzmann pore-scale model by taking into account the nucleation process, and develop a mesoscopic approach to simulate reactive transport processes involving precipitation and/or dissolution of solid phases. The model is then used to simulate the formation of Liesegang precipitation patterns and investigate the effects of gel on the morphology of the precipitates. It is shown that this model can capture the porous structures of the precipitates and can account for the effects of the gel concentration and material. A wide range of precipitation patterns is predicted under different gel concentrations, including regular bands, treelike patterns, and for the first time with numerical models, transition patterns from regular bands to treelike patterns. The model is also applied to study the effect of secondary precipitate on the dissolution of primary mineral. Several types of dissolution and precipitation processes are identified based on the morphology and structures of the precipitates and on the extent to which the precipitates affect the dissolution of the primary mineral. Finally the model is applied to study the formation of pseudomorph. It is demonstrated for the first time by numerical simulation that a

  10. Scale up tools in reactive extrusion and compounding processes. Could 1D-computer modeling be helpful?

    NASA Astrophysics Data System (ADS)

    Pradel, J.-L.; David, C.; Quinebèche, S.; Blondel, P.

    2014-05-01

    Industrial scale-up (or scale down) in Compounding and Reactive Extrusion processes is one of the most critical R&D challenges. Indeed, most of High Performances Polymers are obtained within a reactive compounding involving chemistry: free radical grafting, in situ compatibilization, rheology control... but also side reactions: oxidation, branching, chain scission... As described by basic Arrhenius and kinetics laws, the competition between all chemical reactions depends on residence time distribution and temperature. Then, to ensure the best possible scale up methodology, we need tools to match thermal history of the formulation along the screws from a lab scale twin screw extruder to an industrial one. This paper proposes a comparison between standard scale-up laws and the use of Computer modeling Software such as Ludovic® applied and compared to experimental data. Scaling data from a compounding line to another one, applying general rules (for example at constant specific mechanical energy), shows differences between experimental and computed data, and error depends on the screw speed range. For more accurate prediction, 1D-Computer Modeling could be used to optimize the process conditions to ensure the best scale-up product, especially in temperature sensitive reactive extrusion processes. When the product temperature along the screws is the key, Ludovic® software could help to compute the temperature profile along the screws and extrapolate conditions, even screw profile, on industrial extruders.

  11. Modeling multispecies reactive transport in ground water

    SciTech Connect

    Clement, T.P.; Sun, Y.; Hooker, B.S.; Petersen, J.N.

    1998-12-31

    In this paper, the details of RT3D, a general purpose, multispecies, reactive transport code, are presented. The code uses MODFLOW to simulate flow and several MT3D sub-programs to simulate advection and dispersion. A set of reaction modules were developed and incorporated into RT3D to simulate various types of multispecies reactive transport. This new computer model can be used for analyzing different types of subsurface contaminant reactions, microbial metabolisms, and microbial transport kinetics. Details of the model and numerical solution procedure are presented. The numerical formulation of the code is general enough to allow description of any type of reaction with any number of mobile/immobile species. Several example problems are presented to test the performance of the code, and to illustrate its features. The presented numerical model is shown to be a useful tool for analyzing different types of subsurface bioremediation systems. Prediction based on this model can be used for screening remediation alternatives including natural attenuation and/or for forecasting contaminant exposure levels and environmental risks at sensitive, downgradient receptors.

  12. Reactive solute transport in acidic streams

    USGS Publications Warehouse

    Broshears, R.E.

    1996-01-01

    Spatial and temporal profiles of Ph and concentrations of toxic metals in streams affected by acid mine drainage are the result of the interplay of physical and biogeochemical processes. This paper describes a reactive solute transport model that provides a physically and thermodynamically quantitative interpretation of these profiles. The model combines a transport module that includes advection-dispersion and transient storage with a geochemical speciation module based on MINTEQA2. Input to the model includes stream hydrologic properties derived from tracer-dilution experiments, headwater and lateral inflow concentrations analyzed in field samples, and a thermodynamic database. Simulations reproduced the general features of steady-state patterns of observed pH and concentrations of aluminum and sulfate in St. Kevin Gulch, an acid mine drainage stream near Leadville, Colorado. These patterns were altered temporarily by injection of sodium carbonate into the stream. A transient simulation reproduced the observed effects of the base injection.

  13. Stability and accuracy of 3D neutron transport simulations using the 2D/1D method in MPACT

    NASA Astrophysics Data System (ADS)

    Collins, Benjamin; Stimpson, Shane; Kelley, Blake W.; Young, Mitchell T. H.; Kochunas, Brendan; Graham, Aaron; Larsen, Edward W.; Downar, Thomas; Godfrey, Andrew

    2016-12-01

    A consistent "2D/1D" neutron transport method is derived from the 3D Boltzmann transport equation, to calculate fuel-pin-resolved neutron fluxes for realistic full-core Pressurized Water Reactor (PWR) problems. The 2D/1D method employs the Method of Characteristics to discretize the radial variables and a lower order transport solution to discretize the axial variable. This paper describes the theory of the 2D/1D method and its implementation in the MPACT code, which has become the whole-core deterministic neutron transport solver for the Consortium for Advanced Simulations of Light Water Reactors (CASL) core simulator VERA-CS. Several applications have been performed on both leadership-class and industry-class computing clusters. Results are presented for whole-core solutions of the Watts Bar Nuclear Power Station Unit 1 and compared to both continuous-energy Monte Carlo results and plant data.

  14. Numerical modeling of humic colloid borne americium (III) migration in column experiments using the transport/speciation code K1D and the KICAM model.

    PubMed

    Schüssler, W; Artinger, R; Kim, J I; Bryan, N D; Griffin, D

    2001-02-01

    The humic colloid borne Am(III) transport was investigated in column experiments for Gorleben groundwater/sand systems. It was found that the interaction of Am with humic colloids is kinetically controlled, which strongly influences the migration behavior of Am(III). These kinetic effects have to be taken into account for transport/speciation modeling. The kinetically controlled availability model (KICAM) was developed to describe actinide sorption and transport in laboratory batch and column experiments. Application of the KICAM requires a chemical transport/speciation code, which simultaneously models both kinetically controlled processes and equilibrium reactions. Therefore, the code K1D was developed as a flexible research code that allows the inclusion of kinetic data in addition to transport features and chemical equilibrium. This paper presents the verification of K1D and its application to model column experiments investigating unimpeded humic colloid borne Am migration. Parmeters for reactive transport simulations were determined for a Gorleben groundwater system of high humic colloid concentration (GoHy 2227). A single set of parameters was used to model a series of column experiments. Model results correspond well to experimental data for the unretarded humic borne Am breakthrough.

  15. Numerical modeling of humic colloid borne Americium (III) migration in column experiments using the transport/speciation code K1D and the KICAM model

    NASA Astrophysics Data System (ADS)

    Schüßler, W.; Artinger, R.; Kim, J. I.; Bryan, N. D.; Griffin, D.

    2001-02-01

    The humic colloid borne Am(III) transport was investigated in column experiments for Gorleben groundwater/sand systems. It was found that the interaction of Am with humic colloids is kinetically controlled, which strongly influences the migration behavior of Am(III). These kinetic effects have to be taken into account for transport/speciation modeling. The kinetically controlled availability model (KICAM) was developed to describe actinide sorption and transport in laboratory batch and column experiments. Application of the KICAM requires a chemical transport/speciation code, which simultaneously models both kinetically controlled processes and equilibrium reactions. Therefore, the code K1D was developed as a flexible research code that allows the inclusion of kinetic data in addition to transport features and chemical equilibrium. This paper presents the verification of K1D and its application to model column experiments investigating unimpeded humic colloid borne Am migration. Parameters for reactive transport simulations were determined for a Gorleben groundwater system of high humic colloid concentration (GoHy 2227). A single set of parameters was used to model a series of column experiments. Model results correspond well to experimental data for the unretarded humic borne Am breakthrough.

  16. A Uranium Bioremediation Reactive Transport Benchmark

    SciTech Connect

    Yabusaki, Steven B.; Sengor, Sevinc; Fang, Yilin

    2015-06-01

    A reactive transport benchmark problem set has been developed based on in situ uranium bio-immobilization experiments that have been performed at a former uranium mill tailings site in Rifle, Colorado, USA. Acetate-amended groundwater stimulates indigenous microorganisms to catalyze the reduction of U(VI) to a sparingly soluble U(IV) mineral. The interplay between the flow, acetate loading periods and rates, microbially-mediated and geochemical reactions leads to dynamic behavior in metal- and sulfate-reducing bacteria, pH, alkalinity, and reactive mineral surfaces. The benchmark is based on an 8.5 m long one-dimensional model domain with constant saturated flow and uniform porosity. The 159-day simulation introduces acetate and bromide through the upgradient boundary in 14-day and 85-day pulses separated by a 10 day interruption. Acetate loading is tripled during the second pulse, which is followed by a 50 day recovery period. Terminal electron accepting processes for goethite, phyllosilicate Fe(III), U(VI), and sulfate are modeled using Monod-type rate laws. Major ion geochemistry modeled includes mineral reactions, as well as aqueous and surface complexation reactions for UO2++, Fe++, and H+. In addition to the dynamics imparted by the transport of the acetate pulses, U(VI) behavior involves the interplay between bioreduction, which is dependent on acetate availability, and speciation-controlled surface complexation, which is dependent on pH, alkalinity and available surface complexation sites. The general difficulty of this benchmark is the large number of reactions (74), multiple rate law formulations, a multisite uranium surface complexation model, and the strong interdependency and sensitivity of the reaction processes. Results are presented for three simulators: HYDROGEOCHEM, PHT3D, and PHREEQC.

  17. Box model and 1D longitudinal model of flow and transport in Bosten Lake, China

    NASA Astrophysics Data System (ADS)

    Li, Ning; Kinzelbach, Wolfgang; Li, WenPeng; Dong, XinGuang

    2015-05-01

    Bosten Lake in the southeast of Yanqi Catchment, China, supports the downstream agricultural and natural environments. Over the last few decades the intensive agricultural activities in Yanqi Catchment resulted in decreased lake levels and deteriorated lake water quality. A two-box model is constructed to understand the evolution of lake level and salinity between 1958 and 2008. The two-box model of the lake indicates that the evaporation does have the same trend as the observed lake area and the annual average evaporation agrees with the value obtained from the Penman-Monteith approach. To achieve a correct salt balance, the ratio of outflow concentration and average lake concentration has to be around 0.7. This is due to the incomplete mixing of the lake caused by short-circuiting between tributary inflow and the main outflow via the pump stations abstracting water from the lake. This short-circuiting is investigated in more detail by a 1D numerical flow and transport model of the lake calibrated with observations of lake level and lake concentrations. The distributed model reproduces the correct time-varying outflow concentration. It is used for the assessment of two basic management options: increasing river discharge (by water saving irrigation, reduction of phreatic evaporation or reduction of agricultural area) and diverting saline drainage water to the desert. Increasing river discharge to the lake by 20% reduces the east basin salt concentration by 0.55 kg/m3, while capturing all the drainage water and discharging it to depressions instead of the lake reduces the east basin salt concentration by 0.63 kg/m3. A combination of increasing river inflow and decreasing drainage salt flux is sufficient to bring future lake TDS below the required 1 kg/m3, to keep a lake level that sustains the lake ecosystem, and to supply more water for downstream development and ecosystem rehabilitation.

  18. Reactive transport benchmarks for subsurface environmental simulation

    SciTech Connect

    Steefel, Carl I.; Yabusaki, Steven B.; Mayer, K. U.

    2015-06-01

    Over the last 20 years, we have seen firsthand the evolution of multicomponent reactive transport modeling and the expanding range and increasing complexity of subsurface applications it is being used to address. There is a growing reliance on reactive transport modeling (RTM) to address some of the most compelling issues facing our planet: climate change, nuclear waste management, contaminant remediation, and pollution prevention. While these issues are motivating the development of new and improved capabilities for subsurface environmental modeling using RTM (e.g., biogeochemistry from cell-scale physiology to continental-scale terrestrial ecosystems, nonisothermal multiphase conditions, coupled geomechanics), there remain longstanding challenges in characterizing the natural variability of hydrological, biological, and geochemical properties in subsurface environments and limited success in transferring models between sites and across scales. An equally important trend over the last 20 years is the evolution of modeling from a service sought out after data has been collected to a multifaceted research approach that provides (1) an organizing principle for characterization and monitoring activities; (2) a systematic framework for identifying knowledge gaps, developing and integrating new knowledge; and (3) a mechanistic understanding that represents the collective wisdom of the participating scientists and engineers. There are now large multidisciplinary projects where the research approach is model-driven, and the principal product is a holistic predictive simulation capability that can be used as a test bed for alternative conceptualizations of processes, properties, and conditions. Much of the future growth and expanded role for RTM will depend on its continued ability to exploit technological advancements in the earth and environmental sciences. Advances in measurement technology, particularly in molecular biology (genomics), isotope fractionation, and high

  19. Stability and accuracy of 3D neutron transport simulations using the 2D/1D method in MPACT

    DOE PAGES

    Collins, Benjamin; Stimpson, Shane; Kelley, Blake W.; ...

    2016-08-25

    We derived a consistent “2D/1D” neutron transport method from the 3D Boltzmann transport equation, to calculate fuel-pin-resolved neutron fluxes for realistic full-core Pressurized Water Reactor (PWR) problems. The 2D/1D method employs the Method of Characteristics to discretize the radial variables and a lower order transport solution to discretize the axial variable. Our paper describes the theory of the 2D/1D method and its implementation in the MPACT code, which has become the whole-core deterministic neutron transport solver for the Consortium for Advanced Simulations of Light Water Reactors (CASL) core simulator VERA-CS. We also performed several applications on both leadership-class and industry-classmore » computing clusters. Results are presented for whole-core solutions of the Watts Bar Nuclear Power Station Unit 1 and compared to both continuous-energy Monte Carlo results and plant data.« less

  20. Stability and accuracy of 3D neutron transport simulations using the 2D/1D method in MPACT

    SciTech Connect

    Collins, Benjamin; Stimpson, Shane; Kelley, Blake W.; Young, Mitchell T. H.; Kochunas, Brendan; Graham, Aaron; Larsen, Edward W.; Downar, Thomas; Godfrey, Andrew

    2016-08-25

    We derived a consistent “2D/1D” neutron transport method from the 3D Boltzmann transport equation, to calculate fuel-pin-resolved neutron fluxes for realistic full-core Pressurized Water Reactor (PWR) problems. The 2D/1D method employs the Method of Characteristics to discretize the radial variables and a lower order transport solution to discretize the axial variable. Our paper describes the theory of the 2D/1D method and its implementation in the MPACT code, which has become the whole-core deterministic neutron transport solver for the Consortium for Advanced Simulations of Light Water Reactors (CASL) core simulator VERA-CS. We also performed several applications on both leadership-class and industry-class computing clusters. Results are presented for whole-core solutions of the Watts Bar Nuclear Power Station Unit 1 and compared to both continuous-energy Monte Carlo results and plant data.

  1. GIS-based channel flow and sediment transport simulation using CCHE1D coupled with AnnAGNPS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    CCHE1D (Center for Computational Hydroscience and Engineering 1-Dimensional model) simulates unsteady free-surface flows with nonequilibrium, nonuniform sediment transport in dendritic channel networks. Since early 1990’s, the model and its software packages have been developed and continuously main...

  2. Quantum and semi-classical transport in RTDs using NEMO 1-D

    NASA Technical Reports Server (NTRS)

    Klimeck, G.; Stout, P.; Bowen, R. C.

    2003-01-01

    NEMO 1-D has been developed primarily for the simulation of resonant tunneling diodes, and quantitative and predictive agreements with experimental high performance, high current density devices have been achieved in the past.

  3. Benchmarking a Visual-Basic based multi-component one-dimensional reactive transport modeling tool

    NASA Astrophysics Data System (ADS)

    Torlapati, Jagadish; Prabhakar Clement, T.

    2013-01-01

    We present the details of a comprehensive numerical modeling tool, RT1D, which can be used for simulating biochemical and geochemical reactive transport problems. The code can be run within the standard Microsoft EXCEL Visual Basic platform, and it does not require any additional software tools. The code can be easily adapted by others for simulating different types of laboratory-scale reactive transport experiments. We illustrate the capabilities of the tool by solving five benchmark problems with varying levels of reaction complexity. These literature-derived benchmarks are used to highlight the versatility of the code for solving a variety of practical reactive transport problems. The benchmarks are described in detail to provide a comprehensive database, which can be used by model developers to test other numerical codes. The VBA code presented in the study is a practical tool that can be used by laboratory researchers for analyzing both batch and column datasets within an EXCEL platform.

  4. Geothermal Fluid Interaction with Mafic Rocks in Porous Media - AN Experimental and Reactive Transport Modeling Study

    NASA Astrophysics Data System (ADS)

    Stefansson, A.

    2013-12-01

    Reaction and reactive transport modeling is becoming an increasingly popular method to study fluid-rock interaction and fluid transport on small to large scales. In this study, fluid-rock experiments were carried out and the observations compared with the results of reaction and reactive transport models. The systems studied included fluid-rock interaction of olivine on one hand and basaltic glass on the other hand with dilute aqueous solutions containing CO2 at acid to neutral pH and temperatures from ambient to 250 °C. The experiments were conducted using batch type experiments in closed reactors and 1-D plug experiments in flow-through reactors and the solution chemistry, the reaction progress, secondary mineralization and porosity changes analyzed as a function of time. The reaction and 1-D reactive transport simulations were conducted with the aid of the PHREEQC program. For the simulations the thermodynamic database for mineral reactions was largely updated and the kinetics of mineral dissolution as well as mineral nucleation and crystal growth was incorporated. According to the experimental results and the reactive transport simulations, olivine and basaltic glass progressively dissolves forming secondary minerals and solutes that are partially transported out of them column (system). The exact reaction path was found to depend on solution composition and pH and reaction progress (time). The mass movement of the system at a particular steady state as well as porosity changes may be divided into three stages. Stage I is characterized by initial olivine or basaltic glass leaching, stage II is characterized by progressive mineral formation and decrease in porosity and stage III is characterized by remobilization of the previously formed secondary minerals and eventual increase in porosity. The reaction and reactive transport modeling was found to simulate reasonable the reaction path as a function of reaction time. However, exact mass movement and time

  5. Microbially Mediated Kinetic Sulfur Isotope Fractionation: Reactive Transport Modeling Benchmark

    NASA Astrophysics Data System (ADS)

    Wanner, C.; Druhan, J. L.; Cheng, Y.; Amos, R. T.; Steefel, C. I.; Ajo Franklin, J. B.

    2014-12-01

    Microbially mediated sulfate reduction is a ubiquitous process in many subsurface systems. Isotopic fractionation is characteristic of this anaerobic process, since sulfate reducing bacteria (SRB) favor the reduction of the lighter sulfate isotopologue (S32O42-) over the heavier isotopologue (S34O42-). Detection of isotopic shifts have been utilized as a proxy for the onset of sulfate reduction in subsurface systems such as oil reservoirs and aquifers undergoing uranium bioremediation. Reactive transport modeling (RTM) of kinetic sulfur isotope fractionation has been applied to field and laboratory studies. These RTM approaches employ different mathematical formulations in the representation of kinetic sulfur isotope fractionation. In order to test the various formulations, we propose a benchmark problem set for the simulation of kinetic sulfur isotope fractionation during microbially mediated sulfate reduction. The benchmark problem set is comprised of four problem levels and is based on a recent laboratory column experimental study of sulfur isotope fractionation. Pertinent processes impacting sulfur isotopic composition such as microbial sulfate reduction and dispersion are included in the problem set. To date, participating RTM codes are: CRUNCHTOPE, TOUGHREACT, MIN3P and THE GEOCHEMIST'S WORKBENCH. Preliminary results from various codes show reasonable agreement for the problem levels simulating sulfur isotope fractionation in 1D.

  6. EFDC1D - A ONE DIMENSIONAL HYDRODYNAMIC AND SEDIMENT TRANSPORT MODEL FOR RIVER AND STREAM NETWORKS: MODEL THEORY AND USERS GUIDE

    EPA Science Inventory

    This technical report describes the new one-dimensional (1D) hydrodynamic and sediment transport model EFDC1D. This model that can be applied to stream networks. The model code and two sample data sets are included on the distribution CD. EFDC1D can simulate bi-directional unstea...

  7. Reactive transport modeling for Cs retention: from batch to field experiments

    NASA Astrophysics Data System (ADS)

    De Pourcq, K.; Ayora, C.; Carrera, J.; García-Gutiérrez, M.; Missana, T.; Mingarro, M.

    2012-04-01

    A Permeable Reactive Barrier has been designed to treat 137Cs polluted groundwater. In order to check both reactivity and permeability, laboratory batch and column tests combined with reactive transport modeling have been performed. The trapping mechanism is based on the sorption of cesium mainly on illite-containing clays. Batch experiments were conducted to obtain the partition coefficients (Kd) of different clay samples in solutions with different potassium concentration. A clear correlation of Kd values with potassium content was observed. The results were modeled with a cation-exchange model. The permeability of the reactive material is provided by the dispersion of the clay on a matrix of wooden shavings. Constant head tests allowed obtaining permeability values. Several column experiments with different flow rates were conducted to confirm the 137Cs retention under different conditions. A blind 1D reactive transport model based on the cation-exchange model was able to predict reasonably well the results of column experiments. The reactive transport model, validated with the column experiments, was used to investigate the performance and duration of 1m thick barrier under different scenarios (flow, clay proportion, 137Cs and K concentration). As expected, the sensitivity tests proved that the retention capacity of dissolved 137Cs in groundwater depends linearly on the amount of clay used in the filling material. As well, the operation time increases linearly when decreasing the flow rate. Finally, the concentration of potassium in inflow water has a remarkable and non-linear influence in the retention of 137Cs. Very high concentrations of potassium are the greatest threat and can lead to the unfeasibility of a permeable reactive barrier. Due to the Cs-K competition, the barrier is comparatively more efficient to treat high concentrations of 137Cs. Up to now, preliminary results from a field scale experiment have confirmed the reactivity and permeability

  8. 1D Unsteady Flow and Sediment Transport Model for Channel Network

    NASA Astrophysics Data System (ADS)

    bai, Y.; Duan, J. G.

    2012-12-01

    This paper presents a one-dimensional unsteady flow and sediment transport model for simulating flood routing and sediment transport over mobile alluvium in channel network. The modified St. Venant equation together with the suspended sediment and bed load transport equations are solved simultaneously to obtain flow properties and sediment transport rates. The Godunov-type finite volume method is employed, and the flux terms are discretized by using the upwind and the HLLC schemes. Then, the Exner equation is used to solve for bed elevation changes. In unsteady flow, sediment transport is non-equilibrium, therefore suspended load adaptation coefficient and bed load adaptation length are used to account for the difference between equilibrium and non-equilibrium sediment transport rate. At river confluences, water surface elevations are kept the same, and the law of mass conservation is used as the internal boundary conditions. An unprecedented flood event occurred in the Santa Cruz River, Tucson, Arizona, in July 2006, is used to test the performances of the model. Simulated results of water surface elevation and bed elevation changes show good agreements with the measurements.

  9. Detection and characterization of uranium-humic complexes during 1D transport studies

    SciTech Connect

    Lesher, Emily K.; Honeyman, Bruce D.; Ranville, James F.

    2013-05-01

    The speciation and transport of uranium (VI) through porous media is highly dependent on solution conditions, the presence of complexing ligands, and the nature of the porous media. The dependency on many variables makes prediction of U transport in bench-scale experiments and in the field difficult. In particular, the identification of colloidal U phases poses a technical challenge. Transport of U in the presence and absence of natural organic matter (Suwannee River humic acid, SRHA) through silica sand and hematite coated silica sand was tested at pH 4 and 5 using static columns, where flow is controlled by gravity and residence time between advective pore volume exchanges can be strictly controlled. The column effluents were characterized by traditional techniques including ICPMS quantification of total [U] and [Fe], TOC analysis of [DOC], and pH analysis, and also by non-traditional techniques: flow field flow fractionation with online ICPMS detection (FlFFF-ICPMS) and specific UV absorbance (SUVA) characterization of effluent fractions. Key results include that the transport of U through the columns was enhanced by pre-equilibration with SRHA, and previously deposited U was remobilized by the addition of SRHA. The advanced techniques yielded important insights on the mechanisms of transport: FlFFF-ICPMS identified a U-SRHA complex as the mobile U species and directly quantified relative amounts of the complex, while specific UV absorbance (SUVA) measurements indicated a composition-based fractionation onto the porous media.

  10. Quantum transport through disordered 1D wires: Conductance via localized and delocalized electrons

    SciTech Connect

    Gopar, Víctor A.

    2014-01-14

    Coherent electronic transport through disordered systems, like quantum wires, is a topic of fundamental and practical interest. In particular, the exponential localization of electron wave functions-Anderson localization-due to the presence of disorder has been widely studied. In fact, Anderson localization, is not an phenomenon exclusive to electrons but it has been observed in microwave and acoustic experiments, photonic materials, cold atoms, etc. Nowadays, many properties of electronic transport of quantum wires have been successfully described within a scaling approach to Anderson localization. On the other hand, anomalous localization or delocalization is, in relation to the Anderson problem, a less studied phenomenon. Although one can find signatures of anomalous localization in very different systems in nature. In the problem of electronic transport, a source of delocalization may come from symmetries present in the system and particular disorder configurations, like the so-called Lévy-type disorder. We have developed a theoretical model to describe the statistical properties of transport when electron wave functions are delocalized. In particular, we show that only two physical parameters determine the complete conductance distribution.

  11. Transport of an interacting Bose gas in 1D disordered lattices

    SciTech Connect

    D'Errico, C.; Chaudhuri, S.; Gori, L.; Kumar, A.; Lucioni, E.; Tanzi, L.; Inguscio, M.; Modugno, G.

    2014-08-20

    We use ultracold atoms in a quasiperiodic lattice to study two outstanding problems in the physics of disordered systems: a) the anomalous diffusion of a wavepacket in the presence of disorder, interactions and noise; b) the transport of a disordered superfluid. a) Our results show that the subdiffusion, observed when interaction alone is present, can be modelled with a nonlinear diffusion equation and the peculiar shape of the expanding density profiles can be connected to the microscopic nonlinear diffusion coefficients. Also when noise alone is present we can describe the observed normal diffusion dynamics by existing microscopic models. In the unexplored regime in which noise and interaction are combined, instead, we observe an anomalous diffusion, that we model with a generalized diffusion equation, where noise- and interaction-induced contributions add each other. b) We find that an instability appearing at relatively large momenta can be employed to locate the fluid-insulator crossover driven by disorder. By investigating the momentum-dependent transport, we observe a sharp crossover from a weakly dissipative regime to a strongly unstable one at a disorder-dependent critical momentum. The set of critical disorder and interaction strengths for which such critical momentum vanishes, can be identified with the separation between a fluid regime and an insulating one and can be related to the predicted zero-temperature superfluid-Bose glass transition.

  12. Development of a 3D to 1D Particle Transport Model to Predict Deposition in the Lungs

    NASA Astrophysics Data System (ADS)

    Oakes, Jessica M.; Grandmont, Celine; Shadden, Shawn C.; Vignon-Clementel, Irene E.

    2014-11-01

    Aerosolized particles are commonly used for therapeutic drug delivery as they can be delivered to the body systemically or be used to treat lung diseases. Recent advances in computational resources have allowed for sophisticated pulmonary simulations, however it is currently impossible to solve for airflow and particle transport for all length and time scales of the lung. Instead, multi-scale methods must be used. In our recent work, where computational methods were employed to solve for airflow and particle transport in the rat airways (Oakes et al. (2014), Annals of Biomedical Engineering 42, 899), the number of particles to exit downstream of the 3D domain was determined. In this current work, the time-dependent Lagrangian description of particles was used to numerically solve a 1D convection-diffusion model (trumpet model, Taulbee and Yu (1975), Journal of Applied Physiology, 38, 77) parameterized specifically for the lung. The expansion of the airway dimensions was determined based on data collected from our aerosol exposure experiments (Oakes et al. (2014), Journal of Applied Physiology, 116, 1561). This 3D-1D framework enables us to predict the fate of particles in the whole lung. This work was supported by the Whitaker Foundation at the IIE, a INRIA Associated Team Postdoc Grant, and a UC Presidential Fellowship.

  13. Upscaling of reaction rates in reactive transport using pore-scale reactive transport model

    NASA Astrophysics Data System (ADS)

    Yoon, H.; Dewers, T. A.; Arnold, B. W.; Major, J. R.; Eichhubl, P.; Srinivasan, S.

    2013-12-01

    Dissolved CO2 during geological CO2 storage may react with minerals in fractured rocks, confined aquifers, or faults, resulting in mineral precipitation and dissolution. The overall rate of reaction can be affected by coupled processes among hydrodynamics, transport, and reactions at the (sub) pore-scale. In this research pore-scale modeling of coupled fluid flow, reactive transport, and heterogeneous reaction at the mineral surface is applied to account for permeability alterations caused by precipitation-induced pore-blocking. This work is motivated by the observed CO2 seeps from a natural analog to geologic CO2 sequestration at Crystal Geyser, Utah. A key observation is the lateral migration of CO2 seep sites at a scale of ~ 100 meters over time. A pore-scale model provides fundamental mechanistic explanations of how calcite precipitation alters flow paths by pore plugging under different geochemical compositions and pore configurations. In addition, response function of reaction rates will be constructed from pore-scale simulations which account for a range of reaction regimes characterized by the Damkohler and Peclet numbers. Newly developed response functions will be used in a continuum scale model that may account for large-scale phenomena mimicking lateral migration of surface CO2 seeps. Comparison of field observations and simulations results will provide mechanistic explanations of the lateral migration and enhance our understanding of subsurface processes associated with the CO2 injection. This work is supported as part of the Center for Frontiers of Subsurface Energy Security, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001114. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security

  14. Modeling variably saturated multispecies reactive groundwater solute transport with MODFLOW-UZF and RT3D

    USGS Publications Warehouse

    Bailey, Ryan T.; Morway, Eric D.; Niswonger, Richard G.; Gates, Timothy K.

    2013-01-01

    A numerical model was developed that is capable of simulating multispecies reactive solute transport in variably saturated porous media. This model consists of a modified version of the reactive transport model RT3D (Reactive Transport in 3 Dimensions) that is linked to the Unsaturated-Zone Flow (UZF1) package and MODFLOW. Referred to as UZF-RT3D, the model is tested against published analytical benchmarks as well as other published contaminant transport models, including HYDRUS-1D, VS2DT, and SUTRA, and the coupled flow and transport modeling system of CATHY and TRAN3D. Comparisons in one-dimensional, two-dimensional, and three-dimensional variably saturated systems are explored. While several test cases are included to verify the correct implementation of variably saturated transport in UZF-RT3D, other cases are included to demonstrate the usefulness of the code in terms of model run-time and handling the reaction kinetics of multiple interacting species in variably saturated subsurface systems. As UZF1 relies on a kinematic-wave approximation for unsaturated flow that neglects the diffusive terms in Richards equation, UZF-RT3D can be used for large-scale aquifer systems for which the UZF1 formulation is reasonable, that is, capillary-pressure gradients can be neglected and soil parameters can be treated as homogeneous. Decreased model run-time and the ability to include site-specific chemical species and chemical reactions make UZF-RT3D an attractive model for efficient simulation of multispecies reactive transport in variably saturated large-scale subsurface systems.

  15. Modeling variably saturated multispecies reactive groundwater solute transport with MODFLOW-UZF and RT3D.

    PubMed

    Bailey, Ryan T; Morway, Eric D; Niswonger, Richard G; Gates, Timothy K

    2013-01-01

    A numerical model was developed that is capable of simulating multispecies reactive solute transport in variably saturated porous media. This model consists of a modified version of the reactive transport model RT3D (Reactive Transport in 3 Dimensions) that is linked to the Unsaturated-Zone Flow (UZF1) package and MODFLOW. Referred to as UZF-RT3D, the model is tested against published analytical benchmarks as well as other published contaminant transport models, including HYDRUS-1D, VS2DT, and SUTRA, and the coupled flow and transport modeling system of CATHY and TRAN3D. Comparisons in one-dimensional, two-dimensional, and three-dimensional variably saturated systems are explored. While several test cases are included to verify the correct implementation of variably saturated transport in UZF-RT3D, other cases are included to demonstrate the usefulness of the code in terms of model run-time and handling the reaction kinetics of multiple interacting species in variably saturated subsurface systems. As UZF1 relies on a kinematic-wave approximation for unsaturated flow that neglects the diffusive terms in Richards equation, UZF-RT3D can be used for large-scale aquifer systems for which the UZF1 formulation is reasonable, that is, capillary-pressure gradients can be neglected and soil parameters can be treated as homogeneous. Decreased model run-time and the ability to include site-specific chemical species and chemical reactions make UZF-RT3D an attractive model for efficient simulation of multispecies reactive transport in variably saturated large-scale subsurface systems.

  16. Transport equations for partially ionized reactive plasma in magnetic field

    NASA Astrophysics Data System (ADS)

    Zhdanov, V. M.; Stepanenko, A. A.

    2016-06-01

    Transport equations for partially ionized reactive plasma in magnetic field taking into account the internal degrees of freedom and electronic excitation of plasma particles are derived. As a starting point of analysis the kinetic equation with a binary collision operator written in the Wang-Chang and Uhlenbeck form and with a reactive collision integral allowing for arbitrary chemical reactions is used. The linearized variant of Grad's moment method is applied to deduce the systems of moment equations for plasma and also full and reduced transport equations for plasma species nonequilibrium parameters.

  17. Cumulative relative reactivity: A concept for modeling aquifer-scale reactive transport

    NASA Astrophysics Data System (ADS)

    Loschko, Matthias; Wöhling, Thomas; Rudolph, David L.; Cirpka, Olaf A.

    2016-10-01

    We simulate aquifer-scale reactive transport using an approach based on travel times and relative reactivity. The latter quantifies the intensity of the chemical reaction relative to a reference reaction rate with identical concentrations and can be interpreted as the strength of electron-donor (or electron-acceptor) release by the matrix, scaled by a reference release. In general, the relative reactivity is a spatially variable property reflecting the geology of the formation. In the proposed approach, we track the path of individual water parcels through the aquifer and evaluate the age of the water parcels and the relative reactivity integrated along their trajectories. By switching from spatial discretization to cumulative relative reactivity, advective-reactive transport can be simulated by solving a single system of ordinary differential equations for each combination of concentrations in the inflow. We test the validity of the approach in a two-dimensional test case of steady state groundwater flow and reactive transport involving aerobic respiration and denitrification. Here we compare steady state concentration distributions of the spatially explicit virtual truth, accounting for dispersive mixing, with the approximation based on cumulative relative reactivity and show that the errors introduced by neglecting dispersive mixing are minor if the target quantities are the mass fluxes crossing a control plane or being collected by a well. We further demonstrate the efficiency of the approach in a synthetic three-dimensional case study. The proposed approach is computationally so efficient that ensemble runs to assess statistical distributions of concentration time series of reactive solutes become feasible, which is not practical with a spatially explicit model.

  18. Parameters estimation for reactive transport: A way to test the validity of a reactive model

    NASA Astrophysics Data System (ADS)

    Aggarwal, Mohit; Cheikh Anta Ndiaye, Mame; Carrayrou, Jérôme

    The chemical parameters used in reactive transport models are not known accurately due to the complexity and the heterogeneous conditions of a real domain. We will present an efficient algorithm in order to estimate the chemical parameters using Monte-Carlo method. Monte-Carlo methods are very robust for the optimisation of the highly non-linear mathematical model describing reactive transport. Reactive transport of tributyltin (TBT) through natural quartz sand at seven different pHs is taken as the test case. Our algorithm will be used to estimate the chemical parameters of the sorption of TBT onto the natural quartz sand. By testing and comparing three models of surface complexation, we show that the proposed adsorption model cannot explain the experimental data.

  19. Reactive dispersive contaminant transport in coastal aquifers: numerical simulation of a reactive Henry problem.

    PubMed

    Nick, H M; Raoof, A; Centler, F; Thullner, M; Regnier, P

    2013-02-01

    The reactive mixing between seawater and terrestrial water in coastal aquifers influences the water quality of submarine groundwater discharge. While these waters come into contact at the seawater groundwater interface by density driven flow, their chemical components dilute and react through dispersion. A larger interface and wider mixing zone may provide favorable conditions for the natural attenuation of contaminant plumes. It has been claimed that the extent of this mixing is controlled by both, porous media properties and flow conditions. In this study, the interplay between dispersion and reactive processes in coastal aquifers is investigated by means of numerical experiments. Particularly, the impact of dispersion coefficients, the velocity field induced by density driven flow and chemical component reactivities on reactive transport in such aquifers is studied. To do this, a hybrid finite-element finite-volume method and a reactive simulator are coupled, and model accuracy and applicability are assessed. A simple redox reaction is considered to describe the degradation of a contaminant which requires mixing of the contaminated groundwater and the seawater containing the terminal electron acceptor. The resulting degradation is observed for different scenarios considering different magnitudes of dispersion and chemical reactivity. Three reactive transport regimes are found: reaction controlled, reaction-dispersion controlled and dispersion controlled. Computational results suggest that the chemical components' reactivity as well as dispersion coefficients play a significant role on controlling reactive mixing zones and extent of contaminant removal in coastal aquifers. Further, our results confirm that the dilution index is a better alternative to the second central spatial moment of a plume to describe the mixing of reactive solutes in coastal aquifers.

  20. Interpretation of MSL REMS data using 1D coupled heat and water vapor transport model of Mars subsurface

    NASA Astrophysics Data System (ADS)

    Gloesener, Elodie; Karatekin, Özgür; Dehant, Véronique

    2016-04-01

    MSL Rover Environmental Monitoring Station (REMS) performed high-resolution measurements of temperature and relative humidity during more than one Martian year. In this work, a 1D subsurface model is used to study water vapor exchange between the atmosphere and the subsurface at Gale crater using REMS data. The thermal model used includes several layers of varying thickness with depth and properties that can be changed to correspond to those of Martian rocks at locations studied. It also includes the transport of water vapor through porous Martian regolith and the different phases considered are vapor, ice and adsorbed H2O. The total mass flux is given by the sum of diffusive and advective transport. The role of an adsorbing regolith on water transfer as well as the range of parameters with significant effect on water transport in Martian conditions are investigated. In addition, kinetics of the adsorption process is considered to examine its influence on the water vapor exchange between the subsurface and the atmosphere.

  1. Assessment of phenol infiltration resilience in soil media by HYDRUS-1D transport model for a waste discharge site.

    PubMed

    Adhikari, K; Pal, S; Chakraborty, B; Mukherjee, S N; Gangopadhyay, A

    2014-10-01

    The movement of contaminants through soil imparts a variety of geo-environmental problem inclusive of lithospheric pollution. Near-surface aquifers are often vulnerable to contamination from surface source if overlying soil possesses poor resilience or contaminant attenuation capacity. The prediction of contaminant transport through soil is urged to protect groundwater from sources of pollutants. Using field simulation through column experiments and mathematical modeling like HYDRUS-1D, assessment of soil resilience and movement of contaminants through the subsurface to reach aquifers can be predicted. An outfall site of effluents of a coke oven plant comprising of alarming concentration of phenol (4-12.2 mg/L) have been considered for studying groundwater condition and quality, in situ soil characterization, and effluent characterization. Hydrogeological feature suggests the presence of near-surface aquifers at the effluent discharge site. Analysis of groundwater of nearby locality reveals the phenol concentration (0.11-0.75 mg/L) exceeded the prescribed limit of WHO specification (0.002 mg/L). The in situ soil, used in column experiment, possess higher saturated hydraulic conductivity (KS  = 5.25 × 10(-4) cm/s). The soil containing 47 % silt, 11 % clay, and 1.54% organic carbon content was found to be a poor absorber of phenol (24 mg/kg). The linear phenol adsorption isotherm model showed the best fit (R(2) = 0.977, RMSE = 1.057) to the test results. Column experiments revealed that the phenol removal percent and the length of the mass transfer zone increased with increasing bed heights. The overall phenol adsorption efficiency was found to be 42-49%. Breakthrough curves (BTCs) predicted by HYDRUS-1D model appears to be close fitting with the BTCs derived from the column experiments. The phenol BTC predicted by the HYDRUS-1D model for 1.2 m depth subsurface soil, i.e., up to the depth of groundwater in the study area, showed that the exhaustion

  2. Surrogate model approach for improving the performance of reactive transport simulations

    NASA Astrophysics Data System (ADS)

    Jatnieks, Janis; De Lucia, Marco; Sips, Mike; Dransch, Doris

    2016-04-01

    Reactive transport models can serve a large number of important geoscientific applications involving underground resources in industry and scientific research. It is common for simulation of reactive transport to consist of at least two coupled simulation models. First is a hydrodynamics simulator that is responsible for simulating the flow of groundwaters and transport of solutes. Hydrodynamics simulators are well established technology and can be very efficient. When hydrodynamics simulations are performed without coupled geochemistry, their spatial geometries can span millions of elements even when running on desktop workstations. Second is a geochemical simulation model that is coupled to the hydrodynamics simulator. Geochemical simulation models are much more computationally costly. This is a problem that makes reactive transport simulations spanning millions of spatial elements very difficult to achieve. To address this problem we propose to replace the coupled geochemical simulation model with a surrogate model. A surrogate is a statistical model created to include only the necessary subset of simulator complexity for a particular scenario. To demonstrate the viability of such an approach we tested it on a popular reactive transport benchmark problem that involves 1D Calcite transport. This is a published benchmark problem (Kolditz, 2012) for simulation models and for this reason we use it to test the surrogate model approach. To do this we tried a number of statistical models available through the caret and DiceEval packages for R, to be used as surrogate models. These were trained on randomly sampled subset of the input-output data from the geochemical simulation model used in the original reactive transport simulation. For validation we use the surrogate model to predict the simulator output using the part of sampled input data that was not used for training the statistical model. For this scenario we find that the multivariate adaptive regression splines

  3. Assessment of parametric uncertainty for groundwater reactive transport modeling,

    USGS Publications Warehouse

    Shi, Xiaoqing; Ye, Ming; Curtis, Gary P.; Miller, Geoffery L.; Meyer, Philip D.; Kohler, Matthias; Yabusaki, Steve; Wu, Jichun

    2014-01-01

    The validity of using Gaussian assumptions for model residuals in uncertainty quantification of a groundwater reactive transport model was evaluated in this study. Least squares regression methods explicitly assume Gaussian residuals, and the assumption leads to Gaussian likelihood functions, model parameters, and model predictions. While the Bayesian methods do not explicitly require the Gaussian assumption, Gaussian residuals are widely used. This paper shows that the residuals of the reactive transport model are non-Gaussian, heteroscedastic, and correlated in time; characterizing them requires using a generalized likelihood function such as the formal generalized likelihood function developed by Schoups and Vrugt (2010). For the surface complexation model considered in this study for simulating uranium reactive transport in groundwater, parametric uncertainty is quantified using the least squares regression methods and Bayesian methods with both Gaussian and formal generalized likelihood functions. While the least squares methods and Bayesian methods with Gaussian likelihood function produce similar Gaussian parameter distributions, the parameter distributions of Bayesian uncertainty quantification using the formal generalized likelihood function are non-Gaussian. In addition, predictive performance of formal generalized likelihood function is superior to that of least squares regression and Bayesian methods with Gaussian likelihood function. The Bayesian uncertainty quantification is conducted using the differential evolution adaptive metropolis (DREAM(zs)) algorithm; as a Markov chain Monte Carlo (MCMC) method, it is a robust tool for quantifying uncertainty in groundwater reactive transport models. For the surface complexation model, the regression-based local sensitivity analysis and Morris- and DREAM(ZS)-based global sensitivity analysis yield almost identical ranking of parameter importance. The uncertainty analysis may help select appropriate likelihood

  4. Analytical Solution for Reactive Solute Transport Considering Incomplete Mixing

    NASA Astrophysics Data System (ADS)

    Bellin, A.; Chiogna, G.

    2013-12-01

    The laboratory experiments of Gramling et al. (2002) showed that incomplete mixing at the pore scale exerts a significant impact on transport of reactive solutes and that assuming complete mixing leads to overestimation of product concentration in bimolecular reactions. We consider here the family of equilibrium reactions for which the concentration of the reactants and the product can be expressed as a function of the mixing ratio, the concentration of a fictitious non reactive solute. For this type of reactions we propose, in agreement with previous studies, to model the effect of incomplete mixing at scales smaller than the Darcy scale assuming that the mixing ratio is distributed within an REV according to a Beta distribution. We compute the parameters of the Beta model by imposing that the mean concentration is equal to the value that the concentration assumes at the continuum Darcy scale, while the variance decays with time as a power law. We show that our model reproduces the concentration profiles of the reaction product measured in the Gramling et al. (2002) experiments using the transport parameters obtained from conservative experiments and an instantaneous reaction kinetic. The results are obtained applying analytical solutions both for conservative and for reactive solute transport, thereby providing a method to handle the effect of incomplete mixing on multispecies reactive solute transport, which is simpler than other previously developed methods. Gramling, C. M., C. F. Harvey, and L. C. Meigs (2002), Reactive transport in porous media: A comparison of model prediction with laboratory visualization, Environ. Sci. Technol., 36(11), 2508-2514.

  5. Geophysical Characterization and Reactive Transport Modeling to Quantify Plume Behavior

    NASA Astrophysics Data System (ADS)

    Hubbard, S. S.; Wainwright, H.; Bea, S. A.; Spycher, N.; Li, L.; Sassen, D.; Chen, J.

    2012-12-01

    Predictions of subsurface contaminant plume mobility and remediation often fail due to the inability to tractably characterize heterogeneous flow-and-transport properties and monitor critical geochemical transitions over plume-relevant scales. This study presents two recently developed strategies to quantify and predict states and processes across scales that govern plume behavior. Development of both strategies takes advantage of multi-scale and disparate datasets and has involved the use of reactive transport models, geophysical methods, and stochastic integration approaches. The first approach, called reactive facies, exploits coupled physiochemical heterogeneity to characterize subsurface flow and transport properties that impact plume sorption and thus mobility. We develop and test the reactive facies concept within uranium contaminated Atlantic Coastal Plain sediments that underlie the U.S. Department of Energy Savannah River Site, F-Area, South Carolina. Through analysis of field data (core samples, geophysical well logs, and cross-hole ground penetrating radar and seismic datasets) coupled with laboratory sorption studies, we have identified two reactive facies that have unique distributions of mineralogy, texture, porosity, hydraulic conductivity and geophysical attributes. We develop and use facies-based relationships with geophysical data in a Bayesian framework to spatially distribute reactive facies and their associated transport properties and uncertainties along local and plume-scale geophysical transects. To illustrate the value of reactive facies, we used the geophysically-obtained reactive facies properties to parameterize reactive transport models and simulate the migration of an acidic-U(VI) plume through the 2D domains. Modeling results suggest that each identified reactive facies exerts control on plume evolution, highlighting the usefulness of the reactive facies concept and approach for spatially distributing properties that control flow and

  6. Imaging reactive minerals in the subsurface using inverse reactive transport modeling: an example relevant for arsenic mobilization

    NASA Astrophysics Data System (ADS)

    Fakhreddine, S.; Lee, J. H.; Kitanidis, P. K.; Fendorf, S. E.; Rolle, M.

    2014-12-01

    The spatial distribution of naturally occurring, arsenic-bearing minerals in the subsurface is a key factor for determining the fate and transport of arsenic in groundwater systems. However, the direct measurement and estimation of these heterogeneously distributed minerals are often costly and difficult to obtain. While previous studies have shown the utility of using indirect measurements combined with inverse modeling techniques for tomography of physical properties including hydraulic conductivity, these methods have seldom been used to image geochemical properties. In this study, we use synthetic applications to demonstrate the ability of inverse modeling techniques to image reactive mineral lenses in the subsurface and quantify estimation error using indirect, commonly measured groundwater parameters. Specifically, we simulate the mobilization of arsenic via kinetic oxidative dissolution of arsenopyrite due to dissolved oxygen in the ambient groundwater. The modeling investigation is carried out at various scales and considers different flow-through domains including (i) a 1D lab-scale column (80 cm), (ii) a 2D lab-scale setup (30 cm x 60 cm) and (iii) a 2D field-scale domain (4 m x 20 m). Next, the simulated dissolved oxygen data and forward reactive transport model are used to image the spatial distribution of arsenopyrite using the Principal Component Geostatistical Approach (PCGA) for inverse modeling. The PCGA is a matrix-free geostatistical inversion approach that uses the leading principal components of the prior information to save computational costs and can be easily linked with any simulation software. Our results show that the PCGA can be used to image randomly distributed arsenopyrite lenses at various scales and has the potential to be employed at the field-scale to map complex distributions of reactive minerals in the subsurface based on the measurement of dissolved constituents in groundwater.

  7. Lessons Learned From Reactive Transport Modeling of a Low-Activity Waste Glass Disposal System

    SciTech Connect

    Bacon, Diana H.; McGrail, B PETER.

    2003-04-01

    A set of reactive chemical transport calculations was conducted with the Subsurface Transport Over Reactive Multi-phases (STORM) code to evaluate the long-term performance of a representative low-activity waste glass in a shallow subsurface disposal system located on the Hanford Site. Two different trench designs were considered, one with four rows of small waste packages, the other with three layers of larger waste packages. One-dimensional simulations were carried out to 20,000 years, whereas two-dimensional simulations could only be carried out for several hundred years due to constraints on computational time. Both the 1-D and 2-D simulations predict that the Technetium release rate from the waste packages will be lower for the new trench design at later times. Because the glass corrosion rate is significantly higher at the backfill/glass interfaces, having less interfacial area in the new trench design offsets the effect of the slightly higher pH relative to the old trench design. In the two-dimensional simulations, water can flow around the waste packages, which causes a decrease in the water flux through the waste packages and lower release rates than predicted in the 1-D simulations. This result reinforces the importance of performing multi-dimensional waste form release simulations.

  8. Kinetic theory of transport processes in partially ionized reactive plasma, I: General transport equations

    NASA Astrophysics Data System (ADS)

    Zhdanov, V. M.; Stepanenko, A. A.

    2016-03-01

    In this paper we derive the set of general transport equations for multicomponent partially ionized reactive plasma in the presence of electric and magnetic fields taking into account the internal degrees of freedom and electronic excitation of plasma particles. Our starting point is a generalized Boltzmann equation with the collision integral in the Wang-Chang and Uhlenbeck form and a reactive collision integral. We obtain a set of conservation equations for such plasma and employ a linearized variant of Grad's moment method to derive the system of moment (or transport) equations for the plasma species nonequilibrium parameters. Full and reduced transport equations, resulting from the linearized system of moment equations, are presented, which can be used to obtain transport relations and expressions for transport coefficients of electrons and heavy plasma particles (molecules, atoms and ions) in partially ionized reactive plasma.

  9. Analytical model of reactive transport processes with spatially variable coefficients.

    PubMed

    Simpson, Matthew J; Morrow, Liam C

    2015-05-01

    Analytical solutions of partial differential equation (PDE) models describing reactive transport phenomena in saturated porous media are often used as screening tools to provide insight into contaminant fate and transport processes. While many practical modelling scenarios involve spatially variable coefficients, such as spatially variable flow velocity, v(x), or spatially variable decay rate, k(x), most analytical models deal with constant coefficients. Here we present a framework for constructing exact solutions of PDE models of reactive transport. Our approach is relevant for advection-dominant problems, and is based on a regular perturbation technique. We present a description of the solution technique for a range of one-dimensional scenarios involving constant and variable coefficients, and we show that the solutions compare well with numerical approximations. Our general approach applies to a range of initial conditions and various forms of v(x) and k(x). Instead of simply documenting specific solutions for particular cases, we present a symbolic worksheet, as supplementary material, which enables the solution to be evaluated for different choices of the initial condition, v(x) and k(x). We also discuss how the technique generalizes to apply to models of coupled multispecies reactive transport as well as higher dimensional problems.

  10. Measurements and models of reactive transport in geological media

    NASA Astrophysics Data System (ADS)

    Berkowitz, Brian; Dror, Ishai; Hansen, Scott K.; Scher, Harvey

    2016-12-01

    Reactive chemical transport plays a key role in geological media across scales, from pore scale to aquifer scale. Systems can be altered by changes in solution chemistry and a wide variety of chemical transformations, including precipitation/dissolution reactions that cause feedbacks that directly affect the flow and transport regime. The combination of these processes with advective-dispersive-diffusive transport in heterogeneous media leads to a rich spectrum of complex dynamics. The principal challenge in modeling reactive transport is to account for the subtle effects of fluctuations in the flow field and species concentrations; spatial or temporal averaging generally suppresses these effects. Moreover, it is critical to ground model conceptualizations and test model outputs against laboratory experiments and field measurements. This review emphasizes the integration of these aspects, considering carefully designed and controlled experiments at both laboratory and field scales, in the context of development and solution of reactive transport models based on continuum-scale and particle tracking approaches. We first discuss laboratory experiments and field measurements that define the scope of the phenomena and provide data for model comparison. We continue by surveying models involving advection-dispersion-reaction equation and continuous time random walk formulations. The integration of measurements and models is then examined, considering a series of case studies in different frameworks. We delineate the underlying assumptions, and strengths and weaknesses, of these analyses, and the role of probabilistic effects. We also show the key importance of quantifying the spreading and mixing of reactive species, recognizing the role of small-scale physical and chemical fluctuations that control the initiation of reactions.

  11. From conservative to reactive transport under diffusion-controlled conditions

    NASA Astrophysics Data System (ADS)

    Babey, Tristan; de Dreuzy, Jean-Raynald; Ginn, Timothy R.

    2016-05-01

    We assess the possibility to use conservative transport information, such as that contained in transit time distributions, breakthrough curves and tracer tests, to predict nonlinear fluid-rock interactions in fracture/matrix or mobile/immobile conditions. Reference simulated data are given by conservative and reactive transport simulations in several diffusive porosity structures differing by their topological organization. Reactions includes nonlinear kinetically controlled dissolution and desorption. Effective Multi-Rate Mass Transfer models (MRMT) are calibrated solely on conservative transport information without pore topology information and provide concentration distributions on which effective reaction rates are estimated. Reference simulated reaction rates and effective reaction rates evaluated by MRMT are compared, as well as characteristic desorption and dissolution times. Although not exactly equal, these indicators remain very close whatever the porous structure, differing at most by 0.6% and 10% for desorption and dissolution. At early times, this close agreement arises from the fine characterization of the diffusive porosity close to the mobile zone that controls fast mobile-diffusive exchanges. At intermediate to late times, concentration gradients are strongly reduced by diffusion, and reactivity can be captured by a very limited number of rates. We conclude that effective models calibrated solely on conservative transport information like MRMT can accurately estimate monocomponent kinetically controlled nonlinear fluid-rock interactions. Their relevance might extend to more advanced biogeochemical reactions because of the good characterization of conservative concentration distributions, even by parsimonious models (e.g., MRMT with 3-5 rates). We propose a methodology to estimate reactive transport from conservative transport in mobile-immobile conditions.

  12. Multiscale Models for Reactive Transport in Porous Media

    NASA Astrophysics Data System (ADS)

    Tartakovsky, A. M.

    2012-12-01

    Under certain conditions, Darcy-scale reactive transport equations cannot provide sufficiently accurate predictions of multiphase flow and reactive transport. Pore-scale models are based on fundamental conservation laws and, in general, are more accurate than the Darcy-scale models. But, for domains of practical importance, number of unknowns in the pore-sale models may be on the order of billions or trillions and a direct solution of the pore-scale equations is often unfeasible even on modern super-computes. Several novel multiscale methods including a Langevin approach and a dimension reduction method based on a computational closure will be presented. The purpose of these methods is to provide an accurate description of the system averages while retaining critical pore-scale information. The advantages, range of applicability and limitations of the mentioned above multiscale methods will be discussed.

  13. Cord blood cytokine profile detection in neonates with T1D parents -- monitoring of cellular auto-reactivity using protein microarray.

    PubMed

    Bohmova, K; Hladikova, Z; Cerny, M; Flajsmanova, K; Vrabelova, Z; Skramlikova, T; Spalova, I; Cerna, M; Chudoba, D; Pithova, P; Stadlerova, G; Bartaskova, D; Faresjo, M; Stechova, K

    2007-11-01

    Type 1 diabetes (T1D) is a great medical challenge and its incidence rises rapidly. T lymphocytes and their cytokine production are supposed to play a major role in T1D development. So far, there is no potent tool to recognize the early signs of cellular auto-reactivity which leads to beta-cell damage. The naïve immune system of the newborn (not yet influenced by external factors) can be used as an important model for T1D pathogenesis studies. Cord blood samples of 22 healthy neonates born at term to a diabetic parent (T1DR) and 15 newborns with no family history of any autoimmune disease (controls) were collected. Determination of 23 cytokines was performed before and after the stimulation with diabetogenic autoantigens using protein microarray. We observed lower basal production of all detected cytokines in the T1DR group - granulocyte/macrophage colony-stimulating factor (GM-CSF) (P = 0.025), growth regulated protein (GRO) (P = 0.002), GRO-alpha (P = 0.027), interleukin (IL)-1-alpha (P = 0.051), IL-3 (P = 0.008), IL-7 (P = 0.027), IL-8 (P = 0.042), monocyte chemoattractant proteins (MCP)-3 (P = 0.022), monokine-induced by IFN-gamma (MIG) (P = 0.034) and regulated upon activation normal T-cell express sequence (RANTES) (P = 0.004). Exclusively lower post-stimulative levels of G-CSF (P = 0.030) and GRO-alpha (P = 0.04) were observed in controls in comparison with the basal levels. A significant post-stimulative decrease in G-CSF (P = 0.030) and MCP-2 (P = 0.009) levels was observed in controls in comparison with T1DR neonates. We also observed the interesting impact of the risky genotype on the protein microarray results. Protein microarray seems to be a useful tool to characterize a risk pattern of the immune response for T1D also in newborns.

  14. Fluid-rock interaction: A reactive transport approach

    SciTech Connect

    Steefel, C.; Maher, K.

    2009-04-01

    Fluid-rock interaction (or water-rock interaction, as it was more commonly known) is a subject that has evolved considerably in its scope over the years. Initially its focus was primarily on interactions between subsurface fluids of various temperatures and mostly crystalline rocks, but the scope has broadened now to include fluid interaction with all forms of subsurface materials, whether they are unconsolidated or crystalline ('fluid-solid interaction' is perhaps less euphonious). Disciplines that previously carried their own distinct names, for example, basin diagenesis, early diagenesis, metamorphic petrology, reactive contaminant transport, chemical weathering, are now considered to fall under the broader rubric of fluid-rock interaction, although certainly some of the key research questions differ depending on the environment considered. Beyond the broadening of the environments considered in the study of fluid-rock interaction, the discipline has evolved in perhaps an even more important way. The study of water-rock interaction began by focusing on geochemical interactions in the absence of transport processes, although a few notable exceptions exist (Thompson 1959; Weare et al. 1976). Moreover, these analyses began by adopting a primarily thermodynamic approach, with the implicit or explicit assumption of equilibrium between the fluid and rock. As a result, these early models were fundamentally static rather than dynamic in nature. This all changed with the seminal papers by Helgeson and his co-workers (Helgeson 1968; Helgeson et al. 1969) wherein the concept of an irreversible reaction path was formally introduced into the geochemical literature. In addition to treating the reaction network as a dynamically evolving system, the Helgeson studies introduced an approach that allowed for the consideration of a multicomponent geochemical system, with multiple minerals and species appearing as both reactants and products, at least one of which could be

  15. Electrochemical reactivity and proton transport mechanisms in nanostructured ceria

    NASA Astrophysics Data System (ADS)

    Ding, J.; Strelcov, E.; Kalinin, S. V.; Bassiri-Gharb, N.

    2016-08-01

    Electrochemical reactivity and ionic transport at the nanoscale are essential in many energy applications. In this study, time-resolved Kelvin probe force microscopy (tr-KPFM) is utilized for surface potential mapping of nanostructured ceria, in both space and time domains. The fundamental mechanisms of proton injection and transport are studied as a function of environmental conditions and the presence or absence of triple phase boundaries. Finite element modeling is used to extract physical parameters from the experimental data, allowing not only quantification of the observed processes, but also decoupling of their contributions to the measured signal. The constructed phase diagrams of the parameters demonstrate a thermally activated proton injection reaction at the triple phase boundary, and two transport processes that are responsible for the low-temperature proton conductivity of nanostructured ceria.

  16. Database uncertainty as a limiting factor in reactive transport prognosis

    NASA Astrophysics Data System (ADS)

    Nitzsche, O.; Meinrath, G.; Merkel, B.

    2000-08-01

    The effect of uncertainties in thermodynamic databases on prediction performances of reactive transport modeling of uranium (VI) is investigated with a Monte Carlo approach using the transport code TReaC. TReaC couples the transport model to the speciation code PHREEQC by a particle tracking method. A speciation example is given to illustrate the effect of uncertainty in thermodynamic data on the predicted solution composition. The transport calculations consequently show the prediction uncertainty resulting from uncertainty in thermodynamic data. A conceptually simple scenario of elution of uranium from a sand column is used as an illustrating example. Two different cases are investigated: a carbonate-enriched drinking water and an acid mine water associated with uranium mine remediation problems. Due to the uncertainty in the relative amount of positively charged and neutral solution species, the uncertainty in the thermodynamic data also infers uncertainty in the retardation behavior. The carbonated water system shows the largest uncertainties in speciation calculation. Therefore, the model predictions of total uranium solubility have a broad range. The effect of data uncertainty in transport prediction is further illustrated by a prediction of the time when eluted uranium from the column exceeds a threshold value. All of these Monte Carlo transport calculations consume large amounts of computing time.

  17. Association between amygdala reactivity and a dopamine transporter gene polymorphism

    PubMed Central

    Bergman, O; Åhs, F; Furmark, T; Appel, L; Linnman, C; Faria, V; Bani, M; Pich, E M; Bettica, P; Henningsson, S; Manuck, S B; Ferrell, R E; Nikolova, Y S; Hariri, A R; Fredrikson, M; Westberg, L; Eriksson, E

    2014-01-01

    Essential for detection of relevant external stimuli and for fear processing, the amygdala is under modulatory influence of dopamine (DA). The DA transporter (DAT) is of fundamental importance for the regulation of DA transmission by mediating reuptake inactivation of extracellular DA. This study examined if a common functional variable number tandem repeat polymorphism in the 3′ untranslated region of the DAT gene (SLC6A3) influences amygdala function during the processing of aversive emotional stimuli. Amygdala reactivity was examined by comparing regional cerebral blood flow, measured with positron emission tomography and [15O]water, during exposure to angry and neutral faces, respectively, in a Swedish sample comprising 32 patients with social anxiety disorder and 17 healthy volunteers. In a separate US sample, comprising 85 healthy volunteers studied with blood oxygen level-dependent functional magnetic resonance imaging, amygdala reactivity was assessed by comparing the activity during exposure to threatening faces and neutral geometric shapes, respectively. In both the Swedish and the US sample, 9-repeat carriers displayed higher amygdala reactivity than 10-repeat homozygotes. The results suggest that this polymorphism contributes to individual variability in amygdala reactivity. PMID:25093598

  18. Dopamine D1, D2, D3 Receptors, Vesicular Monoamine Transporter Type-2 (VMAT2) and Dopamine Transporter (DAT) Densities in Aged Human Brain

    PubMed Central

    Sun, Jianjun; Xu, Jinbin; Cairns, Nigel J.; Perlmutter, Joel S.; Mach, Robert H.

    2012-01-01

    The dopamine D1, D2, D3 receptors, vesicular monoamine transporter type-2 (VMAT2), and dopamine transporter (DAT) densities were measured in 11 aged human brains (aged 77–107.8, mean: 91 years) by quantitative autoradiography. The density of D1 receptors, VMAT2, and DAT was measured using [3H]SCH23390, [3H]dihydrotetrabenazine, and [3H]WIN35428, respectively. The density of D2 and D3 receptors was calculated using the D3-preferring radioligand, [3H]WC-10 and the D2-preferring radioligand [3H]raclopride using a mathematical model developed previously by our group. Dopamine D1, D2, and D3 receptors are extensively distributed throughout striatum; the highest density of D3 receptors occurred in the nucleus accumbens (NAc). The density of the DAT is 10–20-fold lower than that of VMAT2 in striatal regions. Dopamine D3 receptor density exceeded D2 receptor densities in extrastriatal regions, and thalamus contained a high level of D3 receptors with negligible D2 receptors. The density of dopamine D1 linearly correlated with D3 receptor density in the thalamus. The density of the DAT was negligible in the extrastriatal regions whereas the VMAT2 was expressed in moderate density. D3 receptor and VMAT2 densities were in similar level between the aged human and aged rhesus brain samples, whereas aged human brain samples had lower range of densities of D1 and D2 receptors and DAT compared with the aged rhesus monkey brain. The differential density of D3 and D2 receptors in human brain will be useful in the interpretation of PET imaging studies in human subjects with existing radiotracers, and assist in the validation of newer PET radiotracers having a higher selectivity for dopamine D2 or D3 receptors. PMID:23185343

  19. Parameterized isoprene and monoterpene emissions from the boreal forest floor: Implementation into a 1D chemistry-transport model and investigation of the influence on atmospheric chemistry

    NASA Astrophysics Data System (ADS)

    Mogensen, Ditte; Aaltonen, Hermanni; Aalto, Juho; Bäck, Jaana; Kieloaho, Antti-Jussi; Gierens, Rosa; Smolander, Sampo; Kulmala, Markku; Boy, Michael

    2015-04-01

    Volatile organic compounds (VOCs) are emitted from the biosphere and can work as precursor gases for aerosol particles that can affect the climate (e.g. Makkonen et al., ACP, 2012). VOC emissions from needles and leaves have gained the most attention, however other parts of the ecosystem also have the ability to emit a vast amount of VOCs. This, often neglected, source can be important e.g. at periods where leaves are absent. Both sources and drivers related to forest floor emission of VOCs are currently limited. It is thought that the sources are mainly due to degradation of organic matter (Isidorov and Jdanova, Chemosphere, 2002), living roots (Asensio et al., Soil Biol. Biochem., 2008) and ground vegetation. The drivers are biotic (e.g. microbes) and abiotic (e.g. temperature and moisture). However, the relative importance of the sources and the drivers individually are currently poorly understood. Further, the relative importance of these factors is highly dependent on the tree species occupying the area of interest. The emission of isoprene and monoterpenes where measured from the boreal forest floor at the SMEAR II station in Southern Finland (Hari and Kulmala, Boreal Env. Res., 2005) during the snow-free period in 2010-2012. We used a dynamic method with 3 automated chambers analyzed by Proton Transfer Reaction - Mass Spectrometer (Aaltonen et al., Plant Soil, 2013). Using this data, we have developed empirical parameterizations for the emission of isoprene and monoterpenes from the forest floor. These parameterizations depends on abiotic factors, however, since the parameterizations are based on field measurements, biotic features are captured. Further, we have used the 1D chemistry-transport model SOSAA (Boy et al., ACP, 2011) to test the seasonal relative importance of inclusion of these parameterizations of the forest floor compared to the canopy crown emissions, on the atmospheric reactivity throughout the canopy.

  20. Assessing conceptual models for subsurface reactive transport of inorganic contaminants

    USGS Publications Warehouse

    Davis, James A.; Yabusaki, Steven B.; Steefel, Carl; Zachara, John M.; Curtis, Gary P.; Redden, George D.; Criscenti, Louise J.; Honeyman, Bruce D.

    2004-01-01

    In many subsurface situations where human health and environmental quality are at risk (e.g., contaminant hydrogeology petroleum extraction, carbon sequestration, etc.),scientists and engineers are being asked by federal agency decision-makers to predict the fate of chemical species under conditions where both reactions and transport are processes of first-order importance.In 2002, a working group (WG) was formed by representatives of the U.S. Geological Survey, Environmental Protection Agency, Department of Energy Nuclear Regulatory Commission, Department of Agriculture, and Army Engineer Research and Development Center to assess the role of reactive transport modeling (RTM) in addressing these situations. Specifically the goals of the WG are to (1) evaluate the state of the art in conceptual model development and parameterization for RTM, as applied to soil,vadose zone, and groundwater systems, and (2) prioritize research directions that would enhance the practical utility of RTM.

  1. Benchmarking reactive transport models at a hillslope scale

    NASA Astrophysics Data System (ADS)

    Kalbacher, T.; He, W.; Nixdorf, E.; Jang, E.; Fleckenstein, J. H.; Kolditz, O.

    2015-12-01

    The hillslope scale is an important transition between the field scale and the catchment scale. The water flow in the unsaturated zone of a hillslope can be highly dynamic, which can lead to dynamic changes of groundwater flow or stream outflow. Additionally, interactions among host rock formation, soil properties and recharge water from precipitation or anthropogenic activities (mining, agriculture etc.) can influence the water quality of groundwater and stream in the long term. To simulate reactive transport processes at such a scale is a challenging task. On the one hand, simulation of water flow in a coupled soil-aquifer system often involves solving of highly non-linear PDEs such as Richards equation; on the other hand, one has to consider complicated biogeochemical reactions (e.g. water-rock interactions, biological degradation, redox reactions). Both aspects are computationally expensive and have high requirements on the numerical precision and stabilities of the employed code. The primary goals of this study are as follows: i) Identify the bottlenecks and quantitatively analyse their influence on simulation of biogeochemical reactions at a hillslope scale; ii) find or suggest practical strategies to deal with these bottlenecks, thus to provide detailed hints for future improvements of reactive transport simulators. To achieve these goals, the parallelized reactive transport simulator OGS#IPhreeqc has been applied to simulate two benchmark examples. The first example is about uranium leaching based on Šimůnek et al. (2012), which considers the leaching of uranium from a mill tailing and accompanied mineral dissolution/precipitation. The geochemical system is then extended to include redox reactions in the second example. Based on these examples, the numerical stability and parallel performance of the tool is analysed. ReferenceŠimůnek, J., Jacques, D., Šejna, M., van Genuchten, M. T.: The HP2 program for HYDRUS (2D/3D), A coupled code for simulating two

  2. Uranium transport in a crushed granodiorite: Experiments and reactive transport modeling

    DOE PAGES

    Dittrich, T. M.; Reimus, P. W.

    2015-02-12

    The primary objective of this study was to develop and demonstrate an experimental method to refine and better parameterize process models for reactive contaminant transport in aqueous subsurface environments and to reduce conservatism in such models without attempting to fully describe the geochemical system.

  3. Langevin model for reactive transport in porous media

    NASA Astrophysics Data System (ADS)

    Tartakovsky, Alexandre M.

    2010-08-01

    Existing continuum models for reactive transport in porous media tend to overestimate the extent of solute mixing and mixing-controlled reactions because the continuum models treat both the mechanical and diffusive mixings as an effective Fickian process. Recently, we have proposed a phenomenological Langevin model for flow and transport in porous media [A. M. Tartakovsky, D. M. Tartakovsky, and P. Meakin, Phys. Rev. Lett. 101, 044502 (2008)10.1103/PhysRevLett.101.044502]. In the Langevin model, the fluid flow in a porous continuum is governed by a combination of a Langevin equation and a continuity equation. Pore-scale velocity fluctuations, the source of mechanical dispersion, are represented by the white noise. The advective velocity (the solution of the Langevin flow equation) causes the mechanical dispersion of a solute. Molecular diffusion and sub-pore-scale Taylor-type dispersion are modeled by an effective stochastic advection-diffusion equation. Here, we propose a method for parameterization of the model for a synthetic porous medium, and we use the model to simulate multicomponent reactive transport in the porous medium. The detailed comparison of the results of the Langevin model with pore-scale and continuum (Darcy) simulations shows that: (1) for a wide range of Peclet numbers the Langevin model predicts the mass of reaction product more accurately than the Darcy model; (2) for small Peclet numbers predictions of both the Langevin and the Darcy models agree well with a prediction of the pore-scale model; and (3) the accuracy of the Langevin and Darcy model deteriorates with the increasing Peclet number but the accuracy of the Langevin model decreases more slowly than the accuracy of the Darcy model. These results show that the separate treatment of advective and diffusive mixing in the stochastic transport model is more accurate than the classical advection-dispersion theory, which uses a single effective diffusion coefficient (the dispersion

  4. Transport and Reactivity of Decontaminants to Provide Hazard Mitigation of Chemical Warfare Agents from Materials

    DTIC Science & Technology

    2016-06-01

    A combined approach was developed that integrated two types of testing—dilute liquid-phase reactor results to determine 18 chemical reactivity...TRANSPORT AND REACTIVITY OF DECONTAMINANTS TO PROVIDE HAZARD MITIGATION OF CHEMICAL ...2013 4. TITLE AND SUBTITLE Transport and Reactivity of Decontaminants to Provide Hazard Mitigation of Chemical Warfare Agents from Materials 5a

  5. End-Member Formulation of Solid Solutions and Reactive Transport

    SciTech Connect

    Lichtner, Peter C.

    2015-09-01

    A model for incorporating solid solutions into reactive transport equations is presented based on an end-member representation. Reactive transport equations are solved directly for the composition and bulk concentration of the solid solution. Reactions of a solid solution with an aqueous solution are formulated in terms of an overall stoichiometric reaction corresponding to a time-varying composition and exchange reactions, equivalent to reaction end-members. Reaction rates are treated kinetically using a transition state rate law for the overall reaction and a pseudo-kinetic rate law for exchange reactions. The composition of the solid solution at the onset of precipitation is assumed to correspond to the least soluble composition, equivalent to the composition at equilibrium. The stoichiometric saturation determines if the solid solution is super-saturated with respect to the aqueous solution. The method is implemented for a simple prototype batch reactor using Mathematica for a binary solid solution. Finally, the sensitivity of the results on the kinetic rate constant for a binary solid solution is investigated for reaction of an initially stoichiometric solid phase with an undersaturated aqueous solution.

  6. Adaptive Mesh Refinement in Reactive Transport Modeling of Subsurface Environments

    NASA Astrophysics Data System (ADS)

    Molins, S.; Day, M.; Trebotich, D.; Graves, D. T.

    2015-12-01

    Adaptive mesh refinement (AMR) is a numerical technique for locally adjusting the resolution of computational grids. AMR makes it possible to superimpose levels of finer grids on the global computational grid in an adaptive manner allowing for more accurate calculations locally. AMR codes rely on the fundamental concept that the solution can be computed in different regions of the domain with different spatial resolutions. AMR codes have been applied to a wide range of problem including (but not limited to): fully compressible hydrodynamics, astrophysical flows, cosmological applications, combustion, blood flow, heat transfer in nuclear reactors, and land ice and atmospheric models for climate. In subsurface applications, in particular, reactive transport modeling, AMR may be particularly useful in accurately capturing concentration gradients (hence, reaction rates) that develop in localized areas of the simulation domain. Accurate evaluation of reaction rates is critical in many subsurface applications. In this contribution, we will discuss recent applications that bring to bear AMR capabilities on reactive transport problems from the pore scale to the flood plain scale.

  7. 1D and 3D anthropometric data application on public transport vehicle layout and on oil and gas laboratories work environment design.

    PubMed

    Pastura, F C H; Guimarães, C P; Zamberlan, M C P; Cid, G L; Santos, V S; Streit, P; Paranhos, A G; Cobbe, R T; Cobbe, K T; Batista, D S

    2012-01-01

    The goal of this paper is to present 1D and 3D anthropometric data applied to two distinct design situations: one related to the interior layout of a public transport vehicle and another one related to oil and gas laboratories work environment design. On this study, the 1D anthropometric data were extracted from the Brazilian anthropometric database developed by INT and the 3D anthropometric data were obtained using a Cyberware 3D whole body scanner. A second purpose of this paper is to present the 3D human scanning data as a tool that can help designers on decision making.

  8. Conservative and reactive solute transport in constructed wetlands

    USGS Publications Warehouse

    Keefe, S.H.; Barber, L.B.; Runkel, R.L.; Ryan, J.N.; McKnight, Diane M.; Wass, R.D.

    2004-01-01

    The transport of bromide, a conservative tracer, and rhodamine WT (RWT), a photodegrading tracer, was evaluated in three wastewater-dependent wetlands near Phoenix, Arizona, using a solute transport model with transient storage. Coupled sodium bromide and RWT tracer tests were performed to establish conservative transport and reactive parameters in constructed wetlands with water losses ranging from (1) relatively impermeable (15%), (2) moderately leaky (45%), and (3) significantly leaky (76%). RWT first-order photolysis rates and sorption coefficients were determined from independent field and laboratory experiments. Individual wetland hydraulic profiles influenced the extent of transient storage interaction in stagnant water areas and consequently RWT removal. Solute mixing and transient storage interaction occurred in the impermeable wetland, resulting in 21% RWT mass loss from main channel and storage zone photolysis (10%) and sorption (11%) reactions. Advection and dispersion governed solute transport in the leaky wetland, limiting RWT photolysis removal (1.2%) and favoring main channel sorption (3.6%). The moderately leaky wetland contained islands parallel to flow, producing channel flow and minimizing RWT losses (1.6%).

  9. Modelling reactive transport in a phosphogypsum dump, Venezia, Italia

    NASA Astrophysics Data System (ADS)

    Calcara, Massimo; Borgia, Andrea; Cattaneo, Laura; Bartolo, Sergio; Clemente, Gianni; Glauco Amoroso, Carlo; Lo Re, Fabio; Tozzato, Elena

    2013-04-01

    We develop a reactive-transport porous media flow model for a phosphogypsum dump located on the intertidal deposits of the Venetian Lagoon: 1. we construct a complex conceptual and geologic model from field data using the GMS™ graphical user interface; 2. the geological model is mapped onto a rectangular MODFLOW grid; 3. using the TMT2 FORTRAN90 code we translate this grid into the MESH, INCON and GENER input files for the TOUGH2 series of codes; 4. we run TOUGH-REACT to model flow and reactive transport in the dump and the sediments below it. The model includes 3 different dump materials (phosphogypsum, bituminous and hazardous wastes) with the pores saturated by specific fluids. The sediments below the dump are formed by an intertidal sequence of calcareous sands and silts, in addition to clays and organic deposits, all of which are initially saturated with lagoon salty waters. The recharge rain-water dilutes the dump fluids. In turn, the percolates from the dump react with the underlying sediments and the sea water that saturates them. Simulation results have been compared with chemical sampled analyses. In fact, in spite of the simplicity of our model we are able to show how the pH becomes neutral at a short distance below the dump, a fact observed during aquifer monitoring. The spatial and temporal evolution of dissolution and precipitation reactions occur in our model much alike reality. Mobility of some elements, such as divalent iron, are reduced by specific and concurrent conditions of pH from near-neutrality to moderately high values and positive redox potential; opposite conditions favour mobility of potentially toxic metals such as Cr, As Cd and Pb. Vertical movement are predominant. Trend should be therefore heavily influenced by pH and Eh values. If conditions are favourable to mobility, concentration of these substances in the bottom strata could be high. However, simulation suggest that the sediments tend to reduce the transport potential of

  10. Treatment of reactive interfaces in pore-scale reactive transport with the phase-field method

    NASA Astrophysics Data System (ADS)

    Huber, C.; Di Palma, P. R.

    2014-12-01

    The two major challenges for continuum reactive transport models are the treatment of interfaces between different phases (multi-fluids like DNAPL-water, or solid-fluid) and the ability to model transient chemical gradients at the pore-scale. Pore-scale models allow us to deal naturally with chemical gradients at the discrete scale and they generally consider interfaces as boundary conditions that satisfy a local, but modified, mass balance equation. In other word grains do not take part in the mass balance of chemical species besides providing a boundary condition for the fluid. For instance, heterogeneous reactions at solid-fluid boundaries are framed as a balance between incoming chemical flux and reactions. Due to complex topology of interfaces in natural porous media, the treatment of heterogeneous reactions depends on the orientation of the interface and therefore requires a special care. It can become complicated and tedious especially when interfaces are allowed to evolve with time. Approaches such as the enthalpy method, which was developed for solving moving interfaces during melting processes, offer the advantage of a treatment that is independent of the shape of the moving interface. Similar methods have been used for modeling multiphase flows with diffuse interface successfully. Here, we expand on these approaches and introduce a phase-field approach to introduce heterogeneous reactions in single and multiphase reactive flows at the pore-scale. Mass conservation is solved in each phase and we introduce interface conditions as a source/sink term in the conservation equation rather than a boundary condition. The advantages are that the method becomes independent of the (time-dependent) topology of the interface and automatically enforces local mass conservation between the different constituents of the domain. We show validations of the model and applications to multispecies reactive transport, isotope fractionation during calcite growth and finally

  11. EVALUATING THE SENSITIVITY OF A SUBSURFACE MULTICOMPONENT REACTIVE TRANSPORT MODEL WITH RESPECT TO TRANSPORT AND REACTION PARAMETERS

    EPA Science Inventory

    The input variables for a numerical model of reactive solute transport in groundwater include both transport parameters, such as hydraulic conductivity and infiltration, and reaction parameters that describe the important chemical and biological processes in the system. These pa...

  12. Nonlocal reactive transport with physical and chemical heterogeneity: Localization errors

    SciTech Connect

    Cushman, J.H.; Hu, B.X.; Deng, F.W.

    1995-09-01

    The origin of nonlocality in {open_quotes}macroscale{close_quotes} models for subsurface chemical transport is illustrated. It is argued that media that are either nonperiodic (e.g., media with evolving heterogeneity) or periodic viewed on a scale wherein a unit cell is discernible must display some nonlocality in the mean. A metaphysical argument suggests that owing to the scarcity of information on natural scales of heterogeneity and on scales of observation associated with an instrument window, constitutive theories for the mean concentration should at the outset of any modeling effort always be considered nonlocal. The intuitive appeal to nonlocality is reinforced with an analytical derivation of the constitutive theory for a conservative tracer without appeal to any mathematical approximations. Comparisons are made between the fully nonlocal (FNL), nonlocal in time (NLT), and fully localized (FL) theories. For conservative transport, there is little difference between the first-order FL and FNL models for spatial moments up to and including the third. However, for conservative transport the first-order NLT model differs significantly from the FNL model in the third spatial moments. For reactive transport, all spatial moments differ between the FNL and FL models. The second transverse-horizontal and third longitudinal-horizontal moments for the NLT model differ from the FNL model. These results suggest that localized first-order transport models for conservative tracers are reasonable if only lower-order moments are desired. However, when the chemical reacts with its environment, the localization approximation can lead to significant error in all moments, and a FNL model will in general be required for accurate simulation. 18 refs., 9 figs., 1 tab.

  13. AN IN-SITU PERMEABLE REACTIVE BARRIER FOR THE TREATMENT OF HEXAVALENT CHROMIUM AND TRICHLOROETHYLENE IN GROUNDWATER: VOLUME 3 MULTICOMPONENT REACTIVE TRANSPORT MODELING

    EPA Science Inventory

    Reactive transport modeling has been conducted to describe the performance of the permeable reactive barrier at the Coast Guard Support Center near Elizabeth City, NC. The reactive barrier was installed to treat groundwater contaminated by hexavalent chromium and chlorinated org...

  14. Reactive transport of aqueous protons in porous media

    NASA Astrophysics Data System (ADS)

    McNeece, Colin J.; Hesse, Marc A.

    2016-11-01

    The sorption of protons determines the surface charge of natural media and is therefore a first-order control on contaminant transport. Significant effort has been extended to develop chemical models that quantify the sorption of protons at the mineral surface. To compare these models' effect on predicted proton transport, we present analytic solutions for column experiments through silica sand. Reaction front morphology is controlled by the functional relationship between the total sorbed and total aqueous proton concentrations. An inflection point in this function near neutral pH leads to a reversal in the classic front formation mechanism under basic conditions, such that proton desorption leads to a self-sharpening front, while adsorption leads to a spreading front. A composite reaction front comprising both a spreading and self-sharpening segment can occur when the injected and initial concentrations straddle the inflection point. This behavior is unique in single component reactive transport and arises due to the auto-ionization of water rather than electrostatic interactions at the mineral surface. We derive a regime diagram illustrating conditions under which different fronts occur, highlighting areas where model predictions diverge. Chemical models are then compared and validated against a systematic set of column experiments.

  15. Kinetic theory of transport processes in partially ionized reactive plasma, II: Electron transport properties

    NASA Astrophysics Data System (ADS)

    Zhdanov, V. M.; Stepanenko, A. A.

    2016-11-01

    The previously obtained in (Zhdanov and Stepanenko, 2016) general transport equations for partially ionized reactive plasma are employed for analysis of electron transport properties in molecular and atomic plasmas. We account for both elastic and inelastic interaction channels of electrons with atoms and molecules of plasma and also the processes of electron impact ionization of neutral particles and three-body ion-electron recombination. The system of scalar transport equations for electrons is discussed and the expressions for non-equilibrium corrections to electron ionization and recombination rates and the diagonal part of the electron pressure tensor are derived. Special attention is paid to analysis of electron energy relaxation during collisions with plasma particles having internal degrees of freedom and the expression for the electron coefficient of inelastic energy losses is deduced. We also derive the expressions for electron vector and tensorial transport fluxes and the corresponding transport coefficients for partially ionized reactive plasma, which represent a generalization of the well-known results obtained by Devoto (1967). The results of numerical evaluation of contribution from electron inelastic collisions with neutral particles to electron transport properties are presented for a series of molecular and atomic gases.

  16. Influence of microbial biofilms on reactive transport in porous media

    NASA Astrophysics Data System (ADS)

    Gerlach, Robin; Cunningham, Al.

    2012-05-01

    Microbial biofilms form in natural and engineered systems and can significantly affect the hydrodynamics in porous media. Subsurface remediation, enhanced oil recovery, abatement of saltwater intrusion, filtration, deep-subsurface sequestration of supercritical carbon dioxide, and biofouling of injection or recovery wells are examples of proposed or implemented beneficial porous media biofilm applications. The thickness of the desired biofilm depends on a number of factors including desirable groundwater flow velocity and residence time of contaminated groundwater within the biofilm barrier as well as the prevailing hydraulic gradient. In order to better understand the influence of biofilms on reactive transport in porous media and ultimately improve biofilm-based porous media technologies, bench and mesoscale studies have been ongoing in our laboratories. This manuscript summarizes some of our past, current, and future efforts in this area and gives an outlook and overview of research and development needs.

  17. Hybrid Models of Reactive Transport in Porous and Fractured Media

    SciTech Connect

    Battiato, Ilenia; Tartakovsky, Daniel M.; Tartakovsky, Alexandre M.; Scheibe, Timothy D.

    2011-02-02

    Darcy-scale models of flow and transport in porous media often fail to describe experimentally observed phenomena, while their pore-scale counterparts are accu- rate but can be computationally prohibitive. Most numerical multi-scale models, which seek to combine these two descriptions, require empirical closures and/or assumptions on the behavior of pore-scale quantities at the continuum (Darcy) scale. We present a general formulation of an iterative hybrid numerical method that links these two scales without resorting to such approximations. The algorithm treats the fluxes exchanged at the internal boundaries between the pore- and continuum-scale domains as unknown, and allows for iteratively determined boundary conditions to be applied at the pore-scale in order to guarantee their continuity. While the algorithm proposed is general, we use it to model Taylor dispersion in a fracture with chemically reactive walls. Results show significant improvement upon standard continuum-scale formulations.

  18. Heterogeneous processes affecting metal ion transport in the presence of organic ligands: Reactive transport modeling

    NASA Astrophysics Data System (ADS)

    Kantar, Cetin

    2007-04-01

    The development of models to accurately simulate metal ion transport through saturated systems under variable chemical conditions, e.g., in systems containing organic ligands (L) such as natural organic matter (NOM), has two essential aspects: (1) establishing the ability to simulate metal ion sorption to aquifer solids over a range of metal/ligand ratios; and (2) to incorporate this ability to simulate metal speciation over a range in chemical conditions (e.g., pH, ligand activity) into mass transport models. Modeling approaches to evaluate metal ion sorption and transport in the presence of NOM include: (1) isotherm-based transport models, and (2) multicomponent (MC) transport models. The accuracy of transport models depends on how well the chemical interactions affecting metal ion transport in the presence of organic ligands (e.g., metal/ligand complexation) are described in transport equations. The isotherm-based transport models often fail to accurately describe metal ion transport in the presence of NOM since these models treat NOM as a single solute despite the fact that NOM is a multicomponent mixture of subcomponents with different chemical and polyfunctional behavior. On the other hand, the calculations presented in this study suggest that a multicomponent reactive transport model, in conjunction with a mechanistic modeling approach for the description of metal ion binding by NOM in a manner conducive to the application of surface complexation modeling (SCM), can effectively be used as an important predictive tool in simulating metal ion sorption and transport under variable chemical conditions in the presence of NOM.

  19. Reactive transport modelling of biogeochemical processes and carbon isotope geochemistry inside a landfill leachate plume

    NASA Astrophysics Data System (ADS)

    van Breukelen, Boris M.; Griffioen, Jasper; Röling, Wilfred F. M.; van Verseveld, Henk W.

    2004-06-01

    The biogeochemical processes governing leachate attenuation inside a landfill leachate plume (Banisveld, the Netherlands) were revealed and quantified using the 1D reactive transport model PHREEQC-2. Biodegradation of dissolved organic carbon (DOC) was simulated assuming first-order oxidation of two DOC fractions with different reactivity, and was coupled to reductive dissolution of iron oxide. The following secondary geochemical processes were required in the model to match observations: kinetic precipitation of calcite and siderite, cation exchange, proton buffering and degassing. Rate constants for DOC oxidation and carbonate mineral precipitation were determined, and other model parameters were optimized using the nonlinear optimization program PEST by means of matching hydrochemical observations closely (pH, DIC, DOC, Na, K, Ca, Mg, NH 4, Fe(II), SO 4, Cl, CH 4, saturation index of calcite and siderite). The modelling demonstrated the relevance and impact of various secondary geochemical processes on leachate plume evolution. Concomitant precipitation of siderite masked the act of iron reduction. Cation exchange resulted in release of Fe(II) from the pristine anaerobic aquifer to the leachate. Degassing, triggered by elevated CO 2 pressures caused by carbonate precipitation and proton buffering at the front of the plume, explained the observed downstream decrease in methane concentration. Simulation of the carbon isotope geochemistry independently supported the proposed reaction network.

  20. Reactive transport modelling of biogeochemical processes and carbon isotope geochemistry inside a landfill leachate plume.

    PubMed

    van Breukelen, Boris M; Griffioen, Jasper; Röling, Wilfred F M; van Verseveld, Henk W

    2004-06-01

    The biogeochemical processes governing leachate attenuation inside a landfill leachate plume (Banisveld, the Netherlands) were revealed and quantified using the 1D reactive transport model PHREEQC-2. Biodegradation of dissolved organic carbon (DOC) was simulated assuming first-order oxidation of two DOC fractions with different reactivity, and was coupled to reductive dissolution of iron oxide. The following secondary geochemical processes were required in the model to match observations: kinetic precipitation of calcite and siderite, cation exchange, proton buffering and degassing. Rate constants for DOC oxidation and carbonate mineral precipitation were determined, and other model parameters were optimized using the nonlinear optimization program PEST by means of matching hydrochemical observations closely (pH, DIC, DOC, Na, K, Ca, Mg, NH4, Fe(II), SO4, Cl, CH4, saturation index of calcite and siderite). The modelling demonstrated the relevance and impact of various secondary geochemical processes on leachate plume evolution. Concomitant precipitation of siderite masked the act of iron reduction. Cation exchange resulted in release of Fe(II) from the pristine anaerobic aquifer to the leachate. Degassing, triggered by elevated CO2 pressures caused by carbonate precipitation and proton buffering at the front of the plume, explained the observed downstream decrease in methane concentration. Simulation of the carbon isotope geochemistry independently supported the proposed reaction network.

  1. Modeling Biodegradation and Reactive Transport: Analytical and Numerical Models

    SciTech Connect

    Sun, Y; Glascoe, L

    2005-06-09

    The computational modeling of the biodegradation of contaminated groundwater systems accounting for biochemical reactions coupled to contaminant transport is a valuable tool for both the field engineer/planner with limited computational resources and the expert computational researcher less constrained by time and computer power. There exists several analytical and numerical computer models that have been and are being developed to cover the practical needs put forth by users to fulfill this spectrum of computational demands. Generally, analytical models provide rapid and convenient screening tools running on very limited computational power, while numerical models can provide more detailed information with consequent requirements of greater computational time and effort. While these analytical and numerical computer models can provide accurate and adequate information to produce defensible remediation strategies, decisions based on inadequate modeling output or on over-analysis can have costly and risky consequences. In this chapter we consider both analytical and numerical modeling approaches to biodegradation and reactive transport. Both approaches are discussed and analyzed in terms of achieving bioremediation goals, recognizing that there is always a tradeoff between computational cost and the resolution of simulated systems.

  2. Quantifying and Predicting Reactive Transport of Uranium in Waste Plumes

    SciTech Connect

    Wan Jiamin; Tokunaga, Tetsu; Steefel, Carl; Burns, Peter

    2005-06-01

    The Hanford Site is the DOE's largest legacy waste site, with uranium (U) from plutonium processing being a major contaminant in its subsurface. Accident release of highly concentrated high level wastes (e.g. 0.5 lb U(VI)/gal) left large quantities of U in the vadose zone under tank farms (e.g. 7-8 tons U(VI) under tank BX-102 (Jones et al., 2001)). The U contamination has been found in groundwater in both 300 and 200 Areas of Hanford, indicating U(VI) was/is mobile. Because excavation costs are enormous, this U will likely be left in-ground for the foreseeable future. Therefore, understanding the contamination processes and the resulting U spatial and temporary distributions and mobility in the heavily contaminated Hanford site is needed in order to forecast its future transport. The overall objective of this research is to develop an experimentally supported conceptual model of U reactive transport, during and after the tank leakage, at heavily U-contaminated areas of the Hanford vadose zone. The conceptual model will incorporate key geochemical and physical controls on the contamination process, explain the current distribution of U in the vadose zone, and guide predictions of its future mobility under the influence of natural recharge. We do not seek to predict the complex flow geometry of any specific waste plume. Instead, our work is trying to identify the hierarchy of processes relevant along U waste plume paths.

  3. Multiple mobility edges in a 1D Aubry chain with Hubbard interaction in presence of electric field: Controlled electron transport

    NASA Astrophysics Data System (ADS)

    Saha, Srilekha; Maiti, Santanu K.; Karmakar, S. N.

    2016-09-01

    Electronic behavior of a 1D Aubry chain with Hubbard interaction is critically analyzed in presence of electric field. Multiple energy bands are generated as a result of Hubbard correlation and Aubry potential, and, within these bands localized states are developed under the application of electric field. Within a tight-binding framework we compute electronic transmission probability and average density of states using Green's function approach where the interaction parameter is treated under Hartree-Fock mean field scheme. From our analysis we find that selective transmission can be obtained by tuning injecting electron energy, and thus, the present model can be utilized as a controlled switching device.

  4. Filtered density function approach for reactive transport in groundwater

    NASA Astrophysics Data System (ADS)

    Suciu, Nicolae; Schüler, Lennart; Attinger, Sabine; Knabner, Peter

    2016-04-01

    Spatial filtering may be used in coarse-grained simulations (CGS) of reactive transport in groundwater, similar to the large eddy simulations (LES) in turbulence. The filtered density function (FDF), stochastically equivalent to a probability density function (PDF), provides a statistical description of the sub-grid, unresolved, variability of the concentration field. Besides closing the chemical source terms in the transport equation for the mean concentration, like in LES-FDF methods, the CGS-FDF approach aims at quantifying the uncertainty over the whole hierarchy of heterogeneity scales exhibited by natural porous media. Practically, that means estimating concentration PDFs on coarse grids, at affordable computational costs. To cope with the high dimensionality of the problem in case of multi-component reactive transport and to reduce the numerical diffusion, FDF equations are solved by particle methods. But, while trajectories of computational particles are modeled as stochastic processes indexed by time, the concentration's heterogeneity is modeled as a random field, with multi-dimensional, spatio-temporal sets of indices. To overcome this conceptual inconsistency, we consider FDFs/PDFs of random species concentrations weighted by conserved scalars and we show that their evolution equations can be formulated as Fokker-Planck equations describing stochastically equivalent processes in concentration-position spaces. Numerical solutions can then be approximated by the density in the concentration-position space of an ensemble of computational particles governed by the associated Itô equations. Instead of sequential particle methods we use a global random walk (GRW) algorithm, which is stable, free of numerical diffusion, and practically insensitive to the increase of the number of particles. We illustrate the general FDF approach and the GRW numerical solution for a reduced complexity problem consisting of the transport of a single scalar in groundwater

  5. Modeling reactive transport with particle tracking and kernel estimators

    NASA Astrophysics Data System (ADS)

    Rahbaralam, Maryam; Fernandez-Garcia, Daniel; Sanchez-Vila, Xavier

    2015-04-01

    Groundwater reactive transport models are useful to assess and quantify the fate and transport of contaminants in subsurface media and are an essential tool for the analysis of coupled physical, chemical, and biological processes in Earth Systems. Particle Tracking Method (PTM) provides a computationally efficient and adaptable approach to solve the solute transport partial differential equation. On a molecular level, chemical reactions are the result of collisions, combinations, and/or decay of different species. For a well-mixed system, the chem- ical reactions are controlled by the classical thermodynamic rate coefficient. Each of these actions occurs with some probability that is a function of solute concentrations. PTM is based on considering that each particle actually represents a group of molecules. To properly simulate this system, an infinite number of particles is required, which is computationally unfeasible. On the other hand, a finite number of particles lead to a poor-mixed system which is limited by diffusion. Recent works have used this effect to actually model incomplete mix- ing in naturally occurring porous media. In this work, we demonstrate that this effect in most cases should be attributed to a defficient estimation of the concentrations and not to the occurrence of true incomplete mixing processes in porous media. To illustrate this, we show that a Kernel Density Estimation (KDE) of the concentrations can approach the well-mixed solution with a limited number of particles. KDEs provide weighting functions of each particle mass that expands its region of influence, hence providing a wider region for chemical reactions with time. Simulation results show that KDEs are powerful tools to improve state-of-the-art simulations of chemical reactions and indicates that incomplete mixing in diluted systems should be modeled based on alternative conceptual models and not on a limited number of particles.

  6. Simulation of reactive processes related to biodegradation in aquifers. 1. Structure of the three-dimensional reactive transport model

    NASA Astrophysics Data System (ADS)

    Schäfer, Dirk; Schäfer, Wolfgang; Kinzelbach, Wolfgang

    1998-05-01

    The reactive transport model TBC (transport, biochemistry, and chemistry) numerically solves the equations for reactive transport in three-dimensional saturated groundwater flow. A finite element approximation and a standard Galerkin method are used. Solute transport is coupled to microbially mediated organic carbon degradation. Microbial growth is assumed to follow Monod-type kinetics. Substrate consumption and release of metabolic products is coupled to microbial growth via yield coefficients and stoichiometric relations. Additionally, the effects of microbial activity on selected inorganic chemical species in the aquifer can be considered. TBC allows the user to specify a wide range of possible biochemical and chemical reactions in the input file. This makes TBC a powerful and flexible simulation tool. It was developed to simulate reactive processes related to in situ bioremediation, but further fields of application are laboratory column studies on redox processes coupled to organic carbon degradation, field cases of intrinsic biodegradation, and early diagenetic processes in sediments.

  7. Status of the solar and infrared radiation submodels in the LLNL 1-D and 2-D chemical-transport models

    SciTech Connect

    Grant, K.E.; Taylor, K.E.; Ellis, J.S.; Wuebbles, D.J.

    1987-07-01

    The authors have implemented a series of state of the art radiation transport submodels in previously developed one dimensional and two dimensional chemical transport models of the troposphere and stratosphere. These submodels provide the capability of calculating accurate solar and infrared heating rates. They are a firm basis for further radiation submodel development as well as for studying interactions between radiation and model dynamics under varying conditions of clear sky, clouds, and aerosols. 37 refs., 3 figs.

  8. Imaging geochemical heterogeneities using inverse reactive transport modeling: An example relevant for characterizing arsenic mobilization and distribution

    NASA Astrophysics Data System (ADS)

    Fakhreddine, Sarah; Lee, Jonghyun; Kitanidis, Peter K.; Fendorf, Scott; Rolle, Massimo

    2016-02-01

    The spatial distribution of reactive minerals in the subsurface is often a primary factor controlling the fate and transport of contaminants in groundwater systems. However, direct measurement and estimation of heterogeneously distributed minerals are often costly and difficult to obtain. While previous studies have shown the utility of using hydrologic measurements combined with inverse modeling techniques for tomography of physical properties including hydraulic conductivity, these methods have seldom been used to image reactive geochemical heterogeneities. In this study, we focus on As-bearing reactive minerals as aquifer contaminants. We use synthetic applications to demonstrate the ability of inverse modeling techniques combined with mechanistic reactive transport models to image reactive mineral lenses in the subsurface and quantify estimation error using indirect, commonly measured groundwater parameters. Specifically, we simulate the mobilization of arsenic via kinetic oxidative dissolution of As-bearing pyrite due to dissolved oxygen in the ambient groundwater, which is an important mechanism for arsenic release in groundwater both under natural conditions and engineering applications such as managed aquifer recharge and recovery operations. The modeling investigation is carried out at various scales and considers different flow-through domains including (i) a 1D lab-scale column (80 cm), (ii) a 2D lab-scale setup (60 cm × 30 cm) and (iii) a 2D field-scale domain (20 m × 4 m). In these setups, synthetic dissolved oxygen data and forward reactive transport simulations are used to image the spatial distribution of As-bearing pyrite using the Principal Component Geostatistical Approach (PCGA) for inverse modeling.

  9. Hyperbolic theory for pH-dependent adsorption in reactive transport in porous media

    NASA Astrophysics Data System (ADS)

    Prigiobbe, V.; Hesse, M. A.; Bryant, S. L.

    2012-12-01

    We use the hyperbolic theory of conservation laws to analyze the transport of strontium (Sr2+) through a porous medium with surface complexation. An hydrophilic iron-oxide surface was considered where Sr2+ and hydrogen (H+) compete for the same site leading to competitive adsorption described by an pH-dependent Langmuir isotherm. Despite the importance of pH-dependent adsorption in environmental applications, the basic structure of the displacement has received little attention. In reactive transport problems with pH-dependent adsorption, one of the conservation laws is for the total hydrogen (cHtot = cH+-cOH-) in the system, also called the acidity. The presence of this equation gives rise to additional nonlinearity in the problems that distinguishes them from other competitive sorption problems where hydrogen is not involved. We analyze a 1D reactive transport model with an incompressible fluid containing H+, Sr2+, sodium (Na+), and chlorine (Cl-) flowing through a reactive porous media made of goethite. Under the assumption of overall charge balance and of only advection for Na+ and Cl-, the mathematical problem reduces to a strictly hyperbolic 3x3 system of partial dierential equations (PDEs) for cHtot, Sr2+ (cSr2+), and effective anions (ca = cCl--cNa+) which are coupled by the adsorption isotherms for H+ and Sr2+ and have the non-linearity in the accumulation terms. One characteristic field is linearly degenerate while the other two are non-genuinely nonlinear due to inflection loci in both isotherms. We derived the complete set of analytical solutions to the Riemann problem (constant initial and injected states) and described the characteristic waves that may arise, concluding that only nine combinations of a contact discontinuity with rarefactions, shocks, shock-rarefactions are possible. The composite shock-rarefaction waves arise from the inflection loci in the isotherms and are absent in classic competitive Langmuir sorption. The inflection loci divide

  10. Multicomponent reactive transport modeling of uranium bioremediation field experiments

    SciTech Connect

    Fang, Yilin; Yabusaki, Steven B.; Morrison, Stan J.; Amonette, James E.; Long, Philip E.

    2009-10-15

    Biostimulation field experiments with acetate amendment are being performed at a former uranium mill tailings site in Rifle, Colorado, to investigate subsurface processes controlling in situ bioremediation of uranium-contaminated groundwater. An important part of the research is identifying and quantifying field-scale models of the principal terminal electron-accepting processes (TEAPs) during biostimulation and the consequent biogeochemical impacts to the subsurface receiving environment. Integrating abiotic chemistry with the microbially mediated TEAPs in the reaction network brings into play geochemical observations (e.g., pH, alkalinity, redox potential, major ions, and secondary minerals) that the reactive transport model must recognize. These additional constraints provide for a more systematic and mechanistic interpretation of the field behaviors during biostimulation. The reaction network specification developed for the 2002 biostimulation field experiment was successfully applied without additional calibration to the 2003 and 2007 field experiments. The robustness of the model specification is significant in that 1) the 2003 biostimulation field experiment was performed with 3 times higher acetate concentrations than the previous biostimulation in the same field plot (i.e., the 2002 experiment), and 2) the 2007 field experiment was performed in a new unperturbed plot on the same site. The biogeochemical reactive transport simulations accounted for four TEAPs, two distinct functional microbial populations, two pools of bioavailable Fe(III) minerals (iron oxides and phyllosilicate iron), uranium aqueous and surface complexation, mineral precipitation, and dissolution. The conceptual model for bioavailable iron reflects recent laboratory studies with sediments from the Old Rifle Uranium Mill Tailings Remedial Action (UMTRA) site that demonstrated that the bulk (~90%) of Fe(III) bioreduction is associated with the phyllosilicates rather than the iron oxides

  11. ATP Binding Cassette Transporter ABCA7 Regulates NKT Cell Development and Function by Controlling CD1d Expression and Lipid Raft Content

    PubMed Central

    Nowyhed, Heba N.; Chandra, Shilpi; Kiosses, William; Marcovecchio, Paola; Andary, Farah; Zhao, Meng; Fitzgerald, Michael L.; Kronenberg, Mitchell; Hedrick, Catherine C.

    2017-01-01

    ABCA7 is an ABC transporter expressed on the plasma membrane, and actively exports phospholipid complexes from the cytoplasmic to the exocytoplasmic leaflet of membranes. Invariant NKT (iNKT) cells are a subpopulation of T lymphocytes that recognize glycolipid antigens in the context of CD1d-mediated antigen presentation. In this study, we demonstrate that ABCA7 regulates the development of NKT cells in a cell-extrinsic manner. We found that in Abca7−/− mice there is reduced expression of CD1d accompanied by an alteration in lipid raft content on the plasma membrane of thymocytes and antigen presenting cells. Together, these alterations caused by absence of ABCA7 negatively affect NKT cell development and function. PMID:28091533

  12. Glucose transporter type I deficiency (G1D) at 25 (1990–2015): Presumptions, facts and the lives of persons with this rare disease

    PubMed Central

    Pascual, Juan M.; Ronen, Gabriel M.

    2015-01-01

    As is often the case for rare diseases, the number of published reviews and case reports of Glucose transporter type I deficiency (G1D) approaches or exceeds that of original research. This can indicate medical interest, but also scientific stagnation. In assessing this state of affairs here, we focus not on what is peculiar or disparate about G1D, but on the assumptions that have reigned thus far undisputed, and critique them as a potential impediment to progress. To summarize the most common G1D phenotype, we trace the 25-year story of G1D in parallel with the natural history of one of two index patients, identified in 1990 by one of us (G.M.R.) and brought up to date by the other (J.M.P.) while later examining widely-repeated but little-scrutinized statements. Among them are those that pertain to assumptions about brain fuels; energy-failure; cerebrospinal glucose concentration; the purpose of ketogenic diet; the role of the defective blood brain barrier; genotype-phenotype correlations; a bewildering array of phenotypes; ictogenesis, seizures and the electroencephalogram; the use of mice to model the disorder; and what treatments may and may not be expected to accomplish. We reach the forgone conclusion that the proper study of mankind - and of one of its ailments (G1D) - is man itself (rather than mice, isolated cells or extrapolated inferences), and propose a framework for rigorous investigation that we hope will lead to a better understanding and to better treatments for this and for rare disorders in general. These considerations, together with experience drawn from other disorders, lead, as a logical consequence, to the nullification of the view that therapeutic development (i.e., trials) for rare diseases could or should be accelerated without the most vigorous scientific scrutiny: Trial and error constitute an inseparable couple, such that, at the present time, hastening the former is bound to precipitate the latter. PMID:26341673

  13. Coupling WEPP and 3ST1D models for improved prediction of flow and sediment transport at watershed scales

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Watershed modeling is a key component of watershed management that involves the simulation of hydrological and fluvial processes for predicting flow and sediment transport within a watershed. For practical purposes, most numerical models have been developed to simulate either runoff and soil erosion...

  14. Discontinuous Finite Elements for a Hyperbolic Problem with Singular Coefficient: a Convergence Theory for 1-D Spherical Neutron Transport

    SciTech Connect

    Machorro, E. A.

    2010-09-07

    A theory of convergence is presented for the discontinuous Galerkin finite element method of solving the non-scattering spherically symmetric Boltzmann transport equation using piecewise constant test and trial functions. Results are then extended to higher order polynomial spaces. Comparisons of numerical properties were presented in earlier work.

  15. Advanced Nodal P3/SP3 Axial Transport Solvers for the MPACT 2D/1D Scheme

    SciTech Connect

    Stimpson, Shane G; Collins, Benjamin S

    2015-01-01

    As part of its initiative to provide multiphysics simulations of nuclear reactor cores, the Consortium for Advanced Simulation of Light Water Reactors (CASL) is developing the Virtual Environment for Reactor Applications Core Simulator (VERA-CS). The MPACT code, which is the primary neutron transport solver of VERA-CS, employs the two-dimensional/one-dimensional (2D/1D) method to solve 3-dimensional neutron transport problems and provide sub-pin-level resolution of the power distribution. While 2D method of characteristics is used to solve for the transport effects within each plane, 1D-nodal methods are used axially. There have been extensive studies of the 2D/1D method with a variety nodal methods, and the P3/SP3 solver has proved to be an effective method of providing higher-fidelity solutions while maintaining a low computational burden.The current implementation in MPACT wraps a one-node nodal expansion method (NEM) kernel for each moment, iterating between them and performing multiple sweeps to resolve flux distributions. However, it has been observed that this approach is more sensitive to convergence problems. This paper documents the theory and application two new nodal P3/SP3 approaches to be used within the 2D/1D method in MPACT. These two approaches aim to provide enhanced stability compared with the pre-existing one-node approach. Results from the HY-NEM-SP3 solver show that the accuracy is consistent with the one-node formulations and provides improved convergence for some problems; but the solver has issues with cases in thin planes. Although the 2N-SENM-SP3 solver is still under development, it is intended to resolve the issues with HY-NEM-SP3 but it will incur some additional computational burden by necessitating an additional 1D-CMFD-P3 solver to generate the second moment cell-averaged scalar flux.

  16. CSDUST3 - A radiation transport code for a dusty medium with 1-D planar, spherical or cylindrical geometry

    NASA Technical Reports Server (NTRS)

    Egan, Michael P.; Leung, Chun Ming; Spagna, George F., Jr.

    1988-01-01

    The program solves the radiation transport problem in a dusty medium with one-dimensional planar, spherical or cylindrical geometry. It determines self-consistently the effects of multiple scattering, absorption, and re-emission of photons on the temperature of dust grains and the characteristics of the internal radiation field. The program can treat radiation field anisotropy, linear anisotropic scattering, and multi-grain components. The program output consists of the dust-temperature distribution, flux spectrum, surface brightness at each frequency and the observed intensities (involving a convolution with a telescope beam pattern).

  17. Spectromicroscopy for addressing the surface and electron transport properties of individual 1-d nanostructures and their networks.

    PubMed

    Kolmakov, Andrei; Potluri, Sai; Barinov, Alexei; Menteş, Tevfik O; Gregoratti, Luca; Niño, Miguel A; Locatelli, Andrea; Kiskinova, Maya

    2008-10-28

    Understanding size/dimensionality-dependent phenomena and processes relevant to chemical sensing and catalysis requires analytical methods with high surface sensitivity, which can exploit the structure and composition of nanomaterials at their natural length scales and working conditions. In the present study, we explored the potentials and complementary capabilities of several surface-sensitive microscopy approaches to shed light on the properties of individual SnO(2) nanowires and their networks. Our results demonstrate the unique opportunities provided by synchrotron-based photoelectron microscopies for surface-sensitive structural and chemical analysis, including in situ characterization of electron transport properties of a nanostructure wired as an active element in chemiresistor devices.

  18. Heptanoate as a neural fuel: energetic and neurotransmitter precursors in normal and glucose transporter I-deficient (G1D) brain

    PubMed Central

    Marin-Valencia, Isaac; Good, Levi B; Ma, Qian; Malloy, Craig R; Pascual, Juan M

    2013-01-01

    It has been postulated that triheptanoin can ameliorate seizures by supplying the tricarboxylic acid cycle with both acetyl-CoA for energy production and propionyl-CoA to replenish cycle intermediates. These potential effects may also be important in other disorders associated with impaired glucose metabolism because glucose supplies, in addition to acetyl-CoA, pyruvate, which fulfills biosynthetic demands via carboxylation. In patients with glucose transporter type I deficiency (G1D), ketogenic diet fat (a source only of acetyl-CoA) reduces seizures, but other symptoms persist, providing the motivation for studying heptanoate metabolism. In this work, metabolism of infused [5,6,7-13C3]heptanoate was examined in the normal mouse brain and in G1D by 13C-nuclear magnetic resonance spectroscopy, gas chromatography-mass spectrometry (GC-MS), and liquid chromatography-mass spectrometry (LC-MS). In both groups, plasma glucose was enriched in 13C, confirming gluconeogenesis from heptanoate. Acetyl-CoA and glutamine levels became significantly higher in the brain of G1D mice relative to normal mice. In addition, brain glutamine concentration and 13C enrichment were also greater when compared with glutamate in both animal groups, suggesting that heptanoate and/or C5 ketones are primarily metabolized by glia. These results enlighten the mechanism of heptanoate metabolism in the normal and glucose-deficient brain and encourage further studies to elucidate its potential antiepileptic effects in disorders of energy metabolism. PMID:23072752

  19. Relating Reactive Transport to Hierarchical Sedimentary Architecture. Part 1. Horizontal Spatial Correlation of Hydraulic and Reactive Transport Parameters

    NASA Astrophysics Data System (ADS)

    Ritzi, R. W., Jr.

    2014-12-01

    A number of studies of the spatial correlation of log permeability (Y) in different sedimentary aquifers are reviewed showing that the spatial correlation structure can be defined by how the proportion of lag transitions crossing different facies (i.e. the cross-transition probability structure) increases with increasing lag distance. The common underlying cross-transition structure can contain substructures with different correlation ranges corresponding to different scales of sedimentary facies within the hierarchy of the sedimentary architecture. For each substructure, the standard deviation in facies length relative to the mean can mostly define the shape, and the proportions and mean length of facies define the range. An illustrative example from the Borden research site shows the horizontal spatial bivariate correlation of Y and of reactive attributes (R) affecting subsurface transport are both defined by the same underlying cross-transition probability structures. Thus, the horizontal Y and R autosemivariograms and the R-Y cross-semivariogram have the same underlying composite correlation structure and substructures (shape and range in the rise to a sill). Such cross-transition probability based correlation structures are used in the companion Part 2 presentation (Soltanian et al.) to develop models which relate the time-dependent effective retardation and the particle displacement variance to hierarchical sedimentary architecture.

  20. Modeling seawater intrusion and the associated reactive solute transport in fractured coastal aquifers

    NASA Astrophysics Data System (ADS)

    Nick, Hamid M.; Regnier, Pierre; Thullner, Martin

    2013-04-01

    In coastal aquifers seawater and terrestrial water get into contact and the reactive mixing between these water bodies controls the water quality of submarine groundwater discharge. The rates of such mixing controlled reactions are depending not only on the properties of the reactive species but also on the density driven flow dynamics and the resulting transport patterns. A prediction of these flow and transport processes and thus of the fate of reactive species is specifically challenged in fracture aquifers as it depends on the focusing of the flow and the local balance of viscous and gravitational forces. To study the influence of fractures on mixing and reactive transport in coastal aquifers we present a reactive discrete fracture and matrix (DFM) model using unstructured spatially adaptively refined finite-element meshes. This model is developed by coupling the Complex System Modelling Platform (CSMP++) utilizing a hybrid FEFV scheme, and a Biogeochemical Reaction Network Simulator (BRNS) capable of solving for kinetically and thermodynamically constrained biogeochemical reactions [1]. The model is applied to simulate the reactive transport in fracture networks embedded in a permeable rock matrix. For virtual coastal aquifers, different fracture data sets are employed to study the effect of fractures and their characteristics on the reactive mixing between fresh water and seawater in coastal aquifers. Obtained results show that the presence of fractures enhances reactive mixing for most cases due to the combined effect of fracture induced flow channeling and dispersion. The magnitude of this effect depends highly on fracture density, spacing and orientation. Furthermore the results indicate that reactive mixing in fractured aquifers is not well described using an effective parameterization of a homogeneous aquifer setup. This suggests that structural information on the fracture network is needed for a sufficient description of reactive transport processes in

  1. Multicomponent reactive transport modeling of uranium bioremediation field experiments

    NASA Astrophysics Data System (ADS)

    Fang, Yilin; Yabusaki, Steven B.; Morrison, Stan J.; Amonette, James P.; Long, Philip E.

    2009-10-01

    A reaction network integrating abiotic and microbially mediated reactions has been developed to simulate biostimulation field experiments at a former Uranium Mill Tailings Remedial Action (UMTRA) site in Rifle, Colorado. The reaction network was calibrated using data from the 2002 field experiment, after which it was applied without additional calibration to field experiments performed in 2003 and 2007. The robustness of the model specification is significant in that (1) the 2003 biostimulation field experiment was performed with 3 times higher acetate concentrations than the previous biostimulation in the same field plot (i.e., the 2002 experiment), and (2) the 2007 field experiment was performed in a new unperturbed plot on the same site. The biogeochemical reactive transport simulations accounted for four terminal electron-accepting processes (TEAPs), two distinct functional microbial populations, two pools of bioavailable Fe(III) minerals (iron oxides and phyllosilicate iron), uranium aqueous and surface complexation, mineral precipitation and dissolution. The conceptual model for bioavailable iron reflects recent laboratory studies with sediments from the UMTRA site that demonstrated that the bulk (˜90%) of initial Fe(III) bioreduction is associated with phyllosilicate rather than oxide forms of iron. The uranium reaction network includes a U(VI) surface complexation model based on laboratory studies with Rifle site sediments and aqueous complexation reactions that include ternary complexes (e.g., calcium-uranyl-carbonate). The bioreduced U(IV), Fe(II), and sulfide components produced during the experiments are strongly associated with the solid phases and may play an important role in long-term uranium immobilization.

  2. Reactive Transport Modeling of Induced Calcite Precipitation Reaction Fronts in Porous Media Using A Parallel, Fully Coupled, Fully Implicit Approach

    NASA Astrophysics Data System (ADS)

    Guo, L.; Huang, H.; Gaston, D.; Redden, G. D.; Fox, D. T.; Fujita, Y.

    2010-12-01

    Inducing mineral precipitation in the subsurface is one potential strategy for immobilizing trace metal and radionuclide contaminants. Generating mineral precipitates in situ can be achieved by manipulating chemical conditions, typically through injection or in situ generation of reactants. How these reactants transport, mix and react within the medium controls the spatial distribution and composition of the resulting mineral phases. Multiple processes, including fluid flow, dispersive/diffusive transport of reactants, biogeochemical reactions and changes in porosity-permeability, are tightly coupled over a number of scales. Numerical modeling can be used to investigate the nonlinear coupling effects of these processes which are quite challenging to explore experimentally. Many subsurface reactive transport simulators employ a de-coupled or operator-splitting approach where transport equations and batch chemistry reactions are solved sequentially. However, such an approach has limited applicability for biogeochemical systems with fast kinetics and strong coupling between chemical reactions and medium properties. A massively parallel, fully coupled, fully implicit Reactive Transport simulator (referred to as “RAT”) based on a parallel multi-physics object-oriented simulation framework (MOOSE) has been developed at the Idaho National Laboratory. Within this simulator, systems of transport and reaction equations can be solved simultaneously in a fully coupled, fully implicit manner using the Jacobian Free Newton-Krylov (JFNK) method with additional advanced computing capabilities such as (1) physics-based preconditioning for solution convergence acceleration, (2) massively parallel computing and scalability, and (3) adaptive mesh refinements for 2D and 3D structured and unstructured mesh. The simulator was first tested against analytical solutions, then applied to simulating induced calcium carbonate mineral precipitation in 1D columns and 2D flow cells as analogs

  3. OS3D/GIMRT software for modeling multicomponent-multidimensional reactive transport

    SciTech Connect

    CI Steefel; SB Yabusaki

    2000-05-17

    OS3D/GIMRT is a numerical software package for simulating multicomponent reactive transport in porous media. The package consists of two principal components: (1) the code OS3D (Operator Splitting 3-Dimensional Reactive Transport) which simulates reactive transport by either splitting the reaction and transport steps in time, i.e., the classic time or operator splitting approach, or by iterating sequentially between reactions and transport, and (2) the code GIMRT (Global Implicit Multicomponent Reactive Transport) which treats up to two dimensional reactive transport with a one step or global implicit approach. Although the two codes do not yet have totally identical capabilities, they can be run from the same input file, allowing comparisons to be made between the two approaches in many cases. The advantages and disadvantages of the two approaches are discussed more fully below, but in general OS3D is designed for simulation of transient concentration fronts, particularly under high Peclet number transport conditions, because of its use of a total variation diminishing or TVD transport algorithm. GIMRT is suited for simulating water-rock alteration over long periods of time where the aqueous concentration field is at or close to a quasi-stationary state and the numerical transport errors are less important. Where water-rock interaction occurs over geological periods of time, GIMRT may be preferable to OS3D because of its ability to take larger time steps.

  4. Variably Saturated Flow and Multicomponent Biogeochemical Reactive Transport Modeling of a Uranium Bioremediation Field Experiment

    SciTech Connect

    Yabusaki, Steven B.; Fang, Yilin; Williams, Kenneth H.; Murray, Christopher J.; Ward, Anderson L.; Dayvault, Richard; Waichler, Scott R.; Newcomer, Darrell R.; Spane, Frank A.; Long, Philip E.

    2011-11-01

    Field experiments at a former uranium mill tailings site have identified the potential for stimulating indigenous bacteria to catalyze the conversion of aqueous uranium in the +6 oxidation state to immobile solid-associated uranium in the +4 oxidation state. This effectively removes uranium from solution resulting in groundwater concentrations below actionable standards. Three-dimensional, coupled variably-saturated flow and biogeochemical reactive transport modeling of a 2008 in situ uranium bioremediation field experiment is used to better understand the interplay of transport rates and biogeochemical reaction rates that determine the location and magnitude of key reaction products. A comprehensive reaction network, developed largely through previous 1-D modeling studies, was used to simulate the impacts on uranium behavior of pulsed acetate amendment, seasonal water table variation, spatially-variable physical (hydraulic conductivity, porosity) and geochemical (reactive surface area) material properties. A principal challenge is the mechanistic representation of biologically-mediated terminal electron acceptor process (TEAP) reactions whose products significantly alter geochemical controls on uranium mobility through increases in pH, alkalinity, exchangeable cations, and highly reactive reduction products. In general, these simulations of the 2008 Big Rusty acetate biostimulation field experiment in Rifle, Colorado confirmed previously identified behaviors including (1) initial dominance by iron reducing bacteria that concomitantly reduce aqueous U(VI), (2) sulfate reducing bacteria that become dominant after {approx}30 days and outcompete iron reducers for the acetate electron donor, (3) continuing iron-reducer activity and U(VI) bioreduction during dominantly sulfate reducing conditions, and (4) lower apparent U(VI) removal from groundwater during dominantly sulfate reducing conditions. New knowledge on simultaneously active metal and sulfate reducers has been

  5. Modification of the finite element heat and mass transfer code (FEHMN) to model multicomponent reactive transport

    SciTech Connect

    Viswanathan, H.S.

    1995-12-31

    The finite element code FEHMN is a three-dimensional finite element heat and mass transport simulator that can handle complex stratigraphy and nonlinear processes such as vadose zone flow, heat flow and solute transport. Scientists at LANL have been developed hydrologic flow and transport models of the Yucca Mountain site using FEHMN. Previous FEHMN simulations have used an equivalent K{sub d} model to model solute transport. In this thesis, FEHMN is modified making it possible to simulate the transport of a species with a rigorous chemical model. Including the rigorous chemical equations into FEHMN simulations should provide for more representative transport models for highly reactive chemical species. A fully kinetic formulation is chosen for the FEHMN reactive transport model. Several methods are available to computationally implement a fully kinetic formulation. Different numerical algorithms are investigated in order to optimize computational efficiency and memory requirements of the reactive transport model. The best algorithm of those investigated is then incorporated into FEHMN. The algorithm chosen requires for the user to place strongly coupled species into groups which are then solved for simultaneously using FEHMN. The complete reactive transport model is verified over a wide variety of problems and is shown to be working properly. The simulations demonstrate that gas flow and carbonate chemistry can significantly affect {sup 14}C transport at Yucca Mountain. The simulations also provide that the new capabilities of FEHMN can be used to refine and buttress already existing Yucca Mountain radionuclide transport studies.

  6. Influence of calcite on uranium(VI) reactive transport in the groundwater–river mixing zone

    SciTech Connect

    Ma, Rui; Liu, Chongxuan; Greskowiak, Janek; Prommer, Henning; Zachara, John M.; Zheng, Chunmiao

    2014-01-23

    Calcite is an important mineral that can affect uranyl reactive transport in subsurface sediments. This study investigated the distribution of calcite and its influence on uranyl adsorption and reactive transport in the groundwater-river mixing zone at US Hanford 300A, Washington State. Simulations using a 2D reactive transport model under field-relevant hydrogeochemical conditions revealed a complex distribution of calcite concentration as a result of dynamic groundwater-river interactions. The calcite concentration distribution in turn affected the spatial and temporal changes in aqueous carbonate, calcium, and pH, which subsequently influenced U(VI) mobility and discharge rates into the river. The results implied that calcite distribution and its concentration dynamics is an important consideration for field characterization, monitoring, and reactive transport prediction.

  7. SELECTION AND CALIBRATION OF SUBSURFACE REACTIVE TRANSPORT MODELS USING A SURROGATE-MODEL APPROACH

    EPA Science Inventory

    While standard techniques for uncertainty analysis have been successfully applied to groundwater flow models, extension to reactive transport is frustrated by numerous difficulties, including excessive computational burden and parameter non-uniqueness. This research introduces a...

  8. CALIBRATION OF SUBSURFACE BATCH AND REACTIVE-TRANSPORT MODELS INVOLVING COMPLEX BIOGEOCHEMICAL PROCESSES

    EPA Science Inventory

    In this study, the calibration of subsurface batch and reactive-transport models involving complex biogeochemical processes was systematically evaluated. Two hypothetical nitrate biodegradation scenarios were developed and simulated in numerical experiments to evaluate the perfor...

  9. Constraining chemical geothermometry with reactive transport models: An example study of the Dixie Valley geothermal area

    NASA Astrophysics Data System (ADS)

    Wanner, C.; Peiffer, L.; Spycher, N.; Sonnenthal, E. L.; Iovenitti, J. L.; Kennedy, B. M.

    2012-12-01

    In this study, 1D and 2D reactive transport simulations of the Dixie Valley geothermal area (Nevada, USA) were performed using Toughreact [1] to evaluate the fluid flow pathways and rates of equilibration of hydrothermal fluids. Modeling studies were combined with new multicomponent geothermometry, which is being used to estimate the temperature of geothermal reservoirs based on chemical analysis of geothermal springs. The concept is based on the assumption of chemical equilibrium between the thermal fluid and minerals of the reservoir rock [2]. If re-equilibration occurs between the reservoir at depth and the surface, then the 'deep' chemical signature of the fluid is lost and the obtained reservoir temperature is underestimated. The simulations were run for a vertical cross-section that has been structurally and geologically characterized. Model calibration was performed using available site information such as chemical analysis of geothermal springs, isotherms inferred from geothermal wells and results of a previous flow simulation study [3]. Model runs included the simulation of typical near-surface processes such as dilution, mixing and salt leaching occurring at the Dixie Valley geothermal area. Each reactive transport model produced 'synthetic' waters that were processed using the multicomponent chemical geothermometer code GeoT [4]. This code computes the saturation indices of reservoir minerals as a function of the temperature. Reservoir temperature is inferred when mineral saturation indices all cluster around zero. GeoT results were also compared with classical solute geothermometers (silica, Na-K-(Ca), K-Mg) [5]. Simulation results reveal that a minimum vertical fluid velocity on the order of a meter per day is needed to preserve the geochemical signature of a geothermal reservoir and to predict its temperature. The simulations also show that deep geochemical signatures are well preserved if fracture surfaces are partially coated by secondary minerals

  10. Uranium transport in a crushed granodiorite: experiments and reactive transport modeling.

    PubMed

    Dittrich, T M; Reimus, P W

    2015-01-01

    The primary objective of this study was to develop and demonstrate an experimental method to refine and better parameterize process models for reactive contaminant transport in aqueous subsurface environments and to reduce conservatism in such models without attempting to fully describe the geochemical system. Uranium was used as an example of a moderately adsorbing contaminant because of its relevance in geologic disposal of spent nuclear fuel. A fractured granodiorite from the Grimsel Test Site (GTS) in Switzerland was selected because this system has been studied extensively and field experiments have been conducted with radionuclides including uranium. We evaluated the role of pH, porous media size fraction, and flow interruptions on uranium transport. Rock cores drilled from the GTS were shipped to Los Alamos National Laboratory, characterized by x-ray diffraction and optical microscopy, and used in uranium batch sorption and column breakthrough experiments. A synthetic water was prepared that represented the porewater that would be present after groundwater interacts with bentonite backfill material near a nuclear waste package. Uranium was conservatively transported at pH8.8. Significant adsorption and subsequent desorption was observed at pH ~7, with long desorption tails resulting after switching the column injection solution to uranium-free groundwater. Our experiments were designed to better interrogate this slow desorption behavior. A three-site model predicted sorption rate constants for a pH7.2 solution with a 75-150 μm granodiorite fraction to be 3.5, 0.012, and 0.012 mL/g-h for the forward reactions and 0.49, 0.0025, and 0.001 h(-1) for the reverse reactions. Surface site densities were 1.3, 0.042, and 0.042 μmol/g for the first, second, and third sites, respectively. 10-year simulations show that including a slow binding site increases the arrival time of a uranium pulse by ~70%.

  11. Uranium transport in a crushed granodiorite: Experiments and reactive transport modeling

    NASA Astrophysics Data System (ADS)

    Dittrich, T. M.; Reimus, P. W.

    2015-04-01

    The primary objective of this study was to develop and demonstrate an experimental method to refine and better parameterize process models for reactive contaminant transport in aqueous subsurface environments and to reduce conservatism in such models without attempting to fully describe the geochemical system. Uranium was used as an example of a moderately adsorbing contaminant because of its relevance in geologic disposal of spent nuclear fuel. A fractured granodiorite from the Grimsel Test Site (GTS) in Switzerland was selected because this system has been studied extensively and field experiments have been conducted with radionuclides including uranium. We evaluated the role of pH, porous media size fraction, and flow interruptions on uranium transport. Rock cores drilled from the GTS were shipped to Los Alamos National Laboratory, characterized by x-ray diffraction and optical microscopy, and used in uranium batch sorption and column breakthrough experiments. A synthetic water was prepared that represented the porewater that would be present after groundwater interacts with bentonite backfill material near a nuclear waste package. Uranium was conservatively transported at pH 8.8. Significant adsorption and subsequent desorption was observed at pH ~ 7, with long desorption tails resulting after switching the column injection solution to uranium-free groundwater. Our experiments were designed to better interrogate this slow desorption behavior. A three-site model predicted sorption rate constants for a pH 7.2 solution with a 75-150 μm granodiorite fraction to be 3.5, 0.012, and 0.012 mL/g-h for the forward reactions and 0.49, 0.0025, and 0.001 h- 1 for the reverse reactions. Surface site densities were 1.3, 0.042, and 0.042 μmol/g for the first, second, and third sites, respectively. 10-year simulations show that including a slow binding site increases the arrival time of a uranium pulse by ~ 70%.

  12. Recent Advances in the Modeling of the Transport of Two-Plasmon-Decay Electrons in the 1-D Hydrodynamic Code LILAC

    NASA Astrophysics Data System (ADS)

    Delettrez, J. A.; Myatt, J. F.; Yaakobi, B.

    2015-11-01

    The modeling of the fast-electron transport in the 1-D hydrodynamic code LILAC was modified because of the addition of cross-beam-energy-transfer (CBET) in implosion simulations. Using the old fast-electron with source model CBET results in a shift of the peak of the hard x-ray (HXR) production from the end of the laser pulse, as observed in experiments, to earlier in the pulse. This is caused by a drop in the laser intensity of the quarter-critical surface from CBET interaction at lower densities. Data from simulations with the laser plasma simulation environment (LPSE) code will be used to modify the source algorithm in LILAC. In addition, the transport model in LILAC has been modified to include deviations from the straight-line algorithm and non-specular reflection at the sheath to take into account the scattering from collisions and magnetic fields in the corona. Simulation results will be compared with HXR emissions from both room-temperature plastic and cryogenic target experiments. This material is based upon work supported by the Department of Energy National Nuclear Security Administration under Award Number DE-NA0001944.

  13. PHT3D-UZF: A reactive transport model for variably-saturated porous media

    USGS Publications Warehouse

    Wu, Ming Zhi; Post, Vincent E. A.; Salmon, S. Ursula; Morway, Eric; Prommer, H.

    2016-01-01

    A modified version of the MODFLOW/MT3DMS-based reactive transport model PHT3D was developed to extend current reactive transport capabilities to the variably-saturated component of the subsurface system and incorporate diffusive reactive transport of gaseous species. Referred to as PHT3D-UZF, this code incorporates flux terms calculated by MODFLOW's unsaturated-zone flow (UZF1) package. A volume-averaged approach similar to the method used in UZF-MT3DMS was adopted. The PHREEQC-based computation of chemical processes within PHT3D-UZF in combination with the analytical solution method of UZF1 allows for comprehensive reactive transport investigations (i.e., biogeochemical transformations) that jointly involve saturated and unsaturated zone processes. Intended for regional-scale applications, UZF1 simulates downward-only flux within the unsaturated zone. The model was tested by comparing simulation results with those of existing numerical models. The comparison was performed for several benchmark problems that cover a range of important hydrological and reactive transport processes. A 2D simulation scenario was defined to illustrate the geochemical evolution following dewatering in a sandy acid sulfate soil environment. Other potential applications include the simulation of biogeochemical processes in variably-saturated systems that track the transport and fate of agricultural pollutants, nutrients, natural and xenobiotic organic compounds and micropollutants such as pharmaceuticals, as well as the evolution of isotope patterns.

  14. PHT3D-UZF: A Reactive Transport Model for Variably-Saturated Porous Media.

    PubMed

    Wu, Ming Zhi; Post, Vincent E A; Salmon, S Ursula; Morway, Eric D; Prommer, Henning

    2016-01-01

    A modified version of the MODFLOW/MT3DMS-based reactive transport model PHT3D was developed to extend current reactive transport capabilities to the variably-saturated component of the subsurface system and incorporate diffusive reactive transport of gaseous species. Referred to as PHT3D-UZF, this code incorporates flux terms calculated by MODFLOW's unsaturated-zone flow (UZF1) package. A volume-averaged approach similar to the method used in UZF-MT3DMS was adopted. The PHREEQC-based computation of chemical processes within PHT3D-UZF in combination with the analytical solution method of UZF1 allows for comprehensive reactive transport investigations (i.e., biogeochemical transformations) that jointly involve saturated and unsaturated zone processes. Intended for regional-scale applications, UZF1 simulates downward-only flux within the unsaturated zone. The model was tested by comparing simulation results with those of existing numerical models. The comparison was performed for several benchmark problems that cover a range of important hydrological and reactive transport processes. A 2D simulation scenario was defined to illustrate the geochemical evolution following dewatering in a sandy acid sulfate soil environment. Other potential applications include the simulation of biogeochemical processes in variably-saturated systems that track the transport and fate of agricultural pollutants, nutrients, natural and xenobiotic organic compounds and micropollutants such as pharmaceuticals, as well as the evolution of isotope patterns.

  15. The effect of modafinil on the rat dopamine transporter and dopamine receptors D1-D3 paralleling cognitive enhancement in the radial arm maze.

    PubMed

    Karabacak, Yasemin; Sase, Sunetra; Aher, Yogesh D; Sase, Ajinkya; Saroja, Sivaprakasam R; Cicvaric, Ana; Höger, Harald; Berger, Michael; Bakulev, Vasiliy; Sitte, Harald H; Leban, Johann; Monje, Francisco J; Lubec, Gert

    2015-01-01

    A series of drugs have been reported to increase memory performance modulating the dopaminergic system and herein modafinil was tested for its working memory (WM) enhancing properties. Reuptake inhibition of dopamine, serotonin (SERT) and norepinephrine (NET) by modafinil was tested. Sixty male Sprague-Dawley rats were divided into six groups (modafinil-treated 1-5-10 mg/kg body weight, trained and untrained and vehicle treated trained and untrained rats; daily injected intraperitoneally for a period of 10 days) and tested in a radial arm maze (RAM), a paradigm for testing spatial WM. Hippocampi were taken 6 h following the last day of training and complexes containing the unphosphorylated or phosphorylated dopamine transporter (DAT-CC and pDAT-CC) and complexes containing the D1-3 dopamine receptor subunits (D1-D3-CC) were determined. Modafinil was binding to the DAT but insignificantly to SERT or NET and dopamine reuptake was blocked specifically (IC50 = 11.11 μM; SERT 1547 μM; NET 182 μM). From day 8 (day 9 for 1 mg/kg body weight) modafinil was decreasing WM errors (WMEs) in the RAM significantly and remarkably at all doses tested as compared to the vehicle controls. WMEs were linked to the D2R-CC and the pDAT-CC. pDAT and D1-D3-CC levels were modulated significantly and modafinil was shown to enhance spatial WM in the rat in a well-documented paradigm at all the three doses and dopamine reuptake inhibition with subsequent modulation of D1-3-CC is proposed as a possible mechanism of action.

  16. \\A Gravity-Related Transport in Reactive Off-Axis Sputtering Deposition

    NASA Technical Reports Server (NTRS)

    Zhu, Shen; Su, C.-H.; Lehozeky, S. L.

    2000-01-01

    An experiment was designed to investigate the transport characterization of reactive off- axis sputtering deposition. Three transport regions were observed when the growth pressures vary from 5 mtorr to 150 mtorr. A new gravity-related phenomenon was revealed in film growth at relatively high growth pressures. This effect is related to the collision process or thermalization of transport species. This study also suggests a design for the substrate holder orientation in the off-axis sputtering system.

  17. Modification of the finite element heat and mass transfer code (FEHM) to model multicomponent reactive transport

    SciTech Connect

    Viswanathan, H.S.

    1996-08-01

    The finite element code FEHMN, developed by scientists at Los Alamos National Laboratory (LANL), is a three-dimensional finite element heat and mass transport simulator that can handle complex stratigraphy and nonlinear processes such as vadose zone flow, heat flow and solute transport. Scientists at LANL have been developing hydrologic flow and transport models of the Yucca Mountain site using FEHMN. Previous FEHMN simulations have used an equivalent Kd model to model solute transport. In this thesis, FEHMN is modified making it possible to simulate the transport of a species with a rigorous chemical model. Including the rigorous chemical equations into FEHMN simulations should provide for more representative transport models for highly reactive chemical species. A fully kinetic formulation is chosen for the FEHMN reactive transport model. Several methods are available to computationally implement a fully kinetic formulation. Different numerical algorithms are investigated in order to optimize computational efficiency and memory requirements of the reactive transport model. The best algorithm of those investigated is then incorporated into FEHMN. The algorithm chosen requires for the user to place strongly coupled species into groups which are then solved for simultaneously using FEHMN. The complete reactive transport model is verified over a wide variety of problems and is shown to be working properly. The new chemical capabilities of FEHMN are illustrated by using Los Alamos National Laboratory`s site scale model of Yucca Mountain to model two-dimensional, vadose zone {sup 14}C transport. The simulations demonstrate that gas flow and carbonate chemistry can significantly affect {sup 14}C transport at Yucca Mountain. The simulations also prove that the new capabilities of FEHMN can be used to refine and buttress already existing Yucca Mountain radionuclide transport studies.

  18. Upscaling Reactive Transport in Porous Media: Laboratory Visualizations and Stochastic Models

    NASA Astrophysics Data System (ADS)

    Oates, P.; Harvey, C. F.

    2007-12-01

    We present a field-scale model of reactive transport that describes the segregation and mixing of reactants at the small-scale by their joint distribution, thereby avoiding the nearly impossible task of explicitly resolving centimeter- scale patterns of reactant concentrations in field-scale models. We tested this model by collecting detailed quantitative images of colorimetric reactions during transport through translucent porous media. These novel experimental results reveal that: (1) The distributions of local solute concentrations are accurately parameterized by beta distributions; (2) The evolution of these distributions is predicted by coupling transport equations for the variance and covariance of local reactant concentrations with conventional transport and chemical reaction equations; and (3) The rate of concentration variance destruction, that drives chemical reaction, quickly equilibrates with the rate of variance production. We demonstrate this reactive-transport model for both our experimental results and through numerical simulation of double-Monod kinetic oxidation of hydrocarbons subject to linear adsorption.

  19. Coupled Reactive Transport Modeling of CO2 Injection in Mt. Simon Sandstone Formation, Midwest USA

    NASA Astrophysics Data System (ADS)

    Liu, F.; Lu, P.; Zhu, C.; Xiao, Y.

    2009-12-01

    CO2 sequestration in deep geological formations is one of the promising options for CO2 emission reduction. While several large scale CO2 injections in saline aquifers have shown to be successful for the short-term, there is still a lack of fundamental understanding on key issues such as CO2 storage capacity, injectivity, and security over multiple spatial and temporal scales that need to be addressed. To advance these understandings, we applied multi-phase coupled reactive mass transport modeling to investigate the fate of injected CO2 and reservoir responses to the injection into Mt. Simon Formation. We developed both 1-D and 2-D reactive transport models in a radial region of 10,000 m surrounding a CO2 injection well to represent the Mt. Simon sandstone formation, which is a major regional deep saline reservoir in the Midwest, USA. Supercritical CO2 is injected into the formation for 100 years, and the modeling continues till 10,000 years to monitor both short-term and long-term behavior of injected CO2 and the associated rock-fluid interactions. CO2 co-injection with H2S and SO2 is also simulated to represent the flue gases from coal gasification and combustion in the Illinois Basin. The injection of CO2 results in acidified zones (pH ~3 and 5) adjacent to the wellbore, causing progressive water-rock interactions in the surrounding region. In accordance with the extensive dissolution of authigenic K-feldspar, sequential precipitations of secondary carbonates and clay minerals are predicted in this zone. The vertical profiles of CO2 show fingering pattern from the top of the reservoir to the bottom due to the density variation of CO2-impregnated brine, which facilitate convection induced mixing and solubility trapping. Most of the injected CO2 remains within a radial distance of 2500 m at the end of 10,000 years and is sequestered and immobilized by solubility and residual trapping. Mineral trapping via secondary carbonates, including calcite, magnesite

  20. Geochemical & Physical Aquifer Property Heterogeneity: A Multiscale Sedimentologic Approach to Reactive Solute Transport

    SciTech Connect

    Murray, Chris; Allen-King, Richelle; Weissmann, Gary

    2006-06-01

    This project is testing the hypothesis that sedimentary lithofacies determine the geochemical and physical hydrologic properties that control reactive solute transport (Figure 1). We are testing that hypothesis for one site, a portion of the saturated zone at the Hanford Site (Ringold Formation), and for a model solute, carbon tetrachloride (CT). The representative geochemical and physical aquifer properties selected for quantification in the proposed project are the properties that control CT transport: hydraulic conductivity (K) and reactivity (sorption distribution coefficient, Kd, and anaerobic transformation rate constant, kn). We are combining observations at outcrop analog sites (to measure lithofacies dimensions and statistical relations) with measurements from archived and fresh core samples (for geochemical experiments and to provide additional constraint to the stratigraphic model) from the Ringold Formation to place local-scale lithofacies successions, and their distinct hydrologic property distributions, into the basinal context, thus allowing us to estimate the spatial distributions of properties that control reactive solute transport in the subsurface.

  1. Pore scale modeling of reactive transport involved in geologic CO2 sequestration

    SciTech Connect

    Kang, Qinjin; Lichtner, Peter C; Viswanathan, Hari S; Abdel-fattah, Amr I

    2009-01-01

    We apply a multi-component reactive transport lattice Boltzmann model developed in previolls studies to modeling the injection of a C02 saturated brine into various porous media structures at temperature T=25 and 80 C. The porous media are originally consisted of calcite. A chemical system consisting of Na+, Ca2+, Mg2+, H+, CO2(aq), and CI-is considered. The fluid flow, advection and diHusion of aqueous species, homogeneous reactions occurring in the bulk fluid, as weB as the dissolution of calcite and precipitation of dolomite are simulated at the pore scale. The effects of porous media structure on reactive transport are investigated. The results are compared with continuum scale modeling and the agreement and discrepancy are discussed. This work may shed some light on the fundamental physics occurring at the pore scale for reactive transport involved in geologic C02 sequestration.

  2. A reactive transport modelling approach to assess the leaching potential of hydraulic fracturing fluids associated with coal seam gas extraction

    NASA Astrophysics Data System (ADS)

    Mallants, Dirk; Simunek, Jirka; Gerke, Kirill

    2015-04-01

    Coal Seam Gas production generates large volumes of "produced" water that may contain compounds originating from the use of hydraulic fracturing fluids. Such produced water also contains elevated concentrations of naturally occurring inorganic and organic compounds, and usually has a high salinity. Leaching of produced water from storage ponds may occur as a result of flooding or containment failure. Some produced water is used for irrigation of specific crops tolerant to elevated salt levels. These chemicals may potentially contaminate soil, shallow groundwater, and groundwater, as well as receiving surface waters. This paper presents an application of scenario modelling using the reactive transport model for variably-saturated media HP1 (coupled HYDRUS-1D and PHREEQC). We evaluate the fate of hydraulic fracturing chemicals and naturally occurring chemicals in soil as a result of unintentional release from storage ponds or when produced water from Coal Seam Gas operations is used in irrigation practices. We present a review of exposure pathways and relevant hydro-bio-geo-chemical processes, a collation of physico-chemical properties of organic/inorganic contaminants as input to a set of generic simulations of transport and attenuation in variably saturated soil profiles. We demonstrate the ability to model the coupled processes of flow and transport in soil of contaminants associated with hydraulic fracturing fluids and naturally occurring contaminants.

  3. STOMP-ECKEChem: An Engineering Perspective on Reactive Transport in Geologic Media

    SciTech Connect

    White, Mark D.; Fang, Yilin

    2012-04-04

    ECKEChem (Equilibrium, Conservation, Kinetic Equation Chemistry) is a reactive transport module for the STOMP suite of multifluid subsurface flow and transport simulators that was developed from an engineering perspective. STOMP comprises a suite of operational modes that are distinguished by the solved coupled conservation equations with capabilities for a variety of subsurface applications (e.g., environmental remediation and stewardship, geologic sequestration of greenhouse gases, gas hydrate production, and oil shale production). The ECKEChem module was designed to provide integrated reactive transport capabilities across the suite of STOMP simulator operational modes. The initial application for the ECKEChem module was in the simulation of the mineralization reactions that occurred with the injection of supercritical carbon dioxide into deep Columbia River basalt formations, where it was implemented in the STOMP-CO2 simulator. The STOMP-ECKEChem solution approach to modeling reactive transport in multifluid geologic media is founded on an engineering perspective: (1) sequential non-iterative coupling between the flow and reactive transport is sufficient, (2) reactive transport can be modeled by operator splitting with local geochemistry and global transport, (3) geochemistry can be expressed as a system of coupled nonlinear equilibrium, conservation and kinetic equations, (4) a limited number of kinetic equation forms are used in geochemical practice. This chapter describes the conceptual approach to converting a geochemical reaction network into a series of equilibrium, conservation and kinetic equations, the implementation of ECKEChem in STOMP, the numerical solution approach, and a demonstration of the simulator on a complex application involving desorption of uranium from contaminated field-textured sediments.

  4. Reactive Transport Modeling: An Essential Tool and a New ResearchApproach for the Earth Sciences

    SciTech Connect

    Steefel, Carl I.; DePaolo, Donald J.; Lichtner, Peter C.

    2005-08-25

    Reactive transport modeling is an essential tool for the analysis of coupled physical, chemical, and biological processes in Earth systems, and has additional potential to better integrate the results from focused fundamental research on Earth materials. Appropriately designed models can describe the interactions of competing processes at a range of spatial and time scales, and hence are critical for connecting the advancing capabilities for materials characterization at the atomic scale with the macroscopic behavior of complex Earth systems. Reactive transport modeling has had a significant impact on the treatment of contaminant retardation in the subsurface, the description of elemental and nutrient fluxes between major Earth reservoirs, and in the treatment of deep Earth processes such as metamorphism and magma transport. Active topics of research include the development of pore scale and hybrid, or multiple continua, models to capture the scale dependence of coupled reactive transport processes. Frontier research questions, that are only now being addressed, include the effects of chemical microenvironments, coupled thermal mechanical chemical processes, controls on mineral fluid reaction rates in natural media, and scaling of reactive transport processes from the microscopic to pore to field scale.

  5. Reactive Gas transport in soil: Kinetics versus Local Equilibrium Approach

    NASA Astrophysics Data System (ADS)

    Geistlinger, Helmut; Jia, Ruijan

    2010-05-01

    Gas transport through the unsaturated soil zone was studied using an analytical solution of the gas transport model that is mathematically equivalent to the Two-Region model. The gas transport model includes diffusive and convective gas fluxes, interphase mass transfer between the gas and water phase, and biodegradation. The influence of non-equilibrium phenomena, spatially variable initial conditions, and transient boundary conditions are studied. The objective of this paper is to compare the kinetic approach for interphase mass transfer with the standard local equilibrium approach and to find conditions and time-scales under which the local equilibrium approach is justified. The time-scale of investigation was limited to the day-scale, because this is the relevant scale for understanding gas emission from the soil zone with transient water saturation. For the first time a generalized mass transfer coefficient is proposed that justifies the often used steady-state Thin-Film mass transfer coefficient for small and medium water-saturated aggregates of about 10 mm. The main conclusion from this study is that non-equilibrium mass transfer depends strongly on the temporal and small-scale spatial distribution of water within the unsaturated soil zone. For regions with low water saturation and small water-saturated aggregates (radius about 1 mm) the local equilibrium approach can be used as a first approximation for diffusive gas transport. For higher water saturation and medium radii of water-saturated aggregates (radius about 10 mm) and for convective gas transport, the non-equilibrium effect becomes more and more important if the hydraulic residence time and the Damköhler number decrease. Relative errors can range up to 100% and more. While for medium radii the local equilibrium approach describes the main features both of the spatial concentration profile and the time-dependence of the emission rate, it fails completely for larger aggregates (radius about 100 mm

  6. A COMSOL-GEMS interface for modeling coupled reactive-transport geochemical processes

    NASA Astrophysics Data System (ADS)

    Azad, Vahid Jafari; Li, Chang; Verba, Circe; Ideker, Jason H.; Isgor, O. Burkan

    2016-07-01

    An interface was developed between COMSOL MultiphysicsTM finite element analysis software and (geo)chemical modeling platform, GEMS, for the reactive-transport modeling of (geo)chemical processes in variably saturated porous media. The two standalone software packages are managed from the interface that uses a non-iterative operator splitting technique to couple the transport (COMSOL) and reaction (GEMS) processes. The interface allows modeling media with complex chemistry (e.g. cement) using GEMS thermodynamic database formats. Benchmark comparisons show that the developed interface can be used to predict a variety of reactive-transport processes accurately. The full functionality of the interface was demonstrated to model transport processes, governed by extended Nernst-Plank equation, in Class H Portland cement samples in high pressure and temperature autoclaves simulating systems that are used to store captured carbon dioxide (CO2) in geological reservoirs.

  7. Simulation of reactive geochemical transport in groundwater using a semi-analytical screening model

    NASA Astrophysics Data System (ADS)

    McNab, Walt W.

    1997-10-01

    A reactive geochemical transport model, based on a semi-analytical solution to the advective-dispersive transport equation in two dimensions, is developed as a screening tool for evaluating the impact of reactive contaminants on aquifer hydrogeochemistry. Because the model utilizes an analytical solution to the transport equation, it is less computationally intensive than models based on numerical transport schemes, is faster, and it is not subject to numerical dispersion effects. Although the assumptions used to construct the model preclude consideration of reactions between the aqueous and solid phases, thermodynamic mineral saturation indices are calculated to provide qualitative insight into such reactions. Test problems involving acid mine drainage and hydrocarbon biodegradation signatures illustrate the utility of the model in simulating essential hydrogeochemical phenomena.

  8. Multi-scale modeling of multi-component reactive transport in geothermal aquifers

    NASA Astrophysics Data System (ADS)

    Nick, Hamidreza M.; Raoof, Amir; Wolf, Karl-Heinz; Bruhn, David

    2014-05-01

    In deep geothermal systems heat and chemical stresses can cause physical alterations, which may have a significant effect on flow and reaction rates. As a consequence it will lead to changes in permeability and porosity of the formations due to mineral precipitation and dissolution. Large-scale modeling of reactive transport in such systems is still challenging. A large area of uncertainty is the way in which the pore-scale information controlling the flow and reaction will behave at a larger scale. A possible choice is to use constitutive relationships relating, for example the permeability and porosity evolutions to the change in the pore geometry. While determining such relationships through laboratory experiments may be limited, pore-network modeling provides an alternative solution. In this work, we introduce a new workflow in which a hybrid Finite-Element Finite-Volume method [1,2] and a pore network modeling approach [3] are employed. Using the pore-scale model, relevant constitutive relations are developed. These relations are then embedded in the continuum-scale model. This approach enables us to study non-isothermal reactive transport in porous media while accounting for micro-scale features under realistic conditions. The performance and applicability of the proposed model is explored for different flow and reaction regimes. References: 1. Matthäi, S.K., et al.: Simulation of solute transport through fractured rock: a higher-order accurate finite-element finite-volume method permitting large time steps. Transport in porous media 83.2 (2010): 289-318. 2. Nick, H.M., et al.: Reactive dispersive contaminant transport in coastal aquifers: Numerical simulation of a reactive Henry problem. Journal of contaminant hydrology 145 (2012), 90-104. 3. Raoof A., et al.: PoreFlow: A Complex pore-network model for simulation of reactive transport in variably saturated porous media, Computers & Geosciences, 61, (2013), 160-174.

  9. Simulating MODFLOW-based reactive transport under radially symmetric flow conditions.

    PubMed

    Wallis, Ilka; Prommer, Henning; Post, Vincent; Vandenbohede, Alexander; Simmons, Craig T

    2013-01-01

    Radially symmetric flow and solute transport around point sources and sinks is an important specialized topic of groundwater hydraulics. Analysis of radial flow fields is routinely used to determine heads and flows in the vicinity of point sources or sinks. Increasingly, studies also consider solute transport, biogeochemical processes, and thermal changes that occur in the vicinity of point sources/sinks. Commonly, the analysis of hydraulic processes involves numerical or (semi-) analytical modeling methods. For the description of solute transport, analytical solutions are only available for the most basic transport phenomena. Solving advanced transport problems numerically is often associated with a significant computational burden. However, where axis-symmetry applies, computational cost can be decreased substantially in comparison with full three-dimensional (3D) solutions. In this study, we explore several techniques of simulating conservative and reactive transport within radial flow fields using MODFLOW as the flow simulator, based on its widespread use and ability to be coupled with multiple solute and reactive transport codes of different complexity. The selected transport simulators are MT3DMS and PHT3D. Computational efficiency and accuracy of the approaches are evaluated through comparisons with full 2D/3D model simulations, analytical solutions, and benchmark problems. We demonstrate that radial transport models are capable of accurately reproducing a wide variety of conservative and reactive transport problems provided that an adequate spatial discretization and advection scheme is selected. For the investigated test problems, the computational load was substantially reduced, with the improvement varying, depending on the complexity of the considered reaction network.

  10. Semi-analytical Solution of One-dimensional Multispecies Reactive Transport in a Permeable Reactive Barrier-aquifer System

    NASA Astrophysics Data System (ADS)

    Mieles, J. M.; Zhan, H.

    2010-12-01

    Permeable reactive barriers (PRBs) have been accepted by the EPA as an effective groundwater remediation technology. Effective implementation of this in-situ technology requires accurate site characterization to identify the chemicals of concern (COCs) present, their interactions (if any), and their required residence time in the PRB to achieve regulatory concentrations at the point of compliance (POC). Therefore, minimizing performance uncertainties in the design phase is key. Among these uncertainties determining the required PRB thickness is the most important and has been examined in other studies. Less attention, however, has been devoted to developing a practical yet rigorous tool for modeling multi-species reactive transport in the barrier-aquifer system. In this study Park and Zhan’s [2009] mass conservative semi-analytical solution - developed to calculate the required PRB thickness based on the decay of one species - is expanded to four reactive species. For example, the expanded solution could be used to model the degradation pathway from tetrachloroethylene (PCE) to vinyl chloride (VC). The solution is presented in two forms: The steady-state solution programmed into Excel can quickly assist designers in determining the required PRB thickness so that all COCs involved in the degradation pathway achieve regulatory limits at the POC. The second form is the transient solution which is solved by numerically inverting the Laplace transform. The semi-analytical solution presented in this study has several advantages over prior solutions. For example, the influent and effluent boundary conditions of the PRB are mass conservative and both dispersion and decay rate differences between the PRB and aquifer are considered. In addition, the transient solution allows for different retardation factors to be considered in both transport media and for each species.

  11. Phase behavior and reactive transport of partial melt in heterogeneous mantle model

    NASA Astrophysics Data System (ADS)

    Jordan, J.; Hesse, M. A.

    2013-12-01

    The reactive transport of partial melt is the key process that leads to the chemical and physical differentiation of terrestrial planets and smaller celestial bodies. The essential role of the lithological heterogeneities during partial melting of the mantle is increasingly recognized. How far can enriched melts propagate while interacting with the ambient mantle? Can the melt flow emanating from a fertile heterogeneity be localized through a reactive infiltration feedback in a model without exogenous factors or contrived initial conditions? A full understanding of the role of heterogeneities requires reactive melt transport models that account for the phase behavior of major elements. Previous work on reactive transport in the mantle focuses on trace element partitioning; we present the first nonlinear chromatographic analysis of reactive melt transport in systems with binary solid solution. Our analysis shows that reactive melt transport in systems with binary solid solution leads to the formation of two separate reaction fronts: a slow melting/freezing front along which enthalpy change is dominant and a fast dissolution/precipitation front along which compositional changes are dominated by an ion-exchange process over enthalpy change. An intermediate state forms between these two fronts with a bulk-rock composition and enthalpy that are not necessarily bounded by the bulk-rock composition and enthalpy of either the enriched heterogeneity or the depleted ambient mantle. The formation of this intermediate state makes it difficult to anticipate the porosity changes and hence the stability of reaction fronts. Therefore, we develop a graphical representation for the solution that allows identification of the intermediate state by inspection, for all possible bulk-rock compositions and enthalpies of the heterogeneity and the ambient mantle. We apply the analysis to the partial melting of an enriched heterogeneity. This leads to the formation of moving precipitation

  12. Core-flood experiment for transport of reactive fluids in rocks.

    PubMed

    Ott, H; de Kloe, K; van Bakel, M; Vos, F; van Pelt, A; Legerstee, P; Bauer, A; Eide, K; van der Linden, A; Berg, S; Makurat, A

    2012-08-01

    Investigation of the transport of reactive fluids in porous rocks is an intriguing but challenging task and relevant in several areas of science and engineering such as geology, hydrogeology, and petroleum engineering. We designed and constructed an experimental setup to investigate physical and chemical processes caused by the flow of reactive and volatile fluids such as supercritical CO(2) and/or H(2)S in geological formations. Potential applications are geological sequestration of CO(2) in the frame of carbon capture and storage and acid-gas injection for sulfur disposal and/or enhanced oil recovery. The present paper outlines the design criteria and the realization of reactive transport experiments on the laboratory scale. We focus on the spatial and time evolution of rock and fluid composition as a result of chemical rock fluid interaction and the coupling of chemistry and fluid flow in porous rocks.

  13. Maximum likelihood Bayesian model averaging and its predictive analysis for groundwater reactive transport models

    SciTech Connect

    Lu, Dan; Ye, Ming; Curtis, Gary P.

    2015-08-01

    While Bayesian model averaging (BMA) has been widely used in groundwater modeling, it is infrequently applied to groundwater reactive transport modeling because of multiple sources of uncertainty in the coupled hydrogeochemical processes and because of the long execution time of each model run. To resolve these problems, this study analyzed different levels of uncertainty in a hierarchical way, and used the maximum likelihood version of BMA, i.e., MLBMA, to improve the computational efficiency. Our study demonstrates the applicability of MLBMA to groundwater reactive transport modeling in a synthetic case in which twenty-seven reactive transport models were designed to predict the reactive transport of hexavalent uranium (U(VI)) based on observations at a former uranium mill site near Naturita, CO. Moreover, these reactive transport models contain three uncertain model components, i.e., parameterization of hydraulic conductivity, configuration of model boundary, and surface complexation reactions that simulate U(VI) adsorption. These uncertain model components were aggregated into the alternative models by integrating a hierarchical structure into MLBMA. The modeling results of the individual models and MLBMA were analyzed to investigate their predictive performance. The predictive logscore results show that MLBMA generally outperforms the best model, suggesting that using MLBMA is a sound strategy to achieve more robust model predictions relative to a single model. MLBMA works best when the alternative models are structurally distinct and have diverse model predictions. When correlation in model structure exists, two strategies were used to improve predictive performance by retaining structurally distinct models or assigning smaller prior model probabilities to correlated models. Since the synthetic models were designed using data from the Naturita site, the results of this study are expected to provide guidance for real-world modeling. Finally, limitations of

  14. Maximum likelihood Bayesian model averaging and its predictive analysis for groundwater reactive transport models

    DOE PAGES

    Lu, Dan; Ye, Ming; Curtis, Gary P.

    2015-08-01

    While Bayesian model averaging (BMA) has been widely used in groundwater modeling, it is infrequently applied to groundwater reactive transport modeling because of multiple sources of uncertainty in the coupled hydrogeochemical processes and because of the long execution time of each model run. To resolve these problems, this study analyzed different levels of uncertainty in a hierarchical way, and used the maximum likelihood version of BMA, i.e., MLBMA, to improve the computational efficiency. Our study demonstrates the applicability of MLBMA to groundwater reactive transport modeling in a synthetic case in which twenty-seven reactive transport models were designed to predict themore » reactive transport of hexavalent uranium (U(VI)) based on observations at a former uranium mill site near Naturita, CO. Moreover, these reactive transport models contain three uncertain model components, i.e., parameterization of hydraulic conductivity, configuration of model boundary, and surface complexation reactions that simulate U(VI) adsorption. These uncertain model components were aggregated into the alternative models by integrating a hierarchical structure into MLBMA. The modeling results of the individual models and MLBMA were analyzed to investigate their predictive performance. The predictive logscore results show that MLBMA generally outperforms the best model, suggesting that using MLBMA is a sound strategy to achieve more robust model predictions relative to a single model. MLBMA works best when the alternative models are structurally distinct and have diverse model predictions. When correlation in model structure exists, two strategies were used to improve predictive performance by retaining structurally distinct models or assigning smaller prior model probabilities to correlated models. Since the synthetic models were designed using data from the Naturita site, the results of this study are expected to provide guidance for real-world modeling. Finally

  15. Maximum likelihood Bayesian model averaging and its predictive analysis for groundwater reactive transport models

    USGS Publications Warehouse

    Curtis, Gary P.; Lu, Dan; Ye, Ming

    2015-01-01

    While Bayesian model averaging (BMA) has been widely used in groundwater modeling, it is infrequently applied to groundwater reactive transport modeling because of multiple sources of uncertainty in the coupled hydrogeochemical processes and because of the long execution time of each model run. To resolve these problems, this study analyzed different levels of uncertainty in a hierarchical way, and used the maximum likelihood version of BMA, i.e., MLBMA, to improve the computational efficiency. This study demonstrates the applicability of MLBMA to groundwater reactive transport modeling in a synthetic case in which twenty-seven reactive transport models were designed to predict the reactive transport of hexavalent uranium (U(VI)) based on observations at a former uranium mill site near Naturita, CO. These reactive transport models contain three uncertain model components, i.e., parameterization of hydraulic conductivity, configuration of model boundary, and surface complexation reactions that simulate U(VI) adsorption. These uncertain model components were aggregated into the alternative models by integrating a hierarchical structure into MLBMA. The modeling results of the individual models and MLBMA were analyzed to investigate their predictive performance. The predictive logscore results show that MLBMA generally outperforms the best model, suggesting that using MLBMA is a sound strategy to achieve more robust model predictions relative to a single model. MLBMA works best when the alternative models are structurally distinct and have diverse model predictions. When correlation in model structure exists, two strategies were used to improve predictive performance by retaining structurally distinct models or assigning smaller prior model probabilities to correlated models. Since the synthetic models were designed using data from the Naturita site, the results of this study are expected to provide guidance for real-world modeling. Limitations of applying MLBMA to the

  16. Triheptanoin for glucose transporter type I deficiency (G1D): Modulation of human ictogenesis, cerebral metabolic rate and cognitive indices by a food supplement

    PubMed Central

    Pascual, Juan M.; Liu, Peiying; Mao, Deng; Kelly, Dorothy; Hernandez, Ana; Sheng, Min; Good, Levi B.; Ma, Qian; Marin-Valencia, Isaac; Zhang, Xuchen; Park, Jason Y.; Hynan, Linda S.; Stavinoha, Peter; Roe, Charles R.; Lu, Hanzhang

    2015-01-01

    Objective G1D is commonly associated with electrographic spike-wave and - less-noticeably – with absence seizures. The G1D syndrome has long been attributed to energy (i.e., ATP-synthetic) failure, as have experimental, toxic-rodent epilepsies to impaired brain metabolism and tricarboxylic acid (TCA) cycle intermediate depletion. Indeed, a (seldom-acknowledged) function of glucose and other substrates is the generation of brain TCAs via carbon-donor reactions collectively named anaplerosis. However, TCAs are preserved in murine G1D. This renders inferences about energy failure premature and suggests a different hypothesis, also grounded on our findings, that consumption of alternate TCA precursors is stimulated, potentially detracting from other functions. Second, common ketogenic diets can ameliorate G1D seizures, but lead to a therapeutically-counterintuitive reduction in blood glucose available to the brain, and they can prove ineffective in 1/3 of cases. While developing G1D treatments, all of this motivated us to: a) uphold (rather than attenuate) the residual brain glucose flux that all G1D patients possess; and b) stimulate the TCA cycle, including anaplerosis. Therefore, we tested the medium-chain triglyceride triheptanoin, a widely-used medical food supplement that can fulfill both of these metabolic roles. The rationale is that ketone bodies derived from ketogenic diets are not anaplerotic, in contrast with triheptanoin metabolites, as we have shown in the G1D mouse brain. Design We supplemented the regular diet of a case series of G1D patients with food-grade triheptanoin. First we confirmed that, despite their frequent electroencephalographic (EEG) presence as spike-waves, most seizures are rarely visible, such that perceptions by patients or others are inadequate for treatment evaluation. Thus, we used EEG, quantitative neuropsychological, blood analytical, and MRI cerebral metabolic rate measurements as main outcomes. Setting Academic and

  17. Multicomponent reactive transport in an in situ zero-valent iron cell

    SciTech Connect

    Yabusaki, Steven B. ); Cantrell, Kirk J. ); Sass, Bruce; Steefel, Carl

    2000-12-01

    Data collected from a field study of in situ zero-valent iron treatment for TCE were analyzed in the context of coupled transport and reaction processes. The focus of this analysis was to understand the behavior of chemical components, including contaminants, in groundwater transported through the iron cell of a pilot-scale funnel and gate treatment system. A multicomponent reactive transport simulator was used to simultaneously model mobile and nonmobile components undergoing equilibrium and kinetic reactions including TCE degradation, parallel iron dissolution reactions, precipitation of secondary minerals, and complexation reactions. The resulting mechanistic model of coupled processes reproduced solution chemistry behavior observed in the iron cell with a minimum of calibration. These observations included the destruction of TCE and cis-1,2-DCE; increases in pH and hydrocarbons; and decreases in EH, alkalinity, dissolved O2 and CO2, and major ions (i.e., Ca, Mg, Cl, sulfate, nitrate). Mineral precipitation in the iron zone was critical to correctly predicting these behaviors. The dominant precipitation products were ferrous hydroxide, siderite, aragonite, brucite, and iron sulfide. In the first few centimeters of the reactive iron cell, these precipitation products are predicted to account for a 3% increase in mineral volume per year, which could have implications for the longevity of favorable barrier hydraulics and reactivity. The inclusion of transport was key to understanding the interplay between rates of transport and rates of reaction in the field.

  18. Coupling Isotopic Fractionation to Multiple-Continuum Reactive Transport Models of Biogeochemical Systems

    NASA Astrophysics Data System (ADS)

    Sonnenthal, E. L.; Wanner, C.

    2014-12-01

    Stable isotopic systems often show an unexpected range in observed fractionation factors associated with biogeochemical systems. In particular, the ranges in such isotopic systems as Cr, Ca, Li, and C have often been attributed to kinetic effects as well as different biogeochemical mechanisms. Reactive transport models developed to capture the sub-micron-scale transport and reaction processes within the macroscale system (e.g., biofilm to cm-scale) have been successful in simulating the biogeochemical processes associated with bacterial growth and the resultant changes in pore-fluid chemistry and redox conditions. Once such multicontinuum reactive transport models are extended to include equilibrium and kinetic isotopic fractionation, diffusive transport, and fluid-gas equilibria, it becomes possible to quantitatively interpret the isotopic changes observed in experimental and natural or engineered biogeochemical systems. We combine a solid-solution approach for isotopic substitution in minerals with the multiple-continuum reactive-transport approach to interpret the effective fractionation factor observed in experimental systems. Although such systems often have poorly constrained inputs (such as the equilibrium fractionation factor and many of the parameters associated with bacterial growth), by combining several independent contraints on reaction rates (such as lactate consumption, 13C/12C and 87Sr/86Sr in calcite), the range of possible interpretations can often be greatly narrowed. Here we present examples of the modeling approaches and their application to experimental systems to examine why the observed fractionation factors are often different from the theoretical values.

  19. An alternative to fully coupled reactive transport simulations for long-term prediction of chemical reactions in complex geological systems

    NASA Astrophysics Data System (ADS)

    De Lucia, Marco; Kempka, Thomas; Kühn, Michael

    2014-05-01

    Fully-coupled reactive transport simulations involving multiphase hydrodynamics and chemical reactions in heterogeneous settings are extremely challenging from a computational point of view. This often leads to oversimplification of the investigated system: coarse spatial discretization, to keep the number of elements in the order of few thousands; simplified chemistry, disregarding many potentially important reactions. A novel approach for coupling non-reactive hydrodynamic simulations with the outcome of single batch geochemical simulations was therefore introduced to assess the potential long-term mineral trapping at the Ketzin pilot site for underground CO2 storage in Germany [1],[2]. The advantage of the coupling is the ability to use multi-million grid non-reactive hydrodynamics simulations on one side and few batch 0D geochemical simulations on the other, so that the complexity of both systems does not need to be reduced. This contribution shows the approach which was taken to validate this simplified coupling scheme. The procedure involved batch simulations of the reference geochemical model, then performing both non-reactive and fully coupled 1D and 3D reactive transport simulations and finally applying the simplified coupling scheme based on the non-reactive and geochemical batch model. The TOUGHREACT/ECO2N [3] simulator was adopted for the validation. The degree of refinement of the spatial grid and the complexity and velocity of the mineral reactions, along with a cut-off value for the minimum concentration of dissolved CO2 allowed to originate precipitates in the simplified approach were found out to be the governing parameters for the convergence of the two schemes. Systematic discrepancies between the approaches are not reducible, simply because there is no feedback between chemistry and hydrodynamics, and can reach 20 % - 30 % in unfavourable cases. However, even such discrepancy is completely acceptable, in our opinion, given the amount of

  20. Reactive transport model of the formation of oxide-type Ni-laterite profiles (Punta Gorda, Moa Bay, Cuba)

    NASA Astrophysics Data System (ADS)

    Domènech, Cristina; Galí, Salvador; Villanova-de-Benavent, Cristina; Soler, Josep M.; Proenza, Joaquín A.

    2017-01-01

    Oxide-type Ni-laterite deposits are characterized by a dominant limonite zone with goethite as the economically most important Ni ore mineral and a thin zone of hydrous Mg silicate-rich saprolite beneath the magnesium discontinuity. Fe, less soluble, is mainly retained forming goethite, while Ni is redeposited at greater depth in a Fe(III) and Ni-rich serpentine (serpentine II) or in goethite, where it adsorbs or substitutes for Fe in the mineral structure. Here, a 1D reactive transport model, using CrunchFlow, of Punta Gorda oxide-type Ni-laterite deposit (Moa Bay, Cuba) formation is presented. The model reproduces the formation of the different laterite horizons in the profile from an initial, partially serpentinized peridotite, in 106 years, validating the conceptual model of the formation of this kind of deposits in which a narrow saprolite horizon rich in Ni-bearing serpentine is formed above peridotite parent rock and a thick limonite horizon is formed over saprolite. Results also confirm that sorption of Ni onto goethite can explain the weight percent of Ni found in the Moa goethite. Sensitivity analyses accounting for the effect of key parameters (composition, dissolution rate, carbonate concentration, quartz precipitation) on the model results are also presented. It is found that aqueous carbonate concentration and quartz precipitation significantly affects the laterization process rate, while the effect of the composition of secondary serpentine or of mineral dissolution rates is minor. The results of this reactive transport modeling have proven useful to validate the conceptual models derived from field observations.

  1. Moving from Batch to Field Using the RT3D Reactive Transport Modeling System

    NASA Astrophysics Data System (ADS)

    Clement, T. P.; Gautam, T. R.

    2002-12-01

    The public domain reactive transport code RT3D (Clement, 1997) is a general-purpose numerical code for solving coupled, multi-species reactive transport in saturated groundwater systems. The code uses MODFLOW to simulate flow and several modules of MT3DMS to simulate the advection and dispersion processes. RT3D employs the operator-split strategy which allows the code solve the coupled reactive transport problem in a modular fashion. The coupling between reaction and transport is defined through a separate module where the reaction equations are specified. The code supports a versatile user-defined reaction option that allows users to define their own reaction system through a Fortran-90 subroutine, known as the RT3D-reaction package. Further a utility code, known as BATCHRXN, allows the users to independently test and debug their reaction package. To analyze a new reaction system at a batch scale, users should first run BATCHRXN to test the ability of their reaction package to model the batch data. After testing, the reaction package can simply be ported to the RT3D environment to study the model response under 1-, 2-, or 3-dimensional transport conditions. This paper presents example problems that demonstrate the methods for moving from batch to field-scale simulations using BATCHRXN and RT3D codes. The first example describes a simple first-order reaction system for simulating the sequential degradation of Tetrachloroethene (PCE) and its daughter products. The second example uses a relatively complex reaction system for describing the multiple degradation pathways of Tetrachloroethane (PCA) and its daughter products. References 1) Clement, T.P, RT3D - A modular computer code for simulating reactive multi-species transport in 3-Dimensional groundwater aquifers, Battelle Pacific Northwest National Laboratory Research Report, PNNL-SA-28967, September, 1997. Available at: http://bioprocess.pnl.gov/rt3d.htm.

  2. Application of a data assimilation method via an ensemble Kalman filter to reactive urea hydrolysis transport modeling

    SciTech Connect

    Juxiu Tong; Bill X. Hu; Hai Huang; Luanjin Guo; Jinzhong Yang

    2014-03-01

    With growing importance of water resources in the world, remediations of anthropogenic contaminations due to reactive solute transport become even more important. A good understanding of reactive rate parameters such as kinetic parameters is the key to accurately predicting reactive solute transport processes and designing corresponding remediation schemes. For modeling reactive solute transport, it is very difficult to estimate chemical reaction rate parameters due to complex processes of chemical reactions and limited available data. To find a method to get the reactive rate parameters for the reactive urea hydrolysis transport modeling and obtain more accurate prediction for the chemical concentrations, we developed a data assimilation method based on an ensemble Kalman filter (EnKF) method to calibrate reactive rate parameters for modeling urea hydrolysis transport in a synthetic one-dimensional column at laboratory scale and to update modeling prediction. We applied a constrained EnKF method to pose constraints to the updated reactive rate parameters and the predicted solute concentrations based on their physical meanings after the data assimilation calibration. From the study results we concluded that we could efficiently improve the chemical reactive rate parameters with the data assimilation method via the EnKF, and at the same time we could improve solute concentration prediction. The more data we assimilated, the more accurate the reactive rate parameters and concentration prediction. The filter divergence problem was also solved in this study.

  3. Upscaling multi-component reactive transport in presence of connected subsurface structures

    NASA Astrophysics Data System (ADS)

    Willmann, M.; Mañé, R.; Tyukhova, A.

    2015-12-01

    Heterogeneity in hydraulic conductivity leads to incomplete mixing. Upscaling using the dispersion tensor in the advection-dispersion equation overestimates local mixing. Modelling multi-component reactive transport leads to an overestimation of reaction rates and overall reactions. Multi-rate mass transfer was shown previously to better represent mixing. But it is still unclear under what conditions this linear model is able to represent the underlying non-linear process. We study explicit multi-component transport in heterogeneous aquifers for the example of calcite-dissolution. We compare different types of heterogeneity from intermediately well connected (multigaussian) fields to very well connected fields. The fundamental difference stems from their connectivity structure. We observe for the well connected field different dominating channels with an almost uniform advective velocity while the multigaussian fields show dominating channels with a varying advective velocity. Then, we compare our results with an effective reactive mass transfer model where the distribution of exchanges rates or the memory function are derived from information of the hydraulic conductivity field only. We see that reactive multi-rate models show a good agreement for the well connected fields where the connected channels are more or less homogeneous and the immobile inclusions are of more or less equal size. We find connectivity important for upscaling reactive transport in highly heterogeneous conductivity fields.

  4. Quantifying Fluxes of Chemical and Biological Species in Great Lakes Watersheds: A Reactive Transport Modeling Framework

    NASA Astrophysics Data System (ADS)

    Niu, J.; Phanikumar, M. S.

    2012-12-01

    Understanding and quantifying the interactions between hydro-climatic processes and the fate and transport of aquatic pollutants and the resultant threats to human and ecosystem health is a high priority research area in many parts of the world. In the Great Lakes region, harmful algal blooms, increased beach closures due to microbiological pollution and drinking water related issues continue to be causes for concern in recent years highlighting the need for accurate transport models. In this presentation we describe the development of a watershed-scale multi-component reactive transport modeling framework to describe fluxes of nutrients and bacteria exported to the Great Lakes. We describe an operator-splitting strategy combined with a particle transport modeling approach with reactions to describe transport in different hydrologic units with interactions between domains. The algorithms are tested using analytical solutions (where available), data from plot-scale experiments and monitoring data from watersheds in the Great Lakes region.

  5. Illuminating reactive microbial transport in saturated porous media: Demonstration of a visualization method and conceptual transport model

    NASA Astrophysics Data System (ADS)

    Oates, Peter M.; Castenson, Catherine; Harvey, Charles F.; Polz, Martin; Culligan, Patricia

    2005-05-01

    We demonstrate a method to study reactive microbial transport in saturated translucent porous media using the bacteria Pseudomonas fluorescens 5RL genetically engineered to carry a plasmid with bioluminescence genes inducible by salicylate. Induced bacteria were injected into a cryolite grain filled chamber saturated with a sterile non-growth-promoting (phosphorus limited) chemical mixture containing salicylate as an aromatic hydrocarbon analogue. The amount of light produced by the bacteria serves as an estimator of the relative efficiency of aerobic biodegradation since bioluminescence is dependent on both salicylate and oxygen but only consumes oxygen. Bioluminescence was captured with a digital camera and analyzed to study the evolving spatial pattern of the bulk oxygen consuming reactions. As fluid flow transported the bacteria through the chamber, bioluminescence was observed to initially increase until an oxygen depletion zone developed behind the advective front. Bacterial transport was modeled with the advection dispersion equation and oxygen concentration was modeled assuming bacterial consumption via Monod kinetics with consideration of additional effects of rate-limited mass transfer from residual gas bubbles. Consistent with previous measurements, bioluminescence was considered proportional to oxygen consumed. Using the observed bioluminescence, model parameters were fit that were consistent with literature values and produced results in good agreement with the experimental data. These findings demonstrate potential for using this method to investigate the complex spatial and temporal dynamics of reactive microbial transport in saturated porous media.

  6. Mineralogical compositions of aquifer matrix as necessary initial conditions in reactive contaminant transport models

    NASA Astrophysics Data System (ADS)

    Zhu, Chen; Burden, David S.

    2001-10-01

    Mineralogical compositions and their spatial distributions are important initial conditions for reactive transport modeling. However, popular Kd-based "reactive" transport models only require contaminant concentrations in the pore fluids as initial conditions, and minerals implicitly represent infinite sources and sinks in these models. That situation results in a general neglect of mineralogical characterization in site investigations. This study uses a coupled multi-component reactive mass transport model to predict the natural attenuation of a ground water plume at a uranium mill tailings site in western USA. Numerous ground water geochemistry data are available at this site, but mineralogical data are sketchy. Even given the well-defined pore fluid chemistry, variations of secondary mineral species and mineral abundances in the aquifer resulted in significantly different modeling outcomes. Results show that the amount of calcite in the aquifer determines the distances of plume migration. The possible presence of jurbanite, an aluminum sulfate phase, can store acidity temporarily but cause more severe contamination on a later date. The surfaces of iron oxyhydroxides can store significant amounts of sulfate and protons and serve as a second source for prolonged contamination. These simulations under field conditions illustrate that mineralogical compositions are an essential requirement for accurate prediction of contaminant fate and transport.

  7. Mineralogical compositions of aquifer matrix as necessary initial conditions in reactive contaminant transport models.

    PubMed

    Zhu, C; Burden, D S

    2001-10-01

    Mineralogical compositions and their spatial distributions are important initial conditions for reactive transport modeling. However, popular Kd-based "reactive" transport models only require contaminant concentrations in the pore fluids as initial conditions, and minerals implicitly represent infinite sources and sinks in these models. That situation results in a general neglect of mineralogical characterization in site investigations. This study uses a coupled multi-component reactive mass transport model to predict the natural attenuation of a ground water plume at a uranium mill tailings site in western USA. Numerous ground water geochemistry data are available at this site, but mineralogical data are sketchy. Even given the well-defined pore fluid chemistry, variations of secondary mineral species and mineral abundances in the aquifer resulted in significantly different modeling outcomes. Results show that the amount of calcite in the aquifer determines the distances of plume migration. The possible presence of jurbanite, an aluminum sulfate phase, can store acidity temporarily but cause more severe contamination on a later date. The surfaces of iron oxyhydroxides can store significant amounts of sulfate and protons and serve as a second source for prolonged contamination. These simulations under field conditions illustrate that mineralogical compositions are an essential requirement for accurate prediction of contaminant fate and transport.

  8. Reactive Transport Modeling of Microbe-mediated Fe (II) Oxidation for Enhanced Oil Recovery

    NASA Astrophysics Data System (ADS)

    Surasani, V.; Li, L.

    2011-12-01

    Microbially Enhanced Oil Recovery (MEOR) aims to improve the recovery of entrapped heavy oil in depleted reservoirs using microbe-based technology. Reservoir ecosystems often contain diverse microbial communities those can interact with subsurface fluids and minerals through a network of nutrients and energy fluxes. Microbe-mediated reactions products include gases, biosurfactants, biopolymers those can alter the properties of oil and interfacial interactions between oil, brine, and rocks. In addition, the produced biomass and mineral precipitates can change the reservoir permeability profile and increase sweeping efficiency. Under subsurface conditions, the injection of nitrate and Fe (II) as the electron acceptor and donor allows bacteria to grow. The reaction products include minerals such as Fe(OH)3 and nitrogen containing gases. These reaction products can have large impact on oil and reservoir properties and can enhance the recovery of trapped oil. This work aims to understand the Fe(II) oxidation by nitrate under conditions relevant to MEOR. Reactive transport modeling is used to simulate the fluid flow, transport, and reactions involved in this process. Here we developed a complex reactive network for microbial mediated nitrate-dependent Fe (II) oxidation that involves both thermodynamic controlled aqueous reactions and kinetic controlled Fe (II) mineral reaction. Reactive transport modeling is used to understand and quantify the coupling between flow, transport, and reaction processes. Our results identify key parameter controls those are important for the alteration of permeability profile under field conditions.

  9. ParFlow.RT: Development and Verification of a New Reactive Transport Model

    NASA Astrophysics Data System (ADS)

    Beisman, J. J., III

    2015-12-01

    In natural subsurface systems, total elemental fluxes are often heavily influenced by areas of disproportionately high reaction rates. These pockets of high reaction rates tend to occur at interfaces, such as the hyporheic zone, where a hydrologic flowpath converges with either a chemically distinct hydrologic flowpath or a reactive substrate. Understanding the affects that these highly reactive zones have on the behavior of shallow subsurface systems is integral to the accurate quantification of nutrient fluxes and biogeochemical cycling. Numerical simulations of these systems may be able to offer some insight. To that end, we have developed a new reactive transport model, ParFlow.RT, by coupling the parallel flow and transport code ParFlow with the geochemical engines of both PFLOTRAN and CrunchFlow. The coupling was accomplished via the Alquimia biogeochemistry API, which provides a unified interface to several geochemical codes and allows a relatively simple implementation of advanced geochemical functionality in flow and transport codes. This model uses an operator-splitting approach, where the transport and reaction steps are solved separately. Here, we present the details of this new model, and the results of verification simulations and biogeochemical cycling simulations of the DOE's East River field site outside of Gothic, CO.

  10. Reprint of : Connection between wave transport through disordered 1D waveguides and energy density inside the sample: A maximum-entropy approach

    NASA Astrophysics Data System (ADS)

    Mello, Pier A.; Shi, Zhou; Genack, Azriel Z.

    2016-08-01

    We study the average energy - or particle - density of waves inside disordered 1D multiply-scattering media. We extend the transfer-matrix technique that was used in the past for the calculation of the intensity beyond the sample to study the intensity in the interior of the sample by considering the transfer matrices of the two segments that form the entire waveguide. The statistical properties of the two disordered segments are found using a maximum-entropy ansatz subject to appropriate constraints. The theoretical expressions are shown to be in excellent agreement with 1D transfer-matrix simulations.

  11. Abiotic/biotic coupling in the rhizosphere: a reactive transport modeling analysis

    USGS Publications Warehouse

    Lawrence, Corey R.; Steefel, Carl; Maher, Kate

    2014-01-01

    A new generation of models is needed to adequately simulate patterns of soil biogeochemical cycling in response changing global environmental drivers. For example, predicting the influence of climate change on soil organic matter storage and stability requires models capable of addressing complex biotic/abiotic interactions of rhizosphere and weathering processes. Reactive transport modeling provides a powerful framework simulating these interactions and the resulting influence on soil physical and chemical characteristics. Incorporation of organic reactions in an existing reactive transport model framework has yielded novel insights into soil weathering and development but much more work is required to adequately capture root and microbial dynamics in the rhizosphere. This endeavor provides many advantages over traditional soil biogeochemical models but also many challenges.

  12. Coupling lattice Boltzmann and continuum equations for flow and reactive transport in porous media.

    SciTech Connect

    Coon, Ethan; Porter, Mark L.; Kang, Qinjun; Moulton, John D.; Lichtner, Peter C.

    2012-06-18

    In spatially and temporally localized instances, capturing sub-reservoir scale information is necessary. Capturing sub-reservoir scale information everywhere is neither necessary, nor computationally possible. The lattice Boltzmann Method for solving pore-scale systems. At the pore-scale, LBM provides an extremely scalable, efficient way of solving Navier-Stokes equations on complex geometries. Coupling pore-scale and continuum scale systems via domain decomposition. By leveraging the interpolations implied by pore-scale and continuum scale discretizations, overlapping Schwartz domain decomposition is used to ensure continuity of pressure and flux. This approach is demonstrated on a fractured medium, in which Navier-Stokes equations are solved within the fracture while Darcy's equation is solved away from the fracture Coupling reactive transport to pore-scale flow simulators allows hybrid approaches to be extended to solve multi-scale reactive transport.

  13. Reactive transport modeling at uranium in situ recovery sites: uncertainties in uranium sorption on iron hydroxides

    USGS Publications Warehouse

    Johnson, Raymond H.; Tutu, Hlanganani; Brown, Adrian; Figueroa, Linda; Wolkersdorfer, Christian

    2013-01-01

    Geochemical changes that can occur down gradient from uranium in situ recovery (ISR) sites are important for various stakeholders to understand when evaluating potential effects on surrounding groundwater quality. If down gradient solid-phase material consists of sandstone with iron hydroxide coatings (no pyrite or organic carbon), sorption of uranium on iron hydroxides can control uranium mobility. Using one-dimensional reactive transport models with PHREEQC, two different geochemical databases, and various geochemical parameters, the uncertainties in uranium sorption on iron hydroxides are evaluated, because these oxidized zones create a greater risk for future uranium transport than fully reduced zones where uranium generally precipitates.

  14. Smoothed Particle Hydrodynamics and its applications for multiphase flow and reactive transport in porous media

    SciTech Connect

    Tartakovsky, Alexandre M.; Trask, Nathaniel; Pan, K.; Jones, Bruce D.; Pan, Wenxiao; Williams, John R.

    2016-03-11

    Smoothed Particle Hydrodynamics (SPH) is a Lagrangian method based on a meshless discretization of partial differential equations. In this review, we present SPH discretization of the Navier-Stokes and Advection-Diffusion-Reaction equations, implementation of various boundary conditions, and time integration of the SPH equations, and we discuss applications of the SPH method for modeling pore-scale multiphase flows and reactive transport in porous and fractured media.

  15. A Reactive-Heat-Pipe for Combined Heat Generation and Transport

    DTIC Science & Technology

    1977-12-01

    Pumping Heights for Different Temperatures. . . 70 22 Effect of Flow Losses on System Thermal Performance with No Argon in the Condenser...73 23 Flow Losses in the Vapor Transport System with Argon in the Condenser ................... 75 24 Temperature Distributions in a Reactive-Heat...shroud flow of inert gas, usually argon. The inert gas is recirculated through a vent system . The outer shroud flow prevents the direct contact

  16. Coupled inverse geochemical and microbial reactive transport models in porous media

    NASA Astrophysics Data System (ADS)

    Samper, J.; Yang, C.

    2007-12-01

    Microbial processes play a major role in controlling geochemical conditions in subsurface systems. Various laboratory and in situ experiments have been performed to evaluate the relevance of microbial processes and derive key microbial parameters. Such experiments are often interpreted by suboptimal trial-and-error curve fitting. Here we present an inverse model for coupled flow, reactive solute transport, geochemical and microbial processes which overcomes the limitations of trial-and-error methods by making data interpretation in a systematic, objective, and efficient manner. It extends the capabilities of existing inverse models which deal mostly with flow and chemically-reactive solute transport. Our inverse model relies on the microbial reactive transport code BIOCORE of Samper et al. (2006a) and improves the inverse reactive transport model INVERSE- CORE of Dai and Samper (2004) by allowing the simultaneous estimation of geochemical and microbial parameters. The inverse model has been implemented in a finite element code, INVERSE-BIOCORE2D and its capabilities have been verified and tested with a synthetic experiment involving equilibrium speciation, kinetic sorption/desorption and kinetic biodegradation reactions. Model results indicate that both chemical and microbial parameters can be estimated accurately for error-free data. Estimation errors of microbial parameters are larger than those of kinetic sorption parameters and generally increase with increasing standard deviation of data noise. Estimation error of yield coefficient is the smallest among all microbial parameter and which does not depend on data noise. The inverse model has been used also to estimate microbial parameters of a laboratory experiment involving sucrose fermentation by yeast. Inverse estimation improves significantly the fit to measured data.

  17. Modeling non-isothermal multiphase multi-species reactive chemical transport in geologic media

    SciTech Connect

    Tianfu Xu; Gerard, F.; Pruess, K.; Brimhall, G.

    1997-07-01

    The assessment of mineral deposits, the analysis of hydrothermal convection systems, the performance of radioactive, urban and industrial waste disposal, the study of groundwater pollution, and the understanding of natural groundwater quality patterns all require modeling tools that can consider both the transport of dissolved species as well as their interactions with solid (or other) phases in geologic media and engineered barriers. Here, a general multi-species reactive transport formulation has been developed, which is applicable to homogeneous and/or heterogeneous reactions that can proceed either subject to local equilibrium conditions or kinetic rates under non-isothermal multiphase flow conditions. Two numerical solution methods, the direct substitution approach (DSA) and sequential iteration approach (SIA) for solving the coupled complex subsurface thermo-physical-chemical processes, are described. An efficient sequential iteration approach, which solves transport of solutes and chemical reactions sequentially and iteratively, is proposed for the current reactive chemical transport computer code development. The coupled flow (water, vapor, air and heat) and solute transport equations are also solved sequentially. The existing multiphase flow code TOUGH2 and geochemical code EQ3/6 are used to implement this SIA. The flow chart of the coupled code TOUGH2-EQ3/6, required modifications of the existing codes and additional subroutines needed are presented.

  18. Investigating ebullition in a sand column using dissolved gas analysis and reactive transport modeling

    USGS Publications Warehouse

    Amos, Richard T.; Mayer, K. Ulrich

    2006-01-01

    Ebullition of gas bubbles through saturated sediments can enhance the migration of gases through the subsurface, affect the rate of biogeochemical processes, and potentially enhance the emission of important greenhouse gases to the atmosphere. To better understand the parameters controlling ebullition, methanogenic conditions were produced in a column experiment and ebullition through the column was monitored and quantified through dissolved gas analysis and reactive transport modeling. Dissolved gas analysis showed rapid transport of CH4 vertically through the column at rates several times faster than the bromide tracer and the more soluble gas CO2, indicating that ebullition was the main transport mechanism for CH4. An empirically derived formulation describing ebullition was integrated into the reactive transport code MIN3P allowing this process to be investigated on the REV scale in a complex geochemical framework. The simulations provided insights into the parameters controlling ebullition and show that, over the duration of the experiment, 36% of the CH4 and 19% of the CO2 produced were transported to the top of the column through ebullition.

  19. Development of a New and Fast Linear Solver for Multi-component Reactive Transport Simulation

    NASA Astrophysics Data System (ADS)

    Qiao, C.; Li, L.; Bao, C.; Hu, X.; Johns, R.; Xu, J.

    2013-12-01

    Reactive transport models (RTM) have been extensively used to understand the coupling between solute transport and (bio) geochemical reactions in complex earth systems. RTM typically involves a large number of primary and secondary species with a complex reaction network in large domains. The computational expenses increase significantly with the number of grid blocks and the number of chemical species. Within both the operator splitting approach (OS) and the global implicit approach (GI) that are commonly used, the steps that involve Newton-Raphson method are typically one of the most time-consuming parts (up to 80% to 90% of CPU times). Under such circumstances, accelerating reactive transport simulation is very essential. In this research, we present a physics-based linear system solution strategy for general reactive transport models with many species. We observed up to five times speed up for the linear solver portion of the simulations in our test cases. Our new linear solver takes advantage of the sparsity of the Jacobian matrix arising from the reaction network. The Jacobian matrix for the speciation problem is typically considered as a dense matrix and solved with a direct method such as Gaussian elimination. For the reactive transport problem, the graph of the local Jacobian matrix has a one-to-one correspondence to the reaction network graph. The Jacobian matrix is commonly sparse and has the same sparsity structure for the same reaction network. We developed a strategy that performs a minimum degree of reordering and symbolic factorization to determine the non-zero pattern at the beginning of the OS and GI simulation. During the speciation calculation in OS, we calculate the L and U factors and solve the triangular matrices according to the non-zero pattern. For GI, our strategy can be applied to inverse the diagonal blocks in the block-Jacobi preconditioner and smoothers of the multigrid preconditioners in iterative solvers. Our strategy is naturally

  20. One-Dimensional Transport with Equilibrium Chemistry (OTEQ) - A Reactive Transport Model for Streams and Rivers

    USGS Publications Warehouse

    Runkel, Robert L.

    2010-01-01

    OTEQ is a mathematical simulation model used to characterize the fate and transport of waterborne solutes in streams and rivers. The model is formed by coupling a solute transport model with a chemical equilibrium submodel. The solute transport model is based on OTIS, a model that considers the physical processes of advection, dispersion, lateral inflow, and transient storage. The equilibrium submodel is based on MINTEQ, a model that considers the speciation and complexation of aqueous species, acid-base reactions, precipitation/dissolution, and sorption. Within OTEQ, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (waterborne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach. The model's ability to simulate pH, precipitation/dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between instream chemistry and hydrologic transport at the field scale. This report details the development and application of OTEQ. Sections of the report describe model theory, input/output specifications, model applications, and installation instructions. OTEQ may be obtained over the Internet at http://water.usgs.gov/software/OTEQ.

  1. Estimating spatially-variable first-order rate constants in groundwater reactive transport systems.

    PubMed

    Bailey, R T; Baù, D

    2011-03-25

    Numerical reactive transport models are often used as tools to assess aquifers contaminated with reactive groundwater solutes as well as investigating mitigation scenarios. The ability to accurately simulate the fate and transport of solutes, however, is often impeded by a lack of information regarding the parameters that define chemical reactions. In this study, we employ a steady-state Ensemble Kalman Filter (EnKF), a data assimilation algorithm, to provide improved estimates of a spatially-variable first-order rate constant λ through assimilation of solute concentration measurement data into reactive transport simulation results. The methodology is applied in a steady-state, synthetic aquifer system in which a contaminant is leached to the saturated zone and undergoes first-order decay. Multiple sources of uncertainty are investigated, including hydraulic conductivity of the aquifer and the statistical parameters that define the spatial structure of the parameter field. For the latter scenario, an iterative method is employed to identify the statistical mean of λ of the reference system. Results from all simulations show that the filter scheme is successful in conditioning the λ ensemble to the reference λ field. Sensitivity analyses demonstrate that the estimation of the λ values is dependent on the number of concentration measurements assimilated, the locations from which the measurement data are collected, the error assigned to the measurement values, and the correlation length of the λ fields.

  2. Influence of Sedimentary Bedding on Reactive Transport Parameters under Unsaturated Conditions

    SciTech Connect

    Mayes, Melanie; Tang, Guoping; Jardine, Philip M; McKay, Larry Donald; Yin, Xiangping Lisa; Pace, M. N.; Parker, Jack C; Zhang, Fan; Mehlhorn, Tonia L; Dansby-Sparks, Royce N

    2009-01-01

    Moisture and contaminant transport in partially saturated, heterogeneous, layered sediments is typically anisotropic. Solute transport parameters, including dispersivity and the adsorption coefficient, and the modeled concentration of reactive minerals may depend on the direction of flow with respect to sedimentary layering. Reaction rates, in contrast, should be independent of flow direction. We determined the influence of flow direction on transport parameters for nonreactive (Br{sup -}) and reactive (cobalt ethylenediaminetetraacetic acid [Co(II)EDTA{sup 2-}]) solutes under partially saturated conditions by imposing flow either parallel to or across sedimentary bedding in 11 intact sediment cores of various textures. Higher dispersivity of nonreactive tracers in parallel-bed cores suggested fluid channeling through permeable layers, while low-conductivity layers dampened channeling in cross-bed samples. Rates of transformation of Co(II)EDTA{sup 2-} into Co(III)EDTA{sup -} and of disassociation of Co{sup 2+} and EDTA{sup 4-} were modeled assuming that the reaction rates were independent of the flow direction. The concentration of Mn oxides that was responsible for the transformation reaction was dependent on the flow direction, which governed the extent of contact between the solution and the solid phase. Similarly, the adsorption constants of Co(II)EDTA{sup 2-} and Co(III)EDTA{sup -} were dependent on the flow direction but were also unique for each experiment. The modeled concentration of reactive minerals was the most sensitive parameter describing the reaction and transformation of Co(II)EDTA{sup 2-}.

  3. THC-MP: High performance numerical simulation of reactive transport and multiphase flow in porous media

    NASA Astrophysics Data System (ADS)

    Wei, Xiaohui; Li, Weishan; Tian, Hailong; Li, Hongliang; Xu, Haixiao; Xu, Tianfu

    2015-07-01

    The numerical simulation of multiphase flow and reactive transport in the porous media on complex subsurface problem is a computationally intensive application. To meet the increasingly computational requirements, this paper presents a parallel computing method and architecture. Derived from TOUGHREACT that is a well-established code for simulating subsurface multi-phase flow and reactive transport problems, we developed a high performance computing THC-MP based on massive parallel computer, which extends greatly on the computational capability for the original code. The domain decomposition method was applied to the coupled numerical computing procedure in the THC-MP. We designed the distributed data structure, implemented the data initialization and exchange between the computing nodes and the core solving module using the hybrid parallel iterative and direct solver. Numerical accuracy of the THC-MP was verified through a CO2 injection-induced reactive transport problem by comparing the results obtained from the parallel computing and sequential computing (original code). Execution efficiency and code scalability were examined through field scale carbon sequestration applications on the multicore cluster. The results demonstrate successfully the enhanced performance using the THC-MP on parallel computing facilities.

  4. Integrating a compressible multicomponent two-phase flow into an existing reactive transport simulator

    NASA Astrophysics Data System (ADS)

    Sin, Irina; Lagneau, Vincent; Corvisier, Jérôme

    2017-02-01

    This work aims to incorporate compressible multiphase flow into the conventional reactive transport framework using an operator splitting approach. This new approach would allow us to retain the general paradigm of the flow module independent of the geochemical processes and to model complex multiphase chemical systems, conserving the versatile structure of conventional reactive transport. The phase flow formulation is employed to minimize the number of mass conservation nonlinear equations arising from the flow module. Applying appropriate equations of state facilitated precise descriptions of the compressible multicomponent phases, their thermodynamic properties and relevant fluxes. The proposed flow coupling method was implemented in the reactive transport software HYTEC. The entire framework preserves its flexibility for further numerical developments. The verification of the coupling was achieved by modeling a problem with a self-similar solution. The simulation of a 2D CO2-injection problem demonstrates the pertinent physical results and computational efficiency of this method. The coupling method was employed for modeling injection of acid gas mixture in carbonated reservoir.

  5. Stable isotope fractionations during reactive transport of phosphate in packed-bed sediment columns

    NASA Astrophysics Data System (ADS)

    Jaisi, Deb P.

    2013-11-01

    Characterizing reactivity and fate of contaminants in subsurface environments that are isolated from direct visualization is a major challenge. Stable isotopes coupled with concentration could be used as a potential tool to quantitatively analyze the chemical variability of the contaminant during reactive transport processes in the subsurface environment. This study was aimed at determining whether abiotic reactions of phosphate during its transport involve fractionation of oxygen isotopes in phosphate (δ18Op). It included the effects of solution chemistry and hydrodynamics on δ18Op values during phosphate transport through a packed-bed column prepared by using natural sediment collected from the Cape Cod aquifer in Massachusetts. Results show that the isotopic fractionation between effluent and influent phosphate at early stage of transport could be ~ 1.3‰ at higher flow rates with isotopically-light phosphate (P16O4) preferentially retained in the sediment column. This fractionation, however, decreased and became insignificant as more phosphate passed through the column. Mobilization of phosphate initially sorbed onto sediments caused a large kinetic isotopic fractionation with isotopically-light phosphate preferentially remobilized from the sediment column, but over longer time periods, this fractionation decreased and became insignificant as well. These results collectively suggest that abiotic reactive transport processes exert minimal influence on the δ18Op composition of subsurface systems. Alternatively, fluctuation in flow rate and subsequent remobilization of phosphate could be detectable through transient changes in δ18Op values. These findings extend the burgeoning application of δ18Op to identify the different sources and geochemical processes of phosphate in the subsurface environments.

  6. Reactive Transport Modeling of CO2-induced Porosity and Permeability Changes in Heterogeneous Carbonate Rocks

    NASA Astrophysics Data System (ADS)

    Hao, Y.; Smith, M. M.; Mason, H. E.; Carroll, S.

    2015-12-01

    It has long been appreciated that chemical interactions have a major effect on rock porosity and permeability evolution and may alter the behavior or performance of both natural and engineered reservoir systems. Such reaction-induced permeability evolution is of particular importance for geological CO2 sequestration and storage associated with enhanced oil recovery. In this study we used a three-dimensional Darcy scale reactive transport model to simulate CO2 core flood experiments in which the CO2-equilibrated brine was injected into dolostone cores collected from the Arbuckle carbonate reservoir, Wellington, Kansas. Heterogeneous distributions of macro pores, fractures, and mineral phases inside the cores were obtained from X-ray computed microtomography (XCMT) characterization data, and then used to construct initial model macroscopic properties including porosity, permeability, and mineral compositions. The reactive transport simulations were performed by using the Nonisothermal Unsaturated Flow and Transport (NUFT) code, and their results were compared with experimental data. It was observed both experimentally and numerically that the dissolution fronts became unstable in highly heterogeneous and less permeable formations, leading to the development of highly porous flow paths or wormholes. Our model results indicate that the continuum-scale reactive transport models are able to adequately capture the evolution of distinct dissolution fronts as observed in carbonate rocks at a core scale. The impacts of rock heterogeneity, chemical kinetics and porosity-permeability relationships were also examined in this study. The numerical model developed in this study will not only help improve understanding of coupled physical and chemical processes controlling carbonate dissolution, but also provide a useful basis for upscaling transport and reaction properties from core scale to field scale. This work was performed under the auspices of the U.S. Department of Energy

  7. Marine phages as excellent tracers for reactive colloidal transport in porous media

    NASA Astrophysics Data System (ADS)

    Ghanem, Nawras; Chatzinotas, Antonis; Harms, Hauke; Wick, Lukas Y.

    2016-04-01

    Question: Here we evaluate marine phages as specific markers of hydrological flow and reactive transport of colloidal particles in the Earth's critical zone (CZ). Marine phages and their bacterial hosts are naturally absent in the CZ, and can be detected with extremely high sensitivity. In the framework of the DFG Collaborative Research Center AquaDiva, we asked the following questions: (1) Are marine phages useful specific markers of hydrological flow and reactive transport in porous media? and (2) Which phage properties are relevant drivers for the transport of marine phages in porous media? Methods: Seven marine phages from different families (as well two commonly used terrestrial phages) were selected based on their morphology, size and physico-chemical surface properties (surface charge and hydrophobicity). Phage properties were assessed by electron microscopy, dynamic light scattering and water contact angle analysis (CA). Sand-filled laboratory percolation columns were used to study transport. The breakthrough curves of the phages were analyzed using the clean bed filtration theory and the XDLVO theory of colloid stability, respectively. Phages were quantified by a modified high- throughput plaque assay and a culture-independent particle counting method approach. Results: Our data show that most marine tested phages exhibited highly variable transport rates and deposition efficiency, yet generally high colloidal stability and viability. We find that size, morphology and hydrophobicity are key factors shaping the transport efficiency of phages. Differing deposition efficiencies of the phages were also supported by calculated XDLVO interaction energy profile. Conclusion: Marine phages have a high potential for the use as sensitive tracers in terrestrial habitats with their surface properties playing a crucial role for their transport. Marine phages however, exhibit differences in their deposition efficiency depending on their morphology, hydrophobicity and

  8. Role of reactive oxygen species in regulation of glucose transport in skeletal muscle during exercise.

    PubMed

    Katz, Abram

    2016-06-01

    Glucose derived from extracellular sources serves as an energy source in virtually all eukaryotic cells, including skeletal muscle. Its contribution to energy turnover increases with exercise intensity up to moderately heavy workloads. However, at very high workloads, the contribution of extracellular glucose to energy turnover is negligible, despite the high rate of glucose transport. Reactive oxygen species (ROS) are involved in the stimulation of glucose transport in isolated skeletal muscle preparations during intense repeated contractions. Consistent with this observation, heavy exercise is associated with significant production of ROS. However, during more mild to moderate stimulation or exercise conditions (in vitro, in situ and in vivo) antioxidants do not affect glucose transport. It is noteworthy that the production of ROS is limited or not observed under these conditions and that the concentration of the antioxidant used was extremely low. The results to date suggest that ROS involvement in activation of glucose transport occurs primarily during intense short-term exercise and that other mechanisms are involved during mild to moderate exercise. What remains puzzling is why ROS-mediated activation of glucose transport would occur under conditions where glucose transport is highest and utilization (i.e. phosphorylation of glucose by hexokinase) is low. Possibly ROS production is involved in priming glucose transport during heavy exercise to accelerate glycogen biogenesis during the initial recovery period after exercise, as well as altering other aspects of intracellular metabolism.

  9. Subsurface Transport Over Reactive Multiphases (STORM): A general, coupled, nonisothermal multiphase flow, reactive transport, and porous medium alteration simulator, Version 2 user's guide

    SciTech Connect

    DH Bacon; MD White; BP McGrail

    2000-03-07

    The Hanford Site, in southeastern Washington State, has been used extensively to produce nuclear materials for the US strategic defense arsenal by the Department of Energy (DOE) and its predecessors, the US Atomic Energy Commission and the US Energy Research and Development Administration. A large inventory of radioactive and mixed waste has accumulated in 177 buried single- and double shell tanks. Liquid waste recovered from the tanks will be pretreated to separate the low-activity fraction from the high-level and transuranic wastes. Vitrification is the leading option for immobilization of these wastes, expected to produce approximately 550,000 metric tons of Low Activity Waste (LAW) glass. This total tonnage, based on nominal Na{sub 2}O oxide loading of 20% by weight, is destined for disposal in a near-surface facility. Before disposal of the immobilized waste can proceed, the DOE must approve a performance assessment, a document that described the impacts, if any, of the disposal facility on public health and environmental resources. Studies have shown that release rates of radionuclides from the glass waste form by reaction with water determine the impacts of the disposal action more than any other independent parameter. This report describes the latest accomplishments in the development of a computational tool, Subsurface Transport Over Reactive Multiphases (STORM), Version 2, a general, coupled non-isothermal multiphase flow and reactive transport simulator. The underlying mathematics in STORM describe the rate of change of the solute concentrations of pore water in a variably saturated, non-isothermal porous medium, and the alteration of waste forms, packaging materials, backfill, and host rocks.

  10. Transport of Oil-in-Water Emulsions Designed to Deliver Reactive Iron Particles in Porous Media

    NASA Astrophysics Data System (ADS)

    Crocker, J. J.; Berge, N. D.; Ramsburg, C. A.

    2007-05-01

    Treatment of subsurface regions contaminated with DNAPL is a significant challenge to environmental restoration. The focus of remediation has recently shifted from technologies that recover the contamination to technologies that destroy the contamination in situ. One method of in situ contaminant destruction employs nano- or submicron-size particles of reactive iron metal. Application of iron-based destruction technologies is currently limited by poor delivery of the reactive particles (i.e., lack of contact between the iron particles and the DNAPL). Encapsulation of the reactive particles within an oil-in-water emulsion is a novel approach that may facilitate delivery. The goal of this project was to investigate the transport behavior of emulsions (Tallow oil, Tween 80, and Span 80) within porous media. One-dimensional column experiments were conducted to evaluate pore-clogging when emulsions containing encapsulated reactive particles were passed through two homogeneous sands with an order of magnitude difference in intrinsic permeability. In these experiments, passing an emulsion through the sand column (4.8 cm i.d.) at a constant flow rate (0.86 mL/min) increased the hydraulic gradient by a factor of approximately three. The hydraulic gradient in each experiment was observed to stabilize after one pore volume of emulsion. Subsequent flushing with water recovered the initial hydraulic gradient. Together, these observations indicate that conductivity reductions during emulsion flushing were the result of viscosity and not the result of extensive pore-clogging. Analysis of effluent samples confirmed that there was minimal retention of the emulsion within the sand column. Results from these experiments suggest that emulsion encapsulation may be an effective means for transporting reactive iron particles within the subsurface environment.

  11. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions.

    PubMed

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C; Brooks, Scott C; Pace, Molly N; Kim, Young-Jin; Jardine, Philip M; Watson, David B

    2007-06-16

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

  12. Reactive species in non-equilibrium atmospheric-pressure plasmas: Generation, transport, and biological effects

    NASA Astrophysics Data System (ADS)

    Lu, X.; Naidis, G. V.; Laroussi, M.; Reuter, S.; Graves, D. B.; Ostrikov, K.

    2016-05-01

    Non-equilibrium atmospheric-pressure plasmas have recently become a topical area of research owing to their diverse applications in health care and medicine, environmental remediation and pollution control, materials processing, electrochemistry, nanotechnology and other fields. This review focuses on the reactive electrons and ionic, atomic, molecular, and radical species that are produced in these plasmas and then transported from the point of generation to the point of interaction with the material, medium, living cells or tissues being processed. The most important mechanisms of generation and transport of the key species in the plasmas of atmospheric-pressure plasma jets and other non-equilibrium atmospheric-pressure plasmas are introduced and examined from the viewpoint of their applications in plasma hygiene and medicine and other relevant fields. Sophisticated high-precision, time-resolved plasma diagnostics approaches and techniques are presented and their applications to monitor the reactive species and plasma dynamics in the plasma jets and other discharges, both in the gas phase and during the plasma interaction with liquid media, are critically reviewed. The large amount of experimental data is supported by the theoretical models of reactive species generation and transport in the plasmas, surrounding gaseous environments, and plasma interaction with liquid media. These models are presented and their limitations are discussed. Special attention is paid to biological effects of the plasma-generated reactive oxygen and nitrogen (and some other) species in basic biological processes such as cell metabolism, proliferation, survival, etc. as well as plasma applications in bacterial inactivation, wound healing, cancer treatment and some others. Challenges and opportunities for theoretical and experimental research are discussed and the authors' vision for the emerging convergence trends across several disciplines and application domains is presented to

  13. Reactive silica transport in fractured porous media: Analytical solutions for a system of parallel fractures

    NASA Astrophysics Data System (ADS)

    Yang, Jianwen

    2012-04-01

    A general analytical solution is derived by using the Laplace transformation to describe transient reactive silica transport in a conceptualized 2-D system involving a set of parallel fractures embedded in an impermeable host rock matrix, taking into account of hydrodynamic dispersion and advection of silica transport along the fractures, molecular diffusion from each fracture to the intervening rock matrix, and dissolution of quartz. A special analytical solution is also developed by ignoring the longitudinal hydrodynamic dispersion term but remaining other conditions the same. The general and special solutions are in the form of a double infinite integral and a single infinite integral, respectively, and can be evaluated using Gauss-Legendre quadrature technique. A simple criterion is developed to determine under what conditions the general analytical solution can be approximated by the special analytical solution. It is proved analytically that the general solution always lags behind the special solution, unless a dimensionless parameter is less than a critical value. Several illustrative calculations are undertaken to demonstrate the effect of fracture spacing, fracture aperture and fluid flow rate on silica transport. The analytical solutions developed here can serve as a benchmark to validate numerical models that simulate reactive mass transport in fractured porous media.

  14. A Modular Computer Code for Simulating Reactive Multi-Species Transport in 3-Dimensional Groundwater Systems

    SciTech Connect

    TP Clement

    1999-06-24

    RT3DV1 (Reactive Transport in 3-Dimensions) is computer code that solves the coupled partial differential equations that describe reactive-flow and transport of multiple mobile and/or immobile species in three-dimensional saturated groundwater systems. RT3D is a generalized multi-species version of the US Environmental Protection Agency (EPA) transport code, MT3D (Zheng, 1990). The current version of RT3D uses the advection and dispersion solvers from the DOD-1.5 (1997) version of MT3D. As with MT3D, RT3D also requires the groundwater flow code MODFLOW for computing spatial and temporal variations in groundwater head distribution. The RT3D code was originally developed to support the contaminant transport modeling efforts at natural attenuation demonstration sites. As a research tool, RT3D has also been used to model several laboratory and pilot-scale active bioremediation experiments. The performance of RT3D has been validated by comparing the code results against various numerical and analytical solutions. The code is currently being used to model field-scale natural attenuation at multiple sites. The RT3D code is unique in that it includes an implicit reaction solver that makes the code sufficiently flexible for simulating various types of chemical and microbial reaction kinetics. RT3D V1.0 supports seven pre-programmed reaction modules that can be used to simulate different types of reactive contaminants including benzene-toluene-xylene mixtures (BTEX), and chlorinated solvents such as tetrachloroethene (PCE) and trichloroethene (TCE). In addition, RT3D has a user-defined reaction option that can be used to simulate any other types of user-specified reactive transport systems. This report describes the mathematical details of the RT3D computer code and its input/output data structure. It is assumed that the user is familiar with the basics of groundwater flow and contaminant transport mechanics. In addition, RT3D users are expected to have some experience in

  15. Using Reactive Transport Modeling to Understand Changes in Electrical Conductivity Associated with Bacterial Growth and Respiration

    NASA Astrophysics Data System (ADS)

    Regberg, A. B.; Singha, K.; Picardal, F.; Brantley, S. L.

    2011-12-01

    Previous research has linked measured changes in the bulk electrical conductivity (σb) of water-saturated sediments to the respiration and growth of anaerobic bacteria. If the mechanism causing this signal is understood and characterized it could be used to identify and monitor zones of bacterial activity in the subsurface. The 1-D reactive transport model PHREEQC was used to understand σb signals by modeling chemical gradients within two column reactors and corresponding changes in effluent chemistry. The flow-through column reactors were packed with Fe(III)-bearing sediment from Oyster, VA and inoculated with an environmental consortia of microorganisms. Influent in the first reactor was amended with 1mM Na-acetate to encourage the growth of iron-reducing bacteria. Influent in the second reactor was amended with 0.1mM Na-Acetate and 2mM NaNO3 to encourage the growth of nitrate-reducing bacteria. While effluent concentrations of acetate, Fe(II), NO3-, NO2-, and NH4+ remained at steady state, we measured a 3-fold increase (0.055 S/m - 0.2 S/m) in σb in the iron-reducing column and a 10-fold increase in σb (0.07 S/m - 0.8 S/m) in the nitrate-reducing column over 198 days. The ionic strength in both reactors remained constant through time indicating that the measured increases in σb were not caused by changing effluent concentrations. PHREEQC successfully matched the measured changes in effluent concentrations for both columns when the reaction database was modified in the following manner. For the iron-reducing column, kinetic expressions governing the rate of iron reduction, the rate of bacterial growth, and the production of methane were added to the reaction database. Additionally, surface adsorption and cation exchange reactions were added so that the model was consistent with measured effluent chemistry. For the nitrate-reducing column, kinetic expressions governing nitrate reduction and bacterial growth were added to the reaction database. Additionally

  16. Post Audit of a Field Scale Reactive Transport Model of Uranium at a Former Mill Site

    NASA Astrophysics Data System (ADS)

    Curtis, G. P.

    2015-12-01

    Reactive transport of hexavalent uranium (U(VI)) in a shallow alluvial aquifer at a former uranium mill tailings site near Naturita CO has been monitored for nearly 30 years by the US Department of Energy and the US Geological Survey. Groundwater at the site has high concentrations of chloride, alkalinity and U(VI) as a owing to ore processing at the site from 1941 to 1974. We previously calibrated a multicomponent reactive transport model to data collected at the site from 1986 to 2001. A two dimensional nonreactive transport model used a uniform hydraulic conductivity which was estimated from observed chloride concentrations and tritium helium age dates. A reactive transport model for the 2km long site was developed by including an equilibrium U(VI) surface complexation model calibrated to laboratory data and calcite equilibrium. The calibrated model reproduced both nonreactive tracers as well as the observed U(VI), pH and alkalinity. Forward simulations for the period 2002-2015 conducted with the calibrated model predict significantly faster natural attenuation of U(VI) concentrations than has been observed by the persistent high U(VI) concentrations at the site. Alternative modeling approaches are being evaluating evaluated using recent data to determine if the persistence can be explained by multirate mass transfer models developed from experimental observations at the column scale(~0.2m), the laboratory tank scale (~2m), the field tracer test scale (~1-4m) or geophysical observation scale (~1-5m). Results of this comparison should provide insight into the persistence of U(VI) plumes and improved management options.

  17. A Benchmarking Initiative for Reactive Transport Modeling Applied to Subsurface Environmental Applications

    NASA Astrophysics Data System (ADS)

    Steefel, C. I.

    2015-12-01

    Over the last 20 years, we have seen the evolution of multicomponent reactive transport modeling and the expanding range and increasing complexity of subsurface environmental applications it is being used to address. Reactive transport modeling is being asked to provide accurate assessments of engineering performance and risk for important issues with far-reaching consequences. As a result, the complexity and detail of subsurface processes, properties, and conditions that can be simulated have significantly expanded. Closed form solutions are necessary and useful, but limited to situations that are far simpler than typical applications that combine many physical and chemical processes, in many cases in coupled form. In the absence of closed form and yet realistic solutions for complex applications, numerical benchmark problems with an accepted set of results will be indispensable to qualifying codes for various environmental applications. The intent of this benchmarking exercise, now underway for more than five years, is to develop and publish a set of well-described benchmark problems that can be used to demonstrate simulator conformance with norms established by the subsurface science and engineering community. The objective is not to verify this or that specific code--the reactive transport codes play a supporting role in this regard—but rather to use the codes to verify that a common solution of the problem can be achieved. Thus, the objective of each of the manuscripts is to present an environmentally-relevant benchmark problem that tests the conceptual model capabilities, numerical implementation, process coupling, and accuracy. The benchmark problems developed to date include 1) microbially-mediated reactions, 2) isotopes, 3) multi-component diffusion, 4) uranium fate and transport, 5) metal mobility in mining affected systems, and 6) waste repositories and related aspects.

  18. In Situ Biostimulation at a Former Uranium Mill Tailings Site: Multicomponent Biogeochemical Reactive Transport Modeling

    NASA Astrophysics Data System (ADS)

    Yabusaki, S.; Fang, Y.; Long, P.

    2005-12-01

    In situ biostimulation at a Former Uranium Mill Tailings Site: Multicomponent Biogeochemical Reactive Transport Modeling Field experiments conducted at a former uranium mill tailings site in western Colorado are being used to investigate microbially mediated immobilization of uranium as a potential future remediation option for such sites. While the general principle of biostimulating microbial communities to reduce aqueous hexavalent uranium to immobile uraninite has been demonstrated in the laboratory and field, the ability to predictably engineer long lasting immobilization will require a more complete understanding of field-scale processes and properties. For this study, numerical simulation of the flow field, geochemical conditions, and micriobial communities is used to interpret field-scale biogeochemical reactive transport observed during experiments performed in 2002 to 2004. One key issue is identifying bioavailable Fe(III) oxide, which is the principal electron acceptor utilized by the acetate- oxidizing Geobacter sp. These organisms are responsible for uranium bioreduction that results in the removal of sufficient U(VI) to lower uranium groundwater concentrations to at or near applicable standards. The depletion of bioavailable Fe(III) leads to succession by sulfate reducers that are considerably less effective at uranium bioreduction. An important modeling consideration are the abiotic reactions (e.g., mineral precipitation and dissolution, aqueous and surface complexation) involving the Fe(II) and sulfide produced during biostimulation. These components, strongly associated with the solid phases, may play an important role in the evolving reactivity of the mineral surfaces that are likely to impact long-term uranium immobilization.

  19. Computational methods for multiphase equilibrium and kinetics calculations for geochemical and reactive transport applications

    NASA Astrophysics Data System (ADS)

    Leal, Allan; Saar, Martin

    2016-04-01

    Computational methods for geochemical and reactive transport modeling are essential for the understanding of many natural and industrial processes. Most of these processes involve several phases and components, and quite often requires chemical equilibrium and kinetics calculations. We present an overview of novel methods for multiphase equilibrium calculations, based on both the Gibbs energy minimization (GEM) approach and on the solution of the law of mass-action (LMA) equations. We also employ kinetics calculations, assuming partial equilibrium (e.g., fluid species in equilibrium while minerals are in disequilibrium) using automatic time stepping to improve simulation efficiency and robustness. These methods are developed specifically for applications that are computationally expensive, such as reactive transport simulations. We show how efficient the new methods are, compared to other algorithms, and how easy it is to use them for geochemical modeling via a simple script language. All methods are available in Reaktoro, a unified open-source framework for modeling chemically reactive systems, which we also briefly describe.

  20. A parametric transfer function methodology for analyzing reactive transport in nonuniform flow.

    PubMed

    Luo, Jian; Cirpka, Olaf A; Fienen, Michael N; Wu, Wei-min; Mehlhorn, Tonia L; Carley, Jack; Jardine, Philip M; Criddle, Craig S; Kitanidis, Peter K

    2006-02-01

    We analyze reactive transport during in-situ bioremediation in a nonuniform flow field, involving multiple extraction and injection wells, by the method of transfer functions. Gamma distributions are used as parametric models of the transfer functions. Apparent parameters of classical transport models may be estimated from those of the gamma distributions by matching temporal moments. We demonstrate the method by application to measured data taken at a field experiment on bioremediation conducted in a multiple-well system in Oak Ridge, TN. Breakthrough curves (BTCs) of a conservative tracer (bromide) and a reactive compound (ethanol) are measured at multi-level sampling (MLS) wells and in extraction wells. The BTCs of both compounds are jointly analyzed to estimate the first-order degradation rate of ethanol. To quantify the tracer loss, we compare the approaches of using a scaling factor and a first-order decay term. Results show that by including a scaling factor both gamma distributions and inverse-Gaussian distributions (transfer functions according to the advection-dispersion equation) are suitable to approximate the transfer functions and estimate the reactive rate coefficients for both MLS and extraction wells. However, using a first-order decay term for tracer loss fails to describe the BTCs at the extraction well, which is affected by the nonuniform distribution of travel paths.

  1. Reactive iron transport in an acidic mountain stream in Summit County, Colorado: A hydrologic perspective

    USGS Publications Warehouse

    McKnight, Diane M.; Bencala, K.E.

    1989-01-01

    A pH perturbation experiment was conducted in an acidic, metal-enriched, mountain stream to identify relative rates of chemical and hydrologic processes as they influence iron transport. During the experiment the pH was lowered from 4.2 to 3.2 for three hours by injection of sulfuric acid. Amorphous iron oxides are abundant on the streambed, and dissolution and photoreduction reactions resulted in a rapid increase in the dissolved iron concentration. The increase occurred simultaneously with the decrease in pH. Ferrous iron was the major aqueous iron species. The changes in the iron concentration during the experiment indicate that variation exists in the solubility properties of the hydrous iron oxides on the streambed with dissolution of at least two compartments of hydrous iron oxides contributing to the iron pulse. Spatial variations of the hydrologic properties along the stream were quantified by simulating the transport of a coinjected tracer, lithium. A simulation of iron transport, as a conservative solute, indicated that hydrologie transport had a significant role in determining downstream changes in the iron pulse. The rapidity of the changes in iron concentration indicates that a model based on dynamic equilibrium may be adequate for simulating iron transport in acid streams. A major challenge for predictive solute transport models of geochemical processes may be due to substantial spatial and seasonal variations in chemical properties of the reactive hydrous oxides in such streams, and in the physical and hydrologic properties of the stream. ?? 1989.

  2. Reactive transport simulations of the evolution of a cementitious repository in clay-rich host rocks

    NASA Astrophysics Data System (ADS)

    Kosakowski, Georg; Berner, Urs; Kulik, Dmitrii A.

    2010-05-01

    In Switzerland, the deep geological disposal in clay-rich rocks is foreseen not only for high-level radioactive waste, but also for intermediate-level (ILW) and low-level (LLW) radioactive waste. Typically, ILW and LLW repositories contain huge amounts of cementitious materials used for waste conditioning, confinement, and as backfill for the emplacement caverns. We are investigating the interactions of such a repository with the surrounding clay rocks and with other clay-rich materials such as sand/bentonite mixtures that are foreseen for backfilling the access tunnels. With the help of a numerical reactive transport model, we are comparing the evolution of cement/clay interfaces for different geochemical and transport conditions. In this work, the reactive transport of chemical components is simulated with the multi-component reactive transport code OpenGeoSys-GEM. It employs the sequential non-iterative approach to couple the mass transport code OpenGeoSys (http://www.ufz.de/index.php?en=18345) with the GEMIPM2K (http://gems.web.psi.ch/) code for thermodynamic modeling of aquatic geochemical systems which is using the Gibbs Energy Minimization (GEM) method. Details regarding code development and verification can be found in Shao et al. (2009). The mineral composition and the pore solution of a CEM I 52.5 N HTS hydrated cement as described by Lothenbach & Wieland (2006) are used as an initial state of the cement compartment. The setup is based on the most recent CEMDATA07 thermodynamic database which includes several ideal solid solutions for hydrated cement minerals and is consistent with the Nagra/PSI thermodynamic database 01/01. The smectite/montmorillonite model includes cation exchange processes and amphotheric≡SOH sites and was calibrated on the basis of data by Bradbury & Baeyens (2002). In other reactive transport codes based on the Law of Mass Action (LMA) for solving geochemical equilibria, cation exchange processes are usually calculated assuming

  3. Coupled Geochemical and Reactive Transport Modeling of Organic Contaminants in a Pyrite-Rich Aquifer

    NASA Astrophysics Data System (ADS)

    Sarioglu, S. M.; Copty, N. K.

    2004-12-01

    Although pH is recognized as a key factor influencing bacterial activity, existing groundwater transport models generally do not directly account for the effect of pH on the biodegradation of organic compounds. The purpose of this study is to develop a coupled reactive transport and geochemical model that explicitly incorporates the effect of spatial and temporal variations of the pH on the biodegradation of organic contaminants. The model consists of two modules: a transport module and a geochemical module. The transport module uses a Crank-Nicholson finite-difference formulation to solve the groundwater flow and transport equations for the hydrocarbon, dissolved oxygen, microbial mass and all reactive groundwater species influencing the hydrocarbon biodegradation and pH distribution. The geochemical module allows for the simulation of both kinetically defined as well as geochemical equilibrium reactions. The governing non-linear system of equations is solved using an iterative multi-step operator-splitting algorithm. Both modules account for heterogeneity in the definition of the hydrogeological and biochemical parameters. For demonstration, the model is applied to a hypothetical pyrite-rich aquifer contaminated with petroleum hydrocarbons. A commonly used practice for the remediation of aquifers contaminated with petroleum hydrocarbons is the delivery of oxygen for the enhanced aerobic biodegradation of the organic contaminant. However, the presence of pyrite may interfere with the intended purpose of the supplied oxygen, leading to undesirable side effects. Specifically, oxygen readily reacts with the sulfide minerals leading to depletion of oxygen and acidification of the subsurface environment and, subsequently, the inadvertent inhibition of the microbial activity. The developed coupled geochemical and reactive transport model is used to quantify these processes and assess the dominance of the various chemical reactions. Both abiotic and biotic pyrite

  4. Influence of ACE I/D Polymorphism on Circulating Levels of Plasminogen Activator Inhibitor 1, D-Dimer, Ultrasensitive C-Reactive Protein and Transforming Growth Factor β1 in Patients Undergoing Hemodialysis

    PubMed Central

    de Carvalho, Sara Santos; Simões e Silva, Ana Cristina; Sabino, Adriano de Paula; Evangelista, Fernanda Cristina Gontijo; Gomes, Karina Braga; Dusse, Luci Maria SantAna; Rios, Danyelle Romana Alves

    2016-01-01

    Background There is substantial evidence that chronic renal and cardiovascular diseases are associated with coagulation disorders, endothelial dysfunction, inflammation and fibrosis. Angiotensin-Converting Enzyme Insertion/Deletion polymorphism (ACE I/D polymorphism) has also be linked to cardiovascular diseases. Therefore, this study aimed to compare plasma levels of ultrassensible C-reactive protein (usCRP), PAI-1, D-dimer and TGF-β1 in patients undergoing HD with different ACE I/D polymorphisms. Methods The study was performed in 138 patients at ESRD under hemodialysis therapy for more than six months. The patients were divided into three groups according to the genotype. Genomic DNA was extracted from blood cells (leukocytes). ACE I/D polymorphism was investigated by single polymerase chain reaction (PCR). Plasma levels of D-dimer, PAI-1 and TGF-β1 were measured by enzyme-linked immunosorbent assay (ELISA), and the determination of plasma levels of usCRP was performed by immunonephelometry. Data were analyzed by the software SigmaStat 2.03. Results Clinical characteristics were similar in patients with these three ACE I/D polymorphisms, except for interdialytic weight gain. I allele could be associated with higher interdialytic weight gain (P = 0.017). Patients genotyped as DD and as ID had significantly higher levels of PAI-1 than those with II genotype. Other laboratory parameters did not significantly differ among the three subgroups (P = 0.033). Despite not reaching statistical significance, plasma levels of usCRP were higher in patients carrying the D allele. Conclusion ACE I/D polymorphisms could be associated with changes in the regulation of sodium, fibrinolytic system, and possibly, inflammation. Our data showed that high levels of PAI-1 are detected when D allele is present, whereas greater interdialytic gain is associated with the presence of I allele. However, further studies with different experimental designs are necessary to elucidate the

  5. Simulation of reactive transport of uranium(VI) in groundwater with variable chemical conditions

    NASA Astrophysics Data System (ADS)

    Curtis, Gary P.; Davis, James A.; Naftz, David L.

    2006-04-01

    The reactive transport of U(VI) in a shallow alluvial aquifer beneath a former U(VI) mill located near Naturita, CO, was simulated using a surface complexation model (SCM) to describe U(VI) adsorption. The groundwater had variable U(VI) concentrations (0.01-20 μM), variable alkalinity (2.5-18 meq/L), and a nearly constant pH equal to 7.1. U(VI) KD values decreased with increasing U(VI) and alkalinity, and these parameters were more important than sediment variability in controlling KD values. Reactive transport simulations were fit to the observed U(VI) and alkalinity by varying the concentration of U(VI) and alkalinity in recharge at the source area. Simulated KD values varied temporally and spatially because of the differential transport of U(VI) and alkalinity and the nonlinearity of U(VI) adsorption. The model also simulated the observed U(VI) tailing, which would not be expected from a constant KD model. The simulated U(VI) concentrations were sensitive to the recharge flux because of the increased flux of U(VI) to the aquifer. The geochemical behavior of U(VI) was most sensitive to the alkalinity and was relatively insensitive to pH.

  6. Highly parameterized inversion of groundwater reactive transport for a complex field site

    NASA Astrophysics Data System (ADS)

    Carniato, Luca; Schoups, Gerrit; van de Giesen, Nick; Seuntjens, Piet; Bastiaens, Leen; Sapion, Hans

    2015-02-01

    In this study a numerical groundwater reactive transport model of a shallow groundwater aquifer contaminated with volatile organic compounds is developed. In addition to advective-dispersive transport, the model includes contaminant release from source areas, natural attenuation, abiotic degradation by a permeable reactive barrier at the site, and dilution by infiltrating rain. Aquifer heterogeneity is parameterized using pilot points for hydraulic conductivity, specific yield and groundwater recharge. A methodology is developed and applied to estimate the large number of parameters from the limited data at the field site (groundwater levels, groundwater concentrations of multiple chemical species, point-scale measurements of soil hydraulic conductivity, and lab-scale derived information on chemical and biochemical reactions). The proposed methodology relies on pilot point parameterization of hydraulic parameters and groundwater recharge, a regularization procedure to reconcile the large number of spatially distributed model parameters with the limited field data, a step-wise approach for integrating the different data sets into the model, and high performance computing. The methodology was proven to be effective in reproducing multiple contaminant plumes and in reducing the prior parameter uncertainty of hydraulic conductivity and groundwater recharge. Our results further indicate that contaminant transport predictions are strongly affected by the choice of the groundwater recharge model and flow parameters should be identified using both head and concentration measurements.

  7. Highly parameterized inversion of groundwater reactive transport for a complex field site.

    PubMed

    Carniato, Luca; Schoups, Gerrit; van de Giesen, Nick; Seuntjens, Piet; Bastiaens, Leen; Sapion, Hans

    2015-02-01

    In this study a numerical groundwater reactive transport model of a shallow groundwater aquifer contaminated with volatile organic compounds is developed. In addition to advective-dispersive transport, the model includes contaminant release from source areas, natural attenuation, abiotic degradation by a permeable reactive barrier at the site, and dilution by infiltrating rain. Aquifer heterogeneity is parameterized using pilot points for hydraulic conductivity, specific yield and groundwater recharge. A methodology is developed and applied to estimate the large number of parameters from the limited data at the field site (groundwater levels, groundwater concentrations of multiple chemical species, point-scale measurements of soil hydraulic conductivity, and lab-scale derived information on chemical and biochemical reactions). The proposed methodology relies on pilot point parameterization of hydraulic parameters and groundwater recharge, a regularization procedure to reconcile the large number of spatially distributed model parameters with the limited field data, a step-wise approach for integrating the different data sets into the model, and high performance computing. The methodology was proven to be effective in reproducing multiple contaminant plumes and in reducing the prior parameter uncertainty of hydraulic conductivity and groundwater recharge. Our results further indicate that contaminant transport predictions are strongly affected by the choice of the groundwater recharge model and flow parameters should be identified using both head and concentration measurements.

  8. Simulation of reactive transport of uranium(VI) in groundwater with variable chemical conditions

    USGS Publications Warehouse

    Curtis, G.P.; Davis, J.A.; Naftz, D.L.

    2006-01-01

    The reactive transport of U(VI) in a shallow alluvial aquifer beneath a former U(VI) mill located near Naturita, CO, was simulated using a surface complexation model (SCM) to describe U(VI) adsorption. The groundwater had variable U(VI) concentrations (0.01-20 ??M), variable alkalinity (2.5-18 meq/L), and a nearly constant pH equal to 7.1. U(VI) KD values decreased with increasing U(VI) and alkalinity, and these parameters were more important than sediment variability in controlling KD values. Reactive transport simulations were fit to the observed U(VI) and alkalinity by varying the concentration of U(VI) and alkalinity in recharge at the source area. Simulated KD values varied temporally and spatially because of the differential transport of U(VI) and alkalinity and the nonlinearity of U(VI) adsorption. The model also simulated the observed U(VI) tailing, which would not be expected from a constant KD model. The simulated U(VI) concentrations were sensitive to the recharge flux because of the increased flux of U(VI) to the aquifer. The geochemical behavior of U(VI) was most sensitive to the alkalinity and was relatively insensitive to pH.

  9. A sequential partly iterative approach for multicomponent reactive transport with CORE2D

    SciTech Connect

    Samper, J.; Xu, T.; Yang, C.

    2008-11-01

    CORE{sup 2D} V4 is a finite element code for modeling partly or fully saturated water flow, heat transport and multicomponent reactive solute transport under both local chemical equilibrium and kinetic conditions. It can handle coupled microbial processes and geochemical reactions such as acid-base, aqueous complexation, redox, mineral dissolution/precipitation, gas dissolution/exsolution, ion exchange, sorption via linear and nonlinear isotherms, sorption via surface complexation. Hydraulic parameters may change due to mineral precipitation/dissolution reactions. Coupled transport and chemical equations are solved by using sequential iterative approaches. A sequential partly-iterative approach (SPIA) is presented which improves the accuracy of the traditional sequential noniterative approach (SNIA) and is more efficient than the general sequential iterative approach (SIA). While SNIA leads to a substantial saving of computing time, it introduces numerical errors which are especially large for cation exchange reactions. SPIA improves the efficiency of SIA because the iteration between transport and chemical equations is only performed in nodes with a large mass transfer between solid and liquid phases. The efficiency and accuracy of SPIA are compared to those of SIA and SNIA using synthetic examples and a case study of reactive transport through the Llobregat Delta aquitard in Spain. SPIA is found to be as accurate as SIA while requiring significantly less CPU time. In addition, SPIA is much more accurate than SNIA with only a minor increase in computing time. A further enhancement of the efficiency of SPIA is achieved by improving the efficiency of the Newton-Raphson method used for solving chemical equations. Such an improvement is obtained by working with increments of log-concentrations and ignoring the terms of the Jacobian matrix containing derivatives of activity coefficients. A proof is given for the symmetry and non-singularity of the Jacobian matrix

  10. Challenges in reactive transport modeling for prediction of geometry evolution in fractured carbonate rocks

    NASA Astrophysics Data System (ADS)

    Peters, C. A.; Deng, H.; Guo, B.; Fitts, J. P.

    2014-12-01

    Carbonate minerals are common in sedimentary rocks including in formations that serve as caprock seals. These formations are intended to stop migration of injected fluids, such as CO2 in the context of geologic carbon sequestration, ensuring permanent isolation from the atmosphere. Fractures in caprocks may allow injected CO2 and pressurized brine to escape. If the caprock contains substantial amounts of carbonates, flow of acidified fluids may cause substantial mineral dissolution which would increase the leakiness over time. Our research seeks to understand this process with particular attention to the evolution of fracture geometry and the implications for flow permeability. Our work combines high-pressure core flow experiments, x-ray imaging methods, reactive transport modeling, and computational fluid dynamics simulations. We have found that fracture permeability can increase substantially as a result of calcite dissolution. However, the extent of permeability increase is affected by complex alterations in fracture geometry. Newly-formed surface roughness and microporosity diminishes flow relative to what would be predicted by conventional practical models such as the local cubic law model. In contrast, channelization could lead to higher-than-expected flow rates because such fractures would stabilize open flow paths against geomechanical closure forces. Modeling these processes requires fine-scale 2D, if not 3D, reactive transport flow models that simulate not only the increase in fracture aperture but also the evolution in fracture geometry. Development of computationally-tractable reactive transport models that accurately predict reaction-induced changes in fracture permeability is an ongoing research priority in our lab.

  11. Coupling between geochemical reactions and multicomponent gas and solute transport in unsaturated media: A reactive transport modeling study

    NASA Astrophysics Data System (ADS)

    Molins, S.; Mayer, K. U.

    2007-05-01

    The two-way coupling that exists between biogeochemical reactions and vadose zone transport processes, in particular gas phase transport, determines the composition of soil gas. To explore these feedback processes quantitatively, multicomponent gas diffusion and advection are implemented into an existing reactive transport model that includes a full suite of geochemical reactions. Multicomponent gas diffusion is described on the basis of the dusty gas model, which accounts for all relevant gas diffusion mechanisms. The simulation of gas attenuation in partially saturated landfill soil covers, methane production, and oxidation in aquifers contaminated by organic compounds (e.g., an oil spill site) and pyrite oxidation in mine tailings demonstrate that both diffusive and advective gas transport can be affected by geochemical reactions. Methane oxidation in landfill covers reduces the existing upward pressure gradient, thereby decreasing the contribution of advective methane emissions to the atmosphere and enhancing the net flux of atmospheric oxygen into the soil column. At an oil spill site, methane oxidation causes a reversal in the direction of gas advection, which results in advective transport toward the zone of oxidation both from the ground surface and the deeper zone of methane production. Both diffusion and advection contribute to supply atmospheric oxygen into the subsurface, and methane emissions to the atmosphere are averted. During pyrite oxidation in mine tailings, pressure reduction in the reaction zone drives advective gas flow into the sediment column, enhancing the oxidation process. In carbonate-rich mine tailings, calcite dissolution releases carbon dioxide, which partly offsets the pressure reduction caused by O2 consumption.

  12. Coupling between geochemical reactions and multicomponent gas and solute transport in unsaturated media: A reactive transport modeling study

    USGS Publications Warehouse

    Molins, S.; Mayer, K.U.

    2007-01-01

    The two-way coupling that exists between biogeochemical reactions and vadose zone transport processes, in particular gas phase transport, determines the composition of soil gas. To explore these feedback processes quantitatively, multicomponent gas diffusion and advection are implemented into an existing reactive transport model that includes a full suite of geochemical reactions. Multicomponent gas diffusion is described on the basis of the dusty gas model, which accounts for all relevant gas diffusion mechanisms. The simulation of gas attenuation in partially saturated landfill soil covers, methane production, and oxidation in aquifers contaminated by organic compounds (e.g., an oil spill site) and pyrite oxidation in mine tailings demonstrate that both diffusive and advective gas transport can be affected by geochemical reactions. Methane oxidation in landfill covers reduces the existing upward pressure gradient, thereby decreasing the contribution of advective methane emissions to the atmosphere and enhancing the net flux of atmospheric oxygen into the soil column. At an oil spill site, methane oxidation causes a reversal in the direction of gas advection, which results in advective transport toward the zone of oxidation both from the ground surface and the deeper zone of methane production. Both diffusion and advection contribute to supply atmospheric oxygen into the subsurface, and methane emissions to the atmosphere are averted. During pyrite oxidation in mine tailings, pressure reduction in the reaction zone drives advective gas flow into the sediment column, enhancing the oxidation process. In carbonate-rich mine tailings, calcite dissolution releases carbon dioxide, which partly offsets the pressure reduction caused by O2 consumption.

  13. The reactive transport of trichloroethene is influenced by residence time and microbial numbers

    NASA Astrophysics Data System (ADS)

    Haest, P. J.; Philips, J.; Springael, D.; Smolders, E.

    2011-01-01

    The dechlorination rate in a flow-through porous matrix can be described by the species specific dechlorination rate observed in a liquid batch unless mass transport limitations prevail. This hypothesis was examined by comparing dechlorination rates in liquid batch with that in column experiments at various flow rates (3-9-12 cm day - 1 ). Columns were loaded with an inoculated sand and eluted with a medium containing 1 mM trichloroethene (TCE) for 247 days. Dechlorination in the column treatments increased with decreasing flow rate, illustrating the effect of the longer residence time. Zeroth order TCE or cis-DCE degradation rates were 4-7 folds larger in columns than in corresponding batch systems which could be explained by the higher measured Geobacter and Dehalococcoides numbers per unit pore volume in the columns. The microbial numbers also explained the variability in dechlorination rate among flow rate treatments marked by a large elution of the dechlorinating species' yield as flow increased. Stop flow events did not reveal mass transport limitations for dechlorination. We conclude that flow rate effects on reactive transport of TCE in this coarse sand are explained by residence time and by microbial transport and that mass transport limitations in this porous matrix are limited.

  14. Convective transport of reactive constituents to the tropical and mid-latitude tropopause region: I. Observations

    NASA Technical Reports Server (NTRS)

    Ridley, B.; Atlas, E.; Selkirk, H.; Pfister, L.; Montzka, D.; Walega, J.; Donnelly, S.; Stroud, V.; Richard, E.; Kelly, K.

    2004-01-01

    Measurements of ozone, reactive carbon and nitrogen, and other trace constituents from flights of the NASA WB-57F aircraft in the upper troposphere and lower stratosphere reveal that convection in the tropics can present a complex mix of surface-emitted constituents right up to the altitude of the lapse rate tropopause. At higher latitudes over the southern US, the strongest transport signal, in terms of constituent mixing ratios, occurred in the potential temperature range of 340-350K or approximately over the altitude range of 9-11km. Weaker convective signals were also seen up to near the tropopause. There was no evidence of convective transport directly into the lower stratosphere from these flights. $CPY 2003 Elsevier Ltd. All rights reserved.

  15. Assessing of Conceptual Models for Subsurface Reactive Transport of Inorganic Contaminants

    NASA Astrophysics Data System (ADS)

    Davis, James A.; Yabusaki, Steven B.; Steefel, Carl I.; Zachara, John M.; Curtis, Gary P.; Redden, George D.; Criscenti, Louise J.; Honeyman, Bruce D.

    2004-11-01

    In many subsurface situations where human health and environmental quality are at risk (e.g., contaminant hydrogeology, petroleum extraction, carbon sequestration, etc.), scientists and engineers are being asked by federal agency decision-makers to predict the fate of chemical species under conditions where both reactions and transport are processes of first-order importance. In 2002, a working group (WG) was formed by representatives of the U.S. Geological Survey, Environmental Protection Agency, Department of Energy, Nuclear Regulatory Commission, Department of Agriculture, and Army Engineer Research and Development Center to assess the role of reactive transport modeling (RTM) in addressing these situations. Specifically, the goals of the WG are to (1) evaluate the state of the art in conceptual model development and parameterization for RTM, as applied to soil, vadose zone, and groundwater systems, and (2) prioritize research directions that would enhance the practical utility of RTM.

  16. A parallelization scheme to simulate reactive transport in the subsurface environment with OGS#IPhreeqc

    NASA Astrophysics Data System (ADS)

    He, W.; Beyer, C.; Fleckenstein, J. H.; Jang, E.; Kolditz, O.; Naumov, D.; Kalbacher, T.

    2015-03-01

    This technical paper presents an efficient and performance-oriented method to model reactive mass transport processes in environmental and geotechnical subsurface systems. The open source scientific software packages OpenGeoSys and IPhreeqc have been coupled, to combine their individual strengths and features to simulate thermo-hydro-mechanical-chemical coupled processes in porous and fractured media with simultaneous consideration of aqueous geochemical reactions. Furthermore, a flexible parallelization scheme using MPI (Message Passing Interface) grouping techniques has been implemented, which allows an optimized allocation of computer resources for the node-wise calculation of chemical reactions on the one hand, and the underlying processes such as for groundwater flow or solute transport on the other hand. The coupling interface and parallelization scheme have been tested and verified in terms of precision and performance.

  17. Testing hypotheses of soil organic matter dynamics in a mechanistic reactive transport model

    NASA Astrophysics Data System (ADS)

    Riley, W. J.; Maggi, F.; Guerry, N.; Torn, M. S.; Kleber, M.

    2012-12-01

    The range of processes hypothesized to be important for long-term soil organic matter dynamics far exceeds the capabilities of current land models integrated in regional- to global-scale climate models. Yet SOM stability and CO2 fluxes from soils to the atmosphere are critical for future projections of climate. Recent syntheses of processes that may influence the trajectory of future soil C storage emphasize mineral interactions, enzyme dynamics, microbial population dynamics, transport, and interactions with plants and nutrient cycles. We contend that evaluating the relative importance of these processes requires a numerical modelling structure that allows for consistent comparison with observations, uncertainty characterization, and as mechanistic as possible a representation of the processes. We will describe a detailed spatially-resolved 3-dimensional reactive transport solver (TOUGHREACT) that represents abiotic and biotic SOM transformations and multi-phase flows. The modelling framework allows for explicit representation of (1) SOM interactions with minerals and their temperature, pH, and redox dependencies; (2) multiple microbial groups with different survival strategies and environmental sensitivities; (3) aqueous, gaseous, and sorbed phases; and (4) disaggregation of litter inputs, depolymerisation productions, and microbial bodies into an arbitrary number of SOM functional groups. The model accurately represented vertically-resolved bulk SOM in grassland and forest ecosystems using a baseline set of parameters. After testing, we used the model to investigate the relative impact of various mechanisms affecting SOM storage. Model predictions highlight the importance of sorption, aqueous transport, and microbial dynamics for the slow turnover of SOM that is observed below the rooting zone. We will also describe (1) model structural and parametric uncertainty; (2) methods to extract low-order model representations from the detailed reactive transport

  18. Reactive Transport Modelling of Heterocyclic Hydrocarbons at a Former Gasworks Site

    NASA Astrophysics Data System (ADS)

    Herold, M.; Ptak, T.; Wendel, T.; Grathwohl, P.

    2007-12-01

    Highly mobile heterocyclic hydrocarbons constitute a persistent threat to groundwater at a former gasworks site in Southern Germany. This area is currently being used as a test site for novel subsurface investigation techniques, as well as for a site-specific enhanced natural attenuation (ENA) remediation approach. The subsurface investigation consisted of direct-push borings and monitoring well installations, tracer tests, and Integral Pumping Tests (IPTs) at multiple control planes, which were positioned at different distances downgradient of the source zone and perpendicular to the contaminant plume transport direction. The numerical inversion of groundwater concentration time series measured during the IPTs, in combination with a groundwater flow and transport model of the test site, leads to estimations of total mass flow rates of contaminants or other groundwater parameters relevant to NA, as well as of average concentrations and concentration distributions along the control planes. Following detailed investigations of the microbial and chemical conditions at the site, an in-situ ENA method involving a circulation well and the use of O2 as a terminal electron acceptor was devised to aid aerobic microbial degradation of the heterocyclic compounds in the otherwise anoxic surroundings. The aims of the study presented here were to verify the proposed conceptual model of interacting physical and biogeochemical processes and to assess the effectiveness of the in-situ remediation approach with the help of multi-component reactive transport modelling, focusing on the situations (i) prior to the implementation of the in- situ remediation scheme and (ii) following the operation of the circulation well with O2 injection. A finite-difference model was devised using the software PMWIN and PHT3D, utilizing the collected data to simulate the relevant processes in two and three dimensions, respectively. Instead of using interpolated point scale concentration measurements

  19. New Reactive Transport Challenges for Acidified Flows in Fractured Carbonate Rocks

    NASA Astrophysics Data System (ADS)

    Peters, C. A.; Deng, H.; Fitts, J. P.

    2013-12-01

    The single most important reactive mineral in the context of permeability evolution of fractures is calcite because it is highly soluble and fast-reacting, it is ubiquitous in sedimentary rocks, and is often sufficiently abundant that dissolution would lead to important porosity changes. Calcite dissolution is promoted not only by low pH such as from injected CO2 but also by low concentration of calcium such as in injection of hydrofracking fluids. Thus, for a calcite-containing rock, if a flow path exists or if a fresh fracture is created during fluid injection or hydrofracking, flows can alter the hydrodynamic properties of the fracture, a process that may or may not be favorable, depending on the application. We have investigated these reaction-induced permeability alterations using reactive transport modeling and fractured core flooding experiments. In all cases, the general finding is that fracture permeability can increase substantially as a result of calcite dissolution, but the extent of this change is dependent on a complex interplay of the initial fracture geometry, mineral spatial heterogeneity and variation, and fluid composition and flow rate. Model simulations show that even with simple geochemical models that account only for calcite as a reactive mineral, complex dynamics arise. The alkalinity increase that results from calcium release causes the calcite dissolution reaction to be self-limiting. This buffering can lead to counter-intuitive findings such as systems with larger volume fractions of calcite having smaller permeability change. Another example of the calcium buffering effect is that a far-from-equilibrium solution may produce less permeability change than a nearer-to-equilibrium solution at the same pH. In the lab, we have used a suite of imaging technologies to observe additional complexities relating to the reactive evolution of the 3D geometry of fractures. These effects are currently not accounted for in any reactive transport model

  20. Nitrate Biogeochemistry and Reactive Transport in California Groundwater: LDRD Final Report

    SciTech Connect

    Esser, B K; Beller, H; Carle, S; Cey, B; Hudson, G B; Leif, R; LeTain, T; Moody-Bartel, C; Moore, K; McNab, W; Moran, J; Tompson, A

    2006-02-24

    Nitrate is the number one drinking water contaminant in the United States. It is pervasive in surface and groundwater systems,and its principal anthropogenic sources have increased dramatically in the last 50 years. In California alone, one third of the public drinking-water wells has been lost since 1988 and nitrate contamination is the most common reason for abandonment. Effective nitrate management in groundwater is complicated by uncertainties related to multiple point and non-point sources, hydrogeologic complexity, geochemical reactivity, and quantification of denitrification processes. In this paper, we review an integrated experimental and simulation-based framework being developed to study the fate of nitrate in a 25 km-long groundwater subbasin south of San Jose, California, a historically agricultural area now undergoing rapid urbanization with increasing demands for groundwater. The modeling approach is driven by a need to integrate new and archival data that support the hypothesis that nitrate fate and transport at the basin scale is intricately related to hydrostratigraphic complexity, variability of flow paths and groundwater residence times, microbial activity, and multiple geochemical reaction mechanisms. This study synthesizes these disparate and multi-scale data into a three-dimensional and highly resolved reactive transport modeling framework.

  1. Challenges of Tracer Analysis for Reach-Scale (Reactive) Transport (Invited)

    NASA Astrophysics Data System (ADS)

    Cirpka, O. A.; Lemke, D.; Liao, Z.; Diem, S.; Knapp, J.; Osenbrueck, K.; Schirmer, M.

    2013-12-01

    Both artificial and natural tracer signals are frequently used to analyze river-groundwater systems. Among the artificial tracer tests, injecting reactive compounds, such as resazurin, together with conservative compounds has recently gained recognition. Ideally, (1) the transformation would take place only in a certain compartment, such as the hyporheic zone (which is not guaranteed), (2) the reactive compounds would undergo only physical transport and a single reaction (but they also undergo unknown reactions and sorb), and (3) the observed reaction rates could uniquely be related to certain metabolic activity (which is difficult to prove). We have performed a series of tracer tests with the resazurin/resorufin system in streams and in sediment-filled columns to identify all processes affecting the tracer signals and develop methods for their quantification. We conclude that this tracer must be combined with other tracers to make a contribution for the understanding of biogeochemical processes in the river-aquifer system. We have also made good experience with the analysis of continuous natural tracer signals, both electric conductivity indicative for travel-time distributions and dissolved oxygen in piezometers and adjacent streams. For River Thur, we could come up with a simple zero-order model of oxygen consumption within the sediments, depending on temperature and discharge. Under conditions in which the time scales of velocity fluctuations and advective transport are comparable, however, a non-stationary analysis of the tracer signals is necessary to determine time-dependent travel-time distributions.

  2. Multiphase flow and multicomponent reactive transport model of the ventilation experiment in Opalinus clay

    SciTech Connect

    Zheng, L.; Samper, J.; Montenegro, L.; Major, J.C.

    2008-10-15

    During the construction and operational phases of a high-level radioactive waste (HLW) repository constructed in a clay formation, ventilation of underground drifts will cause desaturation and oxidation of the rock. The Ventilation Experiment (VE) was performed in a 1.3 m diameter unlined horizontal microtunnel on Opalinus clay at Mont Terri underground research laboratory in Switzerland to evaluate the impact of desaturation on rock properties. A multiphase flow and reactive transport model of VE is presented here. The model accounts for liquid, vapor and air flow, evaporation/condensation and multicomponent reactive solute transport with kinetic dissolution of pyrite and siderite and local-equilibrium dissolution/precipitation of calcite, ferrihydrite, dolomite, gypsum and quartz. Model results reproduce measured vapor flow, liquid pressure and hydrochemical data and capture the trends of measured relative humidities, although such data are slightly overestimated near the rock interface due to uncertainties in the turbulence factor. Rock desaturation allows oxygen to diffuse into the rock and triggers pyrite oxidation, dissolution of calcite and siderite, precipitation of ferrihydrite, dolomite and gypsum and cation exchange. pH in the unsaturated rock varies from 7.8 to 8 and is buffered by calcite. Computed changes in the porosity and the permeability of Opalinus clay in the unsaturated zone caused by oxidation and mineral dissolution/precipitation are smaller than 5%. Therefore, rock properties are not expected to be affected significantly by ventilation of underground drifts during construction and operational phases of a HLW repository in clay.

  3. MODFLOW/MT3DMS-based reactive multicomponent transport modeling.

    PubMed

    Prommer, H; Barry, D A; Zheng, C

    2003-01-01

    This paper presents a three-dimensional, MODFLOW/MT3DMS-based reactive multicomponent transport model for saturated porous media. Based on a split-operator technique, the model, referred to as PHT3D, couples the transport simulator MT3DMS and the geochemical modeling code PHREEQC-2. Through the flexible, generic nature of PHREEQC-2, PHT3D can handle a broad range of equilibrium and kinetically controlled reactive processes, including aqueous complexation, mineral precipitation/dissolution, and ion exchange. The diversity of potential applications is demonstrated through simulation of five existing literature benchmarks and a new three-dimensional sample problem. The model might be applied to simulate the geochemical evolution of pristine and contaminated aquifers as well as their cleanup. The latter problem class includes the natural and enhanced attenuation/remediation schemes of a wide range of organic and inorganic contaminants. Processes/reactions not included in the standard PHREEQC-2 database but typical for this type of application (e.g., NAPL dissolution, microbial growth/decay) can be defined and included via the extensible PHREEQC-2 database file.

  4. Experimental Study and Reactive Transport Modeling of Boric Acid Leaching of Concrete

    NASA Astrophysics Data System (ADS)

    Pabalan, R. T.; Chiang, K.-T. K.

    2013-07-01

    Borated water leakage through spent fuel pools (SFPs) at pressurized water reactors is a concern because it could cause corrosion of reinforcement steel in the concrete structure, compromise the integrity of the structure, or cause unmonitored releases of contaminated water to the environment. Experimental data indicate that pH is a critical parameter that determines the corrosion susceptibility of rebar in borated water and the degree of concrete degradation by boric acid leaching. In this study, reactive transport modeling of concrete leaching by borated water was performed to provide information on the solution pH in the concrete crack or matrix and the degree of concrete degradation at different locations of an SFP concrete structure exposed to borated water. Simulations up to 100 years were performed using different boric acid concentrations, crack apertures, and solution flow rates. Concrete cylinders were immersed in boric acid solutions for several months and the mineralogical changes and boric acid penetration in the concrete cylinder were evaluated as a function of time. The depths of concrete leaching by boric acid solution derived from the reactive transport simulations were compared with the measured boric acid penetration depth.

  5. Simulation of Nitrate Biogeochemistry and Reactive Transport in a California Groundwater Basin

    SciTech Connect

    Tompson, A B; Kane, S R; Beller, H R; Hudson, G B; McNab, W W; Moran, J E; Carle, S F; Esser, B K

    2004-01-16

    Nitrate is the number one drinking water contaminant in the United States. It is pervasive in surface and groundwater systems, and its principal anthropogenic sources have increased dramatically in the last 50 years. In California alone, one third of the public drinking-water wells has been lost since 1988 and nitrate contamination is the most common reason for abandonment. Effective nitrate management in groundwater is complicated by uncertainties related to multiple point and non-point sources, hydrogeologic complexity, geochemical reactivity, and quantification of dentrification processes. In this paper, we review an integrated experimental and simulation-based framework being developed to study the fate of nitrate in a 25 km-long groundwater subbasin south of San Jose, California, a historically agricultural area now undergoing rapid urbanization with increasing demands for groundwater. The modeling approach is driven by a need to integrate new and archival data that support the hypothesis that nitrate fate and transport at the basin scale is intricately related to hydrostratigraphic complexity, variability of flow paths and groundwater residence times, microbial activity, and multiple geochemical reaction mechanisms. This study synthesizes these disparate and multi-scale data into a three-dimensional and highly resolved reactive transport modeling framework.

  6. Understanding Microbial Reservoir Souring and Desouring Processes Using Reactive Transport Modeling

    NASA Astrophysics Data System (ADS)

    Cheng, Y.; Bouskill, N.; Hubbard, C. G.; Hubbard, S. S.; Ajo Franklin, J. B.; Li, L.; Engelbrektson, A. L.; Coates, J. D.; Surasani, V.

    2013-12-01

    Microbial sulfate reduction is the major metabolic process that leads to oil reservoir souring. Souring typically occurs when (sea)water is injected into the oil reservoir to maintain pressure and sweep remnant oil through the reservoir. Because biogenesis of hydrogen sulfide has detrimental impacts on oil production operations and can cause significant environmental and health problems, we strive to develop predictive understanding of reservoir souring and associated mitigation processes. Recent laboratory sediment column experiments have demonstrated the effectiveness of nitrate, chlorate and perchlorate treatments as souring control strategies. In this study, we describe the development of a reactive transport model that is based on the reaction mechanisms and kinetics revealed through the column experimental data. The model was used to simulate the temporal and spatial evolution of the primary chemical species (e.g. sulfate, sulfide, nitrate, chlorate and perchlorate) and the microbial dynamics involved in the souring and desouring processes. The growth and inhibition dynamics of the sulfate reducing bacterial population are explicitly simulated and constrained by energetics. Simulation of the laboratory experimental results show that the model captured the spatio-temporal trend of the chemical species and microbial guilds during both souring and desouring. Ongoing research is focusing on extending the reactive transport model to mechanistically understand, quantify, and predict souring and desouring processes within heterogeneous reservoirs as a step toward optimizing field scale souring control strategies.

  7. Characterizing biogeochemical processes in the hyporheic zone using flume experiments and reactive transport modeling

    NASA Astrophysics Data System (ADS)

    Quick, A. M.; Reeder, W. J.; Farrell, T. B.; Feris, K. P.; Tonina, D.; Benner, S. G.

    2015-12-01

    The hyporheic zones of streams are hotspots of biogeochemical cycling, where reactants from surface water and groundwater are continually brought into contact with microbial populations on the surfaces of stream sediments and reaction products are removed by hyporheic flow and degassing. Using large flume experiments we have documented the complex redox dynamics associated with dune-scale hyporheic flow. Observations, coupled with reactive transport modeling, provide insight into how flow dictates spatio-temporal distribution of redox reactions and the associated consumption and production of reactants and products. Dune hyporheic flow was experimentally produced by maintaining control over flow rates, slopes, sediment grain size, bedform geomorphology, and organic carbon content. An extensive in-situ monitoring array combined with sampling events over time elucidated redox-sensitive processes including constraints on the spatial distribution and magnitude of aerobic respiration, organic carbon consumption, sulfide deposition, and denitrification. Reactive transport modeling reveals further insight into the influence of system geometry and reaction rate. As an example application of the model, the relationship between residence times and reaction rates may be used to generate Damköhler numbers that are related to biogeochemical processes, such as the potential of streambed morphology and nitrate loading to influence production of the greenhouse gas nitrous oxide via incomplete denitrification.

  8. Moffett Field Funnel and Gate TCE Treatment System: Interpretation of Field Performance using Reactive Transport Modeling

    SciTech Connect

    Yabusaki, Steven B.; Cantrell, Kirk J.; Sass, B. M.

    2001-06-30

    A multicomponent reactive transport simulator was used to understand the behavior of chemical components, including TCE and cis-1,2-DCE, in groundwater transported through the pilot-scale funnel and gate chemical treatment system at Moffett Field, California. Field observations indicated that zero-valent iron emplaced in the gate to effect the destruction of chlorinated hydrocarbons also resulted in increases in pH and hydrocarbons, as well as decreases in EH, alkalinity, dissolved O2 and CO2, and major ions (i.e., Ca, Mg, Cl, sulfate, nitrate). Of concern are chemical transformations that may reduce the effectiveness or longevity of the iron cell and/or create secondary contaminants. A coupled model of transport and reaction processes was developed to account for mobile and immobile components undergoing equilibrium and kinetic reactions including TCE degradation, parallel iron dissolution reactions, precipitation of secondary minerals, and complexation reactions. The model reproduced solution chemistry observed in the iron cell using reaction parameters from the literature and laboratory studies. Mineral precipitation in the iron zone, which is critical to correctly predicting the aqueous concentrations, was predicted to account for up to 3 percent additional mineral volume annually. Interplay between rates of transport and rates of reaction in the field was key to understanding system behavior.

  9. Measurement and modelling of reactive transport in geological barriers for nuclear waste containment.

    PubMed

    Xiong, Qingrong; Joseph, Claudia; Schmeide, Katja; Jivkov, Andrey P

    2015-11-11

    Compacted clays are considered as excellent candidates for barriers to radionuclide transport in future repositories for nuclear waste due to their very low hydraulic permeability. Diffusion is the dominant transport mechanism, controlled by a nano-scale pore system. Assessment of the clays' long-term containment function requires adequate modelling of such pore systems and their evolution. Existing characterisation techniques do not provide complete pore space information for effective modelling, such as pore and throat size distributions and connectivity. Special network models for reactive transport are proposed here using the complimentary character of the pore space and the solid phase. This balances the insufficient characterisation information and provides the means for future mechanical-physical-chemical coupling. The anisotropy and heterogeneity of clays is represented using different length parameters and percentage of pores in different directions. Resulting networks are described as mathematical graphs with efficient discrete calculus formulation of transport. Opalinus Clay (OPA) is chosen as an example. Experimental data for the tritiated water (HTO) and U(vi) diffusion through OPA are presented. Calculated diffusion coefficients of HTO and uranium species are within the ranges of the experimentally determined data in different clay directions. This verifies the proposed pore network model and validates that uranium complexes are diffusing as neutral species in OPA. In the case of U(vi) diffusion the method is extended to account for sorption and convection. Rather than changing pore radii by coarse grained mathematical formula, physical sorption is simulated in each pore, which is more accurate and realistic.

  10. Macropore system characteristics controls on non-reactive solute transport at different flow rates

    NASA Astrophysics Data System (ADS)

    Larsbo, Mats; Koestel, John

    2014-05-01

    Preferential flow and transport in macroporous soils are important pathways for the leaching of agrochemicals through soils. Preferential solute transport in soil is to a large extent determined by the macropore system characteristics and the water flow conditions. The importance of different characteristics of the macropore system is likely to vary with the flow conditions. The objective of this study was to determine which properties of the macropore system that control the shape of non-reactive tracer solute breakthrough curves at different steady-state flow rates. We sampled five undisturbed columns (20 cm high, 20 cm diameter) from the soil surface of four soils with clay contents between 21 and 50 %. Solute transport experiments were carried out under unsaturated conditions at 2, 4, 6, 8 and 12 mm h-1 flow rates. For each flow rate a pulse of potassium bromide solution was applied at the soil surface and the electrical conductivity was measured with high temporal resolution in the column effluent. We used the 5 % arrival time and the holdback factor to estimate the degree of preferential transport from the resulting breakthrough curves. Unsaturated hydraulic conductivities were measured at the soil surface of the columns using a tension disc infiltrometer. The macropore system was imaged by industrial X-ray computed tomography at a resolution of 125 μm in all directions. Measures of the macropore system characteristics including measures of pore continuity were calculated from these images using the ImageJ software. Results show that the degree of preferential transport is generally increasing with flow rate when larger pores become active in the transport. The degree of preferential flow was correlated to measures of macropore topology. This study show that conclusions drawn from experiments carried out at one flow rate should generally not be extrapolated to other flow rates.

  11. Development of a numerical reactive transport modelling framework - Concept & Case Studies

    NASA Astrophysics Data System (ADS)

    Kalbacher, T.; Jang, E.; He, W.; Shao, H.; Zolfaghari, R.; Kolditz, O.

    2014-12-01

    Civilization and in particular agriculture worldwide depends on the availability of clean freshwater resources stored in the underlying soil and aquifer systems. Unfortunately, water quality is often deteriorating, which is e.g. due to the extensive use of fertilizers or pesticides in agriculture or infiltrating waste water from cities and industries. All groundwater bodies commonly discharge into the nearby surface-water bodies like streams, lakes, or springs, and soil water is a direct water source for the biosphere. Therefore, bio-hydro-geochemical reaction systems along flow paths of the unsaturated as well as the saturated zone can have a strong impact on aquatic and terrestrial ecosystems. The simulation of such reactive transport problems in different hydrological compartments can help to understanding the comprehensive processes chain. One way to evaluate the water quality in space and time is to model the mass transport in soil and/or groundwater together with the contemporaneous chemical reactions numerically. Such physical and bio- hydro- geochemical driven forward simulations are usually solved by standard finite differences, finite element or finite volume methods, but simulating these scenarios at catchment scales is a challenging task due to the extreme computational load, numerical stability issues and different scale-dependencies. The main focus of the present study is the numerical simulation of reactive transport processes in heterogeneous porous media at large scales, i.e. from field scale, over hill slopes towards catchment scale. The objective of the study is, to develop a robust modelling framework which allows to identify appropriate levels of heterogeneity as well as the possibly dominating structural features (e.g. S-shaped clay lenses) with respect to specific reaction systems. The presented modelling framework will describe the functional interaction of different numerical methods and high performing computing (HPC) techniques by the use

  12. Coupled thermohaline groundwater flow and single-species reactive solute transport in fractured porous media

    NASA Astrophysics Data System (ADS)

    Graf, Thomas; Therrien, René

    2007-04-01

    SummaryA 3D numerical model has been developed to solve coupled fluid flow, heat and single-species reactive mass transport with variable fluid density and viscosity. We focus on a single reaction between quartz and its aqueous form silica. The fluid density and viscosity and the dissolution rate constant, equilibrium constant and activity coefficient are calculated as a function of the concentrations of major ions and temperature. Reaction and flow parameters, such as mineral surface area and permeability, are updated at the end of each time step with explicitly calculated reaction rates. Adaptive time stepping is used to increase or decrease the time step size according to the rate of temporal variation of the solution to prevent physically unrealistic results. The time step size depends on maximum changes in matrix porosity and/or fracture aperture. The model is verified against existing analytical solutions of heat transfer and reactive transport in fractured porous media. The complexity of the model formulation allows studying chemical reactions and variable-density flow in a more realistic way than done previously. The newly developed model has been used to simulate illustrative examples of coupled thermohaline flow and reactive transport in fractured porous media. Simulations indicate that thermohaline (double-diffusive) transport impacts both buoyancy-driven flow and chemical reactions. Hot zones correspond to upwelling and to quartz dissolution while in cooler zones, the plume sinks and silica precipitates. The silica concentration is inversely proportional to salinity in high-salinity regions and proportional to temperature in low-salinity regions. Density contrasts are generally small and fractures do not act like preferential pathways but contribute to transverse dispersion of the plume. Results of a long-term (100 years) simulation indicate that the coexistence of dissolution and precipitation leads to self-sealing of fractures. Salt mass fluxes

  13. Reactive transport model of growth and methane production by high-temperature methanogens in hydrothermal regions of the subseafloor

    NASA Astrophysics Data System (ADS)

    Stewart, L. C.; Algar, C. K.; Topçuoğlu, B. D.; Fortunato, C. S.; Larson, B. I.; Proskurowski, G. K.; Butterfield, D. A.; Vallino, J. J.; Huber, J. A.; Holden, J. F.

    2014-12-01

    Hydrogenotrophic methanogens are keystone high-temperature autotrophs in deep-sea hydrothermal vents and tracers of habitability and biogeochemical activity in the hydrothermally active subseafloor. At Axial Seamount, nearly all thermophilic methanogens are Methanothermococcus and Methanocaldococcus species, making this site amenable to modeling through pure culture laboratory experiments coupled with field studies. Based on field microcosm incubations with 1.2 mM, 20 μM, or no hydrogen, the growth of methanogens at 55°C and 80°C is limited primarily by temperature and hydrogen availability, with ammonium amendment showing no consistent effect on total methane output. The Arrhenius constants for methane production by Methanocaldococcus jannaschii (optimum 82°C) and Methanothermococcus thermolithotrophicus (optimum 65°C) were determined in pure culture bottle experiments. The Monod constants for hydrogen concentration were measured by growing both organisms in a 2-liter chemostat at two dilution rates; 55°C, 65°C and 82°C; and variable hydrogen concentrations. M. jannaschii showed higher ks and Vmax constants than M. thermolithotrophicus. In the field, hydrogen and methane concentrations in hydrothermal end-member and low-temperature diffuse fluids were measured, and the concentrations of methanogens that grow at 55°C and 80°C in diffuse fluids were determined using most-probable-number estimates. Methane concentration anomalies in diffuse fluids relative to end-member hydrothermal concentrations and methanogen cell concentrations are being used to constrain a 1-D reactive transport model using the laboratory-determined Arrhenius and Monod constants for methane production by these organisms. By varying flow path length and subseafloor cell concentrations in the model, our goal is to determine solutions for the potential depth of the subseafloor biosphere coupled with the amount of methanogenic biomass it contains.

  14. Reactive transport modeling of uranium 238 and radium 226 in groundwater of the Königstein uranium mine, Germany

    NASA Astrophysics Data System (ADS)

    Nitzsche, O.; Merkel, B.

    Knowledge of the transport behavior of radionuclides in groundwater is needed for both groundwater protection and remediation of abandoned uranium mines and milling sites. Dispersion, diffusion, mixing, recharge to the aquifer, and chemical interactions, as well as radioactive decay, should be taken into account to obtain reliable predictions on transport of primordial nuclides in groundwater. This paper demonstrates the need for carrying out rehabilitation strategies before closure of the Königstein in-situ leaching uranium mine near Dresden, Germany. Column experiments on drilling cores with uranium-enriched tap water provided data about the exchange behavior of uranium. Uranium breakthrough was observed after more than 20 pore volumes. This strong retardation is due to the exchange of positively charged uranium ions. The code TReAC is a 1-D, 2-D, and 3-D reactive transport code that was modified to take into account the radioactive decay of uranium and the most important daughter nuclides, and to include double-porosity flow. TReAC satisfactorily simulated the breakthrough curves of the column experiments and provided a first approximation of exchange parameters. Groundwater flow in the region of the Königstein mine was simulated using the FLOWPATH code. Reactive transport behavior was simulated with TReAC in one dimension along a 6000-m path line. Results show that uranium migration is relatively slow, but that due to decay of uranium, the concentration of radium along the flow path increases. Results are highly sensitive to the influence of double-porosity flow. Résumé La protection des eaux souterraines et la restauration des sites miniers et de prétraitement d'uranium abandonnés nécessitent de connaître le comportement des radionucléides au cours de leur transport dans les eaux souterraines. La dispersion, la diffusion, le mélange, la recharge de l'aquifère et les interactions chimiques, de même que la décroissance radioactive, doivent être

  15. Kinetic parameter estimation in N. europaea biofilms using a 2-D reactive transport model.

    PubMed

    Lauchnor, Ellen G; Semprini, Lewis; Wood, Brian D

    2015-06-01

    Biofilms of the ammonia oxidizing bacterium Nitrosomonas europaea were cultivated to study microbial processes associated with ammonia oxidation in pure culture. We explored the hypothesis that the kinetic parameters of ammonia oxidation in N. europaea biofilms were in the range of those determined with batch suspended cells. Oxygen and pH microelectrodes were used to measure dissolved oxygen (DO) concentrations and pH above and inside biofilms and reactive transport modeling was performed to simulate the measured DO and pH profiles. A two dimensional (2-D) model was used to simulate advection parallel to the biofilm surface and diffusion through the overlying fluid while reaction and diffusion were simulated in the biofilm. Three experimental studies of microsensor measurements were performed with biofilms: i) NH3 concentrations near the Ksn value of 40 μM determined in suspended cell tests ii) Limited buffering capacity which resulted in a pH gradient within the biofilms and iii) NH3 concentrations well below the Ksn value. Very good fits to the DO concentration profiles both in the fluid above and in the biofilms were achieved using the 2-D model. The modeling study revealed that the half-saturation coefficient for NH3 in N. europaea biofilms was close to the value measured in suspended cells. However, the third study of biofilms with low availability of NH3 deviated from the model prediction. The model also predicted shifts in the DO profiles and the gradient in pH that resulted for the case of limited buffering capacity. The results illustrate the importance of incorporating both key transport and chemical processes in a biofilm reactive transport model.

  16. Modeling reactive geochemical transport of concentrated aqueous solutions in variably saturated media

    SciTech Connect

    Zhang, Guoxiang; Zheng, Zuoping; Wan, Jiamin

    2004-01-28

    Concentrated aqueous solutions (CAS) have unique thermodynamic and physical properties. Chemical components in CAS are incompletely dissociated, especially those containing divalent or polyvalent ions. The problem is further complicated by the interaction between CAS flow processes and the naturally heterogeneous sediments. As the CAS migrates through the porous media, the composition may be altered subject to fluid-rock interactions. To effectively model reactive transport of CAS, we must take into account ion-interaction. A combination of the Pitzer ion-interaction and the ion-association model would be an appropriate way to deal with multiple-component systems if the Pitzer' parameters and thermodynamic data of dissolved components and the related minerals are available. To quantify the complicated coupling of CAS flow and transport, as well as the involved chemical reactions in natural and engineered systems, we have substantially extended an existing reactive biogeochemical transport code, BIO-CORE{sup 2D}{copyright}, by incorporating a comprehensive Pitzer ion-interaction model. In the present paper, the model, and two test cases against measured data were briefly introduced. Finally we present an application to simulate a laboratory column experiment studying the leakage of the high alkaline waste fluid stored in Hanford (a site of the U.S. Department of Energy, located in Washington State, USA). With the Pitzer ion-interaction ionic activity model, our simulation captures measured pH evolution. The simulation indicates that all the reactions controlling the pH evolution, including cation exchanges, mineral precipitation and dissolution, are coupled.

  17. Evaluating remedial alternatives for an acid mine drainage stream: Application of a reactive transport model

    USGS Publications Warehouse

    Runkel, R.L.; Kimball, B.A.

    2002-01-01

    A reactive transport model based on one-dimensional transport and equilibrium chemistry is applied to synoptic data from an acid mine drainage stream. Model inputs include streamflow estimates based on tracer dilution, inflow chemistry based on synoptic sampling, and equilibrium constants describing acid/base, complexation, precipitation/dissolution, and sorption reactions. The dominant features of observed spatial profiles in pH and metal concentration are reproduced along the 3.5-km study reach by simulating the precipitation of Fe(III) and Al solid phases and the sorption of Cu, As, and Pb onto freshly precipitated iron-(III) oxides. Given this quantitative description of existing conditions, additional simulations are conducted to estimate the streamwater quality that could result from two hypothetical remediation plans. Both remediation plans involve the addition of CaCO3 to raise the pH of a small, acidic inflow from ???2.4 to ???7.0. This pH increase results in a reduced metal load that is routed downstream by the reactive transport model, thereby providing an estimate of post-remediation water quality. The first remediation plan assumes a closed system wherein inflow Fe(II) is not oxidized by the treatment system; under the second remediation plan, an open system is assumed, and Fe(II) is oxidized within the treatment system. Both plans increase instream pH and substantially reduce total and dissolved concentrations of Al, As, Cu, and Fe(II+III) at the terminus of the study reach. Dissolved Pb concentrations are reduced by ???18% under the first remediation plan due to sorption onto iron-(III) oxides within the treatment system and stream channel. In contrast, iron(III) oxides are limiting under the second remediation plan, and removal of dissolved Pb occurs primarily within the treatment system. This limitation results in an increase in dissolved Pb concentrations over existing conditions as additional downstream sources of Pb are not attenuated by

  18. Numerical simulation of fracture permeability evolution due to reactive transport and pressure solution processes

    NASA Astrophysics Data System (ADS)

    Watanabe, N.; Sun, Y.; Taron, J.; Shao, H.; Kolditz, O.

    2013-12-01

    Modeling fracture permeability evolution is of great interest in various geotechnical applications including underground waste repositories, carbon capture and storage, and engineered geothermal systems where fractures dominate transport behaviors. In this study, a numerical model is presented to simulate fracture permeability evolution due to reactive transport and pressure solution processes in single fractures. The model was developed within the international benchmarking project for radioactive waste disposals, DECOVALEX 2015 (Task C1). The model combines bulk behavior in pore spaces with intergranular process at asperity contacts. Hydraulic flow and reactive transport including mineral dissolution and precipitation in fracture pore space are simulated using the Galerkin finite element method. A pressure solution model developed by Taron and Elsworth (2010 JGR) is applied to simulating stress-enhanced dissolution, solute exchange with pore space, and volume removal at grain contacts. Fracture aperture and contact area ratio are updated as a result of the pore-space reaction and intergranular dissolution. In order to increase robustness and time step size, relevant processes are monolithically coupled with the simulations. The model is implemented in a scientific open-source project OpenGeoSys (www.opengeosys.org) for numerical simulation of thermo-hydro-mechanical/chemical processes in porous and fractured media. Numerical results are compared to previous experiment performed by Yasuhara et al. (2006) on flow through fractures in the Arkansas novaculite sample. The novaculite is approximated as pure quartz aggregates. Only with fitted quartz dissolution rate constants and solubility is the current model capable of reproducing observed hydraulic aperture reduction and aqueous silicate concentrations. Future work will examine reaction parameters and further validate the model against experimental results.

  19. A heterocyclic compound CE-103 inhibits dopamine reuptake and modulates dopamine transporter and dopamine D1-D3 containing receptor complexes.

    PubMed

    Sase, Ajinkya; Aher, Yogesh D; Saroja, Sivaprakasam R; Ganesan, Minu Karthika; Sase, Sunetra; Holy, Marion; Höger, Harald; Bakulev, Vasiliy; Ecker, Gerhard F; Langer, Thierry; Sitte, Harald H; Leban, Johann; Lubec, Gert

    2016-03-01

    A series of compounds have been reported to enhance memory via the DA system and herein a heterocyclic compound was tested for working memory (WM) enhancement. 2-((benzhydrylsulfinyl)methyl)thiazole (CE-103) was synthesized in a six-step synthesis. Binding of CE-103 to the dopamine (DAT), serotonin (SERT) and norepinephrine (NET) transporters and dopamine reuptake inhibition was tested as well as blood brain permeation and a screen for GPCR targets. 60 male Sprague Dawley rats were divided into six groups: CE-103 treated 1-10 mg/kg body weight, trained (TDI) and yoked (YDI) and vehicle treated, trained (TVI) and yoked (YVI) rats. Daily single intraperitoneal injections for a period of 10 days were administered and rats were tested in a radial arm maze (RAM). Hippocampi were taken 6 h following the last day of training and complexes containing the unphosphorylated or phosphorylated dopamine transporter (DAT) and complexes containing the D1-3 dopamine receptor subunits were determined. CE-103 was binding to the DAT but insignificantly to SERT or NET and dopamine reuptake was blocked specifically (IC50 = 14.73 μM). From day eight the compound was decreasing WM errors in the RAM significantly at both doses tested as compared to the vehicle controls. In the trained CE-103-treated group levels of the complex containing the phosphorylated dopamine transporter (pDAT) as well as D1R were decreased while levels of complexes containing D2R and D3R were significantly increased. CE-103 was shown to enhance spatial WM and DA reuptake inhibition with subsequent modulation of D1-3 receptors is proposed as a possible mechanism of action.

  20. Suppressor mutations in the Glutamine Dumper1 protein dissociate disturbance in amino acid transport from other characteristics of the Gdu1D phenotype.

    PubMed

    Yu, Shi; Pratelli, Réjane; Denbow, Cynthia; Pilot, Guillaume

    2015-01-01

    Intracellular amino acid transport across plant membranes is critical for metabolic pathways which are often split between different organelles. In addition, transport of amino acids across the plasma membrane enables the distribution of organic nitrogen through the saps between leaves and developing organs. Amino acid importers have been studied for more than two decades, and their role in this process is well-documented. While equally important, amino acid exporters are not well-characterized. The over-expression of GDU1, encoding a small membrane protein with one transmembrane domain, leads to enhancement of amino acid export by Arabidopsis cells, glutamine secretion at the leaf margin, early senescence and size reduction of the plant, possibly caused by the stimulation of amino acid exporter(s). Previous work reported the identification of suppressor mutations of the GDU1 over-expression phenotype, which affected the GDU1 and LOG2 genes, the latter encoding a membrane-bound ubiquitin ligase interacting with GDU1. The present study focuses on the characterization of three additional suppressor mutations affecting GDU1. Size, phenotype, glutamine transport and amino acid tolerance were recorded for recapitulation plants and over-expressors of mutagenized GDU1 proteins. Unexpectedly, the over-expression of most mutated GDU1 led to plants with enhanced amino acid export, but failing to display secretion of glutamine and size reduction. The results show that the various effects triggered by GDU1 over-expression can be dissociated from one another by mutagenizing specific residues. The fact that these residues are not necessarily conserved suggests that the diverse biochemical properties of the GDU1 protein are not only born by the characterized transmembrane and VIMAG domains. These data provide a better understanding of the structure/function relationships of GDU1 and may enable modifying amino acid export in plants without detrimental effects on plant fitness.

  1. A conservative, positivity preserving scheme for reactive solute transport problems in moving domains

    NASA Astrophysics Data System (ADS)

    Mabuza, Sibusiso; Kuzmin, Dmitri; Čanić, Sunčica; Bukač, Martina

    2014-11-01

    We study the mathematical models and numerical schemes for reactive transport of a soluble substance in deformable media. The medium is a channel with compliant adsorbing walls. The solutes are dissolved in the fluid flowing through the channel. The fluid, which carries the solutes, is viscous and incompressible. The reactive process is described as a general physico-chemical process taking place on the compliant channel wall. The problem is modeled by a convection-diffusion adsorption-desorption equation in moving domains. We present a conservative, positivity preserving, high resolution ALE-FCT scheme for this problem in the presence of dominant transport processes and wall reactions on the moving wall. A Patankar type time discretization is presented, which provides conservative treatment of nonlinear reactive terms. We establish CFL-type constraints on the time step, and show the mass conservation of the time discretization scheme. Numerical simulations are performed to show validity of the schemes against effective models under various scenarios including linear adsorption-desorption, irreversible wall reaction, infinite adsorption kinetics, and nonlinear Langmuir kinetics. The grid convergence of the numerical scheme is studied for the case of fixed meshes and moving meshes in fixed domains. Finally, we simulate reactive transport in moving domains under linear and nonlinear chemical reactions at the wall, and show that the motion of the compliant channel wall enhances adsorption of the solute from the fluid to the channel wall. Consequences of this result are significant in the area of, e.g., nano-particle cancer drug delivery. Our result shows that periodic excitation of the cancerous tissue using, e.g., ultrasound, may enhance adsorption of cancer drugs carried by nano-particles via the human vasculature. For Taylor dispersion and for other convection dominated flows, numerical schemes for solute transport may lead to undesirable numerical artefacts. These

  2. Transient Modeling of Reactive Solute Transport in a Submarine Groundwater Discharge Zone

    NASA Astrophysics Data System (ADS)

    Colman, J. A.; Bratton, J. F.; Crusius, J.; Kroeger, K. D.; Baldwin, S.; Lee, K.

    2009-12-01

    Submarine groundwater discharge (SGD) is the dominant means of freshwater delivery to many coastal embayments on the glaciated coast of Cape Cod (Mass.). This discharge is the focus of considerable research, in part because the common disposal of sewage via septic systems has led to elevated concentrations of nutrients in groundwater. Subsurface mixing and chemical reactivity prior to discharge can affect the amounts of nutrients entering the embayments. Water-quality problems including eutrophication and harmful algal blooms appear to be controlled by the timing and intensity of SGD at our field site, Salt Pond, a weakly stratified estuary 8.2 ha in area with a maximum depth of 9 m and tidal amplitude of 2 m. The site is located at the northern (inland) end of Nauset Marsh on outer Cape Cod. We estimated mixing and reaction rates in the discharge area by fitting a 2-D reactive-solute-transport model (PHAST) to chemical observations in the intertidal subsurface using hydrologic forcing from aquifer recharge and tides. Chemical measurements in the subsurface, taken at 5 intervals spanning the seasons from a multilevel-sampler (MLS) array, 20 m long by 6 m deep, indicate a change in the position of the groundwater salt front on both tidal and seasonal time scales, with a maximum horizontal movement of approximately 4 m. Observed movement of the salt front corresponded with simulated movement modeled by changing seasonal recharge to the aquifer. Kinetics of oxygen consumption in the subsurface were modeled using end-member concentrations of oxygen in upgradient fresh groundwater and in water-column saltwater, assumed biological oxygen demand in saltwater, and model-determined residence time in the subsurface. High measured concentrations of nitrate (up to 7 mg/L as N) in intertidal groundwater were unaffected by denitrification prior to discharge based on both chemical analysis of denitrification indicators in MLS samples, and model results. This work demonstrates

  3. Reactive Transport Models with Geomechanics to Mitigate Risks of CO2 Utilization and Storage

    SciTech Connect

    Deo, Milind; Huang, Hai; Kweon, Hyukmin; Guo, Luanjing

    2016-03-28

    Reactivity of carbon dioxide (CO2), rocks and brine is important in a number of practical situations in carbon dioxide sequestration. Injectivity of CO2 will be affected by near wellbore dissolution or precipitation. Natural fractures or faults containing specific minerals may reactivate leading to induced seismicity. In this project, we first examined if the reactions between CO2, brine and rocks affect the nature of the porous medium and properties including petrophysical properties in the timeframe of the injection operations. This was done by carrying out experiments at sequestration conditions (2000 psi for corefloods and 2400 psi for batch experiments, and 600°C) with three different types of rocks – sandstone, limestone and dolomite. Experiments were performed in batch mode and corefloods were conducted over a two-week period. Batch experiments were performed with samples of differing surface area to understand the impact of surface area on overall reaction rates. Toughreact, a reactive transport model was used to interpret and understand the experimental results. The role of iron in dissolution and precipitation reactions was observed to be significant. Iron containing minerals – siderite and ankerite dissolved resulting in changes in porosity and permeability. Corefloods and batch experiments revealed similar patterns. With the right cationic balance, there is a possibility of precipitation of iron bearing carbonates. The results indicate that during injection operations mineralogical changes may lead to injectivity enhancements near the wellbore and petrophysical changes elsewhere in the system. Limestone and dolomite cores showed consistent dissolution at the entrance of the core. The dissolution led to formation of wormholes and interconnected dissolution zones. Results indicate that near wellbore dissolution in these rock-types may lead to rock failure. Micro-CT images of the cores before and after the experiments

  4. Comparing approaches for simulating the reactive transport of U(VI) in ground water

    USGS Publications Warehouse

    Curtis, G.P.; Kohler, M.; Davis, J.A.

    2009-01-01

    The reactive transport of U(VI) in a well-characterized shallow alluvial aquifer at a former U(VI) mill located near Naturita, CO, was predicted for comparative purposes using a surface complexation model (SCM) and a constant K d approach to simulate U(VI) adsorption. The ground water at the site had U(VI) concentrations that ranged from 0.01 to 20 ??M, alkalinities that ranged from 2.5 to 18 meq/L, and a nearly constant pH of 7.1. The SCM used to simulate U(VI) adsorption was previously determined independently using laboratory batch adsorption experiments. Simulations obtained using the SCM approach were compared with simulations that used a constant K d approach to simulate adsorption using previously determined site-specific K d values. In both cases, the ground water flow and transport models used a conceptual model that was previously calibrated to a chloride plume present at the site. Simulations with the SCM approach demonstrated that the retardation factor varied temporally and spatially because of the differential transport of alkalinity and dissolved U(VI) and the nonlinearity of the U(VI) adsorption. The SCM model also simulated a prolonged slow decline in U(VI) concentration, which was not simulated using a constant K d model. Simulations using the SCM approach and the constant K d approach were similar after 20 years of transport but diverged significantly after 60 years. The simulations demonstrate the need for site-specific geochemical information on U(VI) adsorption to produce credible simulations of future transport. ?? 2009 Springer-Verlag.

  5. Accelerating flow propagator measurements for the investigation of reactive transport in porous media

    NASA Astrophysics Data System (ADS)

    Colbourne, A. A.; Sederman, A. J.; Mantle, M. D.; Gladden, L. F.

    2016-11-01

    NMR propagator measurements are widely used for identifying the distribution of molecular displacements over a given observation time, characterising a flowing system. However, where high q-space resolution is required, the experiments are time consuming and therefore unsuited to the study of dynamic systems. Here, it is shown that with an appropriately sampled subset of the q-space points in a high-resolution flow propagator measurement, one can quickly and robustly reconstruct the fully sampled propagator through interpolation of the acquired raw data. It was found that exponentially sampling ∼4% of the original data-points allowed a reconstruction with the deviation from the fully sampled propagator below the noise level, in this case reducing the required experimental time from ∼2.8 h to <7 min. As a demonstration, this approach is applied to observe the temporal evolution of the reactive flow of acid through an Estaillades rock core plug. It is shown that 'wormhole' formation in the rock core plug provides a channel for liquid flow such that the remaining pore space is by-passed, thereby causing the flow velocity of the liquid in the remaining part of the plug to become stagnant. The propagator measurements are supported by both 1D profiles and 2D imaging data. Such insights are of importance in understanding well acidisation and CO2 sequestration processes.

  6. Reactive Transport and Coupled THM Processes in Engineering Barrier Systems (EBS)

    SciTech Connect

    Steefel, Carl; Rutqvist, Jonny; Tsang, Chin-Fu; Liu, Hui-Hai; Sonnenthal, Eric; Houseworth, Jim; Birkholzer, Jens

    2010-08-31

    Geological repositories for disposal of high-level nuclear wastes generally rely on a multi-barrier system to isolate radioactive wastes from the biosphere. The multi-barrier system typically consists of a natural barrier system, including repository host rock and its surrounding subsurface environment, and an engineering barrier system (EBS). EBS represents the man-made, engineered materials placed within a repository, including the waste form, waste canisters, buffer materials, backfill and seals (OECD, 2003). EBS plays a significant role in the containment and long-term retardation of radionuclide release. EBS is involved in complex thermal, hydrogeological, mechanical, chemical and biological processes, such as heat release due to radionuclide decay, multiphase flow (including gas release due to canister corrosion), swelling of buffer materials, radionuclide diffusive transport, waste dissolution and chemical reactions. All these processes are related to each other. An in-depth understanding of these coupled processes is critical for the performance assessment (PA) for EBS and the entire repository. Within the EBS group of Used Fuel Disposition (UFD) Campaign, LBNL is currently focused on (1) thermal-hydraulic-mechanical-chemical (THMC) processes in buffer materials (bentonite) and (2) diffusive transport in EBS associated with clay host rock, with a long-term goal to develop a full understanding of (and needed modeling capabilities to simulate) impacts of coupled processes on radionuclide transport in different components of EBS, as well as the interaction between near-field host rock (e.g., clay) and EBS and how they effect radionuclide release. This final report documents the progress that LBNL has made in its focus areas. Specifically, Section 2 summarizes progress on literature review for THMC processes and reactive-diffusive radionuclide transport in bentonite. The literature review provides a picture of the state-of-the-art of the relevant research areas

  7. Experimental investigation of the link between pore scale velocities, transport and reactivity in porous media

    NASA Astrophysics Data System (ADS)

    Meheust, Y.; Turuban, R.; Jimenez-Martinez, J.; De Anna, P.; Tabuteau, H.; Le Borgne, T.

    2014-12-01

    Pore scale characterization of flow velocities and concentration spatial distributions is a key to understanding non-Fickian transport and mixing in porous media. We present a millifluidic setup aimed at investigating those processes in transparent porous media, at the pore scale. The porous media are quasi-2D, consisting of a Hele-Shaw cell containing cylindrical grains. They are made by soft lithography from a numerical model and provide full control on the geometry (medium porosity, permeability and heterogeneity). The setup allows for the study of primary drainage/imbibition, or the joint continuous injection of two fluids (e. g. water and air). A camera records the distributions of fluid phases, the position of solid tracers, and spatially-resolved images of light emissions inside the flow cell. The pore scale velocity field is thus measured from particle tracking, while pore scale concentration fields are measured accurately in passive transport experiments, using fluorescein; both continuous injection and finite volume solute injections can be achieved. Using two chemo-luminescent liquids, the reaction of which produces photons in addition to the reaction product, we are also able to study the local production rate of the reaction product as the reactive liquids flow through the system [1]. Pressure drops across the medium are also measured. This complete characterization (phase distributions, velocity and concentration fields, pressure drops) of the system allows to explain non-Fickian behaviors and test models that upscale transport and mixing properties from pore scale data. As examples, we shall discuss the upscaling of transport from the knowledge of Lagrangian velocities and the relationships between conservative and reactive transport under mixing-limited conditions (very large Damkhöler number). Other applications include the prediction of the mixing rate from the sole knowledge of the flow stretching [2], and the characterization of mixing by

  8. Modeling the transport of chemical warfare agents and simulants in polymeric substrates for reactive decontamination

    NASA Astrophysics Data System (ADS)

    Pearl, Thomas; Mantooth, Brent; Varady, Mark; Willis, Matthew

    2014-03-01

    Chemical warfare agent simulants are often used for environmental testing in place of highly toxic agents. This work sets the foundation for modeling decontamination of absorbing polymeric materials with the focus on determining relationships between agents and simulants. The correlations of agents to simulants must consider the three way interactions in the chemical-material-decontaminant system where transport and reaction occur in polymer materials. To this end, diffusion modeling of the subsurface transport of simulants and live chemical warfare agents was conducted for various polymer systems (e.g., paint coatings) with and without reaction pathways with applied decontamination. The models utilized 1D and 2D finite difference diffusion and reaction models to simulate absorption and reaction in the polymers, and subsequent flux of the chemicals out of the polymers. Experimental data including vapor flux measurements and dynamic contact angle measurements were used to determine model input parameters. Through modeling, an understanding of the relationship of simulant to live chemical warfare agent was established, focusing on vapor emission of agents and simulants from materials.

  9. Towards a realistic approach to validation of reactive transport models for performance assessment

    SciTech Connect

    Siegel, M.D.

    1993-12-31

    Performance assessment calculations are based on geochemical models that assume that interactions among radionuclides, rocks and groundwaters under natural conditions, can be estimated or bound by data obtained from laboratory-scale studies. The data include radionuclide distribution coefficients, measured in saturated batch systems of powdered rocks, and retardation factors measured in short-term column experiments. Traditional approaches to model validation cannot be applied in a straightforward manner to the simple reactive transport models that use these data. An approach to model validation in support of performance assessment is described in this paper. It is based on a recognition of different levels of model validity and is compatible with the requirements of current regulations for high-level waste disposal. Activities that are being carried out in support of this approach include (1) laboratory and numerical experiments to test the validity of important assumptions inherent in current performance assessment methodologies,(2) integrated transport experiments, and (3) development of a robust coupled reaction/transport code for sensitivity analyses using massively parallel computers.

  10. Modeling reactive transport of reclaimed water through large soil columns with different low-permeability layers

    NASA Astrophysics Data System (ADS)

    Hu, Haizhu; Mao, Xiaomin; Barry, D. A.; Liu, Chengcheng; Li, Pengxiang

    2015-03-01

    The efficacy of different proportions of silt-loam/bentonite mixtures overlying a vadose zone in controlling solute leaching to groundwater was quantified. Laboratory experiments were carried out using three large soil columns, each packed with 200-cm-thick riverbed soil covered by a 2-cm-thick bentonite/silt-loam mixture as the low-permeability layer (with bentonite mass accounting for 12, 16 and 19 % of the total mass of the mixture). Reclaimed water containing ammonium (NH4 +), nitrate (NO3 -), organic matter (OM), various types of phosphorus and other inorganic salts was applied as inflow. A one-dimensional mobile-immobile multi-species reactive transport model was used to predict the preferential flow and transport of typical pollutants through the soil columns. The simulated results show that the model is able to predict the solute transport in such conditions. Increasing the amount of bentonite in the low-permeability layer improves the removal of NH4 + and total phosphorous (TP) because of the longer contact time and increased adsorption capacity. The removal of NH4 + and OM is mainly attributed to adsorption and biodegradation. The increase of TP and NO3 - concentration mainly results from discharge and nitrification in riverbed soils, respectively. This study underscores the role of low-permeability layers as barriers in groundwater protection. Neglect of fingers or preferential flow may cause underestimation of pollution risk.

  11. Modeling hydrology and reactive transport in roads: the effect of cracks, the edge, and contaminant properties.

    PubMed

    Apul, Defne S; Gardner, Kevin H; Eighmy, T Taylor

    2007-01-01

    The goal of this research was to provide a tool for regulators to evaluate the groundwater contamination from the use of virgin and secondary materials in road construction. A finite element model, HYDRUS2D, was used to evaluate generic scenarios for secondary material use in base layers. Use of generic model results for particular applications was demonstrated through a steel slag example. The hydrology and reactive transport of contaminants were modeled in a two-dimensional cross section of a road. Model simulations showed that in an intact pavement, lateral velocities from the edge towards the centerline may transport contaminants in the base layer. The dominant transport mechanisms are advection closer to the edge and diffusion closer to the centerline. A shoulder joint in the pavement allows 0.03 to 0.45 m(3)/day of infiltration per meter of joint length as a function of the base and subgrade hydrology and the rain intensity. Scenario simulations showed that salts in the base layer of pavements are depleted by 99% in the first 20 years, whereas the metals may not reach the groundwater in 20 years at any significant concentrations if the pavement is built on adsorbing soils.

  12. Modeling hydrology and reactive transport in roads: The effect of cracks, the edge, and contaminant properties

    SciTech Connect

    Apul, Defne S. Gardner, Kevin H. Eighmy, T. Taylor

    2007-07-01

    The goal of this research was to provide a tool for regulators to evaluate the groundwater contamination from the use of virgin and secondary materials in road construction. A finite element model, HYDRUS2D, was used to evaluate generic scenarios for secondary material use in base layers. Use of generic model results for particular applications was demonstrated through a steel slag example. The hydrology and reactive transport of contaminants were modeled in a two-dimensional cross section of a road. Model simulations showed that in an intact pavement, lateral velocities from the edge towards the centerline may transport contaminants in the base layer. The dominant transport mechanisms are advection closer to the edge and diffusion closer to the centerline. A shoulder joint in the pavement allows 0.03 to 0.45 m{sup 3}/day of infiltration per meter of joint length as a function of the base and subgrade hydrology and the rain intensity. Scenario simulations showed that salts in the base layer of pavements are depleted by 99% in the first 20 years, whereas the metals may not reach the groundwater in 20 years at any significant concentrations if the pavement is built on adsorbing soils.

  13. Geophysical monitoring and reactive transport modeling of ureolytically-driven calcium carbonate precipitation

    PubMed Central

    2011-01-01

    Ureolytically-driven calcium carbonate precipitation is the basis for a promising in-situ remediation method for sequestration of divalent radionuclide and trace metal ions. It has also been proposed for use in geotechnical engineering for soil strengthening applications. Monitoring the occurrence, spatial distribution, and temporal evolution of calcium carbonate precipitation in the subsurface is critical for evaluating the performance of this technology and for developing the predictive models needed for engineering application. In this study, we conducted laboratory column experiments using natural sediment and groundwater to evaluate the utility of geophysical (complex resistivity and seismic) sensing methods, dynamic synchrotron x-ray computed tomography (micro-CT), and reactive transport modeling for tracking ureolytically-driven calcium carbonate precipitation processes under site relevant conditions. Reactive transport modeling with TOUGHREACT successfully simulated the changes of the major chemical components during urea hydrolysis. Even at the relatively low level of urea hydrolysis observed in the experiments, the simulations predicted an enhanced calcium carbonate precipitation rate that was 3-4 times greater than the baseline level. Reactive transport modeling results, geophysical monitoring data and micro-CT imaging correlated well with reaction processes validated by geochemical data. In particular, increases in ionic strength of the pore fluid during urea hydrolysis predicted by geochemical modeling were successfully captured by electrical conductivity measurements and confirmed by geochemical data. The low level of urea hydrolysis and calcium carbonate precipitation suggested by the model and geochemical data was corroborated by minor changes in seismic P-wave velocity measurements and micro-CT imaging; the latter provided direct evidence of sparsely distributed calcium carbonate precipitation. Ion exchange processes promoted through NH4

  14. Geophysical monitoring and reactive transport modeling of ureolytically-driven calcium carbonate precipitation

    SciTech Connect

    Wu, Y.; Ajo-Franklin, J.B.; Spycher, N.; Hubbard, S.S.; Zhang, G.; Williams, K.H.; Taylor, J.; Fujita, Y.; Smith, R.

    2011-07-15

    Ureolytically-driven calcium carbonate precipitation is the basis for a promising in-situ remediation method for sequestration of divalent radionuclide and trace metal ions. It has also been proposed for use in geotechnical engineering for soil strengthening applications. Monitoring the occurrence, spatial distribution, and temporal evolution of calcium carbonate precipitation in the subsurface is critical for evaluating the performance of this technology and for developing the predictive models needed for engineering application. In this study, we conducted laboratory column experiments using natural sediment and groundwater to evaluate the utility of geophysical (complex resistivity and seismic) sensing methods, dynamic synchrotron x-ray computed tomography (micro-CT), and reactive transport modeling for tracking ureolytically-driven calcium carbonate precipitation processes under site relevant conditions. Reactive transport modeling with TOUGHREACT successfully simulated the changes of the major chemical components during urea hydrolysis. Even at the relatively low level of urea hydrolysis observed in the experiments, the simulations predicted an enhanced calcium carbonate precipitation rate that was 3-4 times greater than the baseline level. Reactive transport modeling results, geophysical monitoring data and micro-CT imaging correlated well with reaction processes validated by geochemical data. In particular, increases in ionic strength of the pore fluid during urea hydrolysis predicted by geochemical modeling were successfully captured by electrical conductivity measurements and confirmed by geochemical data. The low level of urea hydrolysis and calcium carbonate precipitation suggested by the model and geochemical data was corroborated by minor changes in seismic P-wave velocity measurements and micro-CT imaging; the latter provided direct evidence of sparsely distributed calcium carbonate precipitation. Ion exchange processes promoted through NH{sub 4}{sup

  15. Are reactive transport models reliable tools for reconstructing historical contamination scenarios?

    NASA Astrophysics Data System (ADS)

    Clement, P.

    2009-12-01

    This presentation will be based on a recent project effort that I completed while serving as a member of National Academy of Sciences and Engineering panel. The primary goal of this congressionally-mandated project effort was to review scientific evidence on the association between adverse health effect s and exposure to a contaminated water supply system at the U.S. Marine Corps Base Camp Lejeune (CLJ) in North Carolina. The detailed NRC study report was released in June 2009, and is available at this NRC weblink: http://www.nap.edu/catalog.php?record_id=12618. Multiple water supply systems at this Marine Base were contaminated with harmful chemicals, such as PCE, TCE and other waste products, since the early 50s. In 1982, a routine water quality survey completed at the site indicated the presence of several volatile organic compounds including PCE and TCE. Further investigations revealed that there are several waste disposal facilities located on-site that have discharged TCE and other waste products into groundwater systems. In addition, there was also an off-site dry cleaning facility located close to the Tarawa Terrace in-take well locations that disposed PCE into the subsurface environment. The dry cleaner has been using PCE since 1953 and disposed various forms of PCE-contaminated wastes in a septic tank and in several shallow pits. Therefore, the residents who lived in Tarawa Terrace on-site family housing units had the potential to be exposed to these harmful environmental contaminants through the drinking water source. In late 1980s, the concerns raised by CLJ public lead to an epidemiological study to evaluate the potential associations of utero and infant exposures to the VOCs and childhood cancers and birth defects. The study included births occurring during the period of 1968-1985 to women who were pregnant while they resided at the base. Since there was no monitoring data available for the study period (1968-1982), researchers used reactive transport

  16. Dissolution-precipitation processes in tank experiments for testing numerical models for reactive transport calculations: Experiments and modelling

    NASA Astrophysics Data System (ADS)

    Poonoosamy, Jenna; Kosakowski, Georg; Van Loon, Luc R.; Mäder, Urs

    2015-06-01

    In the context of testing reactive transport codes and their underlying conceptual models, a simple 2D reactive transport experiment was developed. The aim was to use simple chemistry and design a reproducible and fast to conduct experiment, which is flexible enough to include several process couplings: advective-diffusive transport of solutes, effect of liquid phase density on advective transport, and kinetically controlled dissolution/precipitation reactions causing porosity changes. A small tank was filled with a reactive layer of strontium sulfate (SrSO4) of two different grain sizes, sandwiched between two layers of essentially non-reacting quartz sand (SiO2). A highly concentrated solution of barium chloride was injected to create an asymmetric flow field. Once the barium chloride reached the reactive layer, it forced the transformation of strontium sulfate into barium sulfate (BaSO4). Due to the higher molar volume of barium sulfate, its precipitation caused a decrease of porosity and lowered the permeability. Changes in the flow field were observed with help of dye tracer tests. The experiments were modelled using the reactive transport code OpenGeosys-GEM. Tests with non-reactive tracers performed prior to barium chloride injection, as well as the density-driven flow (due to the high concentration of barium chloride solution), could be well reproduced by the numerical model. To reproduce the mineral bulk transformation with time, two populations of strontium sulfate grains with different kinetic rates of dissolution were applied. However, a default porosity permeability relationship was unable to account for measured pressure changes. Post mortem analysis of the strontium sulfate reactive medium provided useful information on the chemical and structural changes occurring at the pore scale at the interface that were considered in our model to reproduce the pressure evolution with time.

  17. Dissolution-precipitation processes in tank experiments for testing numerical models for reactive transport calculations: Experiments and modelling.

    PubMed

    Poonoosamy, Jenna; Kosakowski, Georg; Van Loon, Luc R; Mäder, Urs

    2015-01-01

    In the context of testing reactive transport codes and their underlying conceptual models, a simple 2D reactive transport experiment was developed. The aim was to use simple chemistry and design a reproducible and fast to conduct experiment, which is flexible enough to include several process couplings: advective-diffusive transport of solutes, effect of liquid phase density on advective transport, and kinetically controlled dissolution/precipitation reactions causing porosity changes. A small tank was filled with a reactive layer of strontium sulfate (SrSO4) of two different grain sizes, sandwiched between two layers of essentially non-reacting quartz sand (SiO2). A highly concentrated solution of barium chloride was injected to create an asymmetric flow field. Once the barium chloride reached the reactive layer, it forced the transformation of strontium sulfate into barium sulfate (BaSO4). Due to the higher molar volume of barium sulfate, its precipitation caused a decrease of porosity and lowered the permeability. Changes in the flow field were observed with help of dye tracer tests. The experiments were modelled using the reactive transport code OpenGeosys-GEM. Tests with non-reactive tracers performed prior to barium chloride injection, as well as the density-driven flow (due to the high concentration of barium chloride solution), could be well reproduced by the numerical model. To reproduce the mineral bulk transformation with time, two populations of strontium sulfate grains with different kinetic rates of dissolution were applied. However, a default porosity permeability relationship was unable to account for measured pressure changes. Post mortem analysis of the strontium sulfate reactive medium provided useful information on the chemical and structural changes occurring at the pore scale at the interface that were considered in our model to reproduce the pressure evolution with time.

  18. A reactive transport model for mercury fate in soil--application to different anthropogenic pollution sources.

    PubMed

    Leterme, Bertrand; Blanc, Philippe; Jacques, Diederik

    2014-11-01

    Soil systems are a common receptor of anthropogenic mercury (Hg) contamination. Soils play an important role in the containment or dispersion of pollution to surface water, groundwater or the atmosphere. A one-dimensional model for simulating Hg fate and transport for variably saturated and transient flow conditions is presented. The model is developed using the HP1 code, which couples HYDRUS-1D for the water flow and solute transport to PHREEQC for geochemical reactions. The main processes included are Hg aqueous speciation and complexation, sorption to soil organic matter, dissolution of cinnabar and liquid Hg, and Hg reduction and volatilization. Processes such as atmospheric wet and dry deposition, vegetation litter fall and uptake are neglected because they are less relevant in the case of high Hg concentrations resulting from anthropogenic activities. A test case is presented, assuming a hypothetical sandy soil profile and a simulation time frame of 50 years of daily atmospheric inputs. Mercury fate and transport are simulated for three different sources of Hg (cinnabar, residual liquid mercury or aqueous mercuric chloride), as well as for combinations of these sources. Results are presented and discussed with focus on Hg volatilization to the atmosphere, Hg leaching at the bottom of the soil profile and the remaining Hg in or below the initially contaminated soil layer. In the test case, Hg volatilization was negligible because the reduction of Hg(2+) to Hg(0) was inhibited by the low concentration of dissolved Hg. Hg leaching was mainly caused by complexation of Hg(2+) with thiol groups of dissolved organic matter, because in the geochemical model used, this reaction only had a higher equilibrium constant than the sorption reactions. Immobilization of Hg in the initially polluted horizon was enhanced by Hg(2+) sorption onto humic and fulvic acids (which are more abundant than thiols). Potential benefits of the model for risk management and remediation of

  19. Microbial respiration and dissolution precipitation reactions of minerals: thermo-kinetics and reactive transport modelling

    NASA Astrophysics Data System (ADS)

    Azaroual, M. M.; Parmentier, M.; Andre, L.; Croiset, N.; Pettenati, M.; Kremer, S.

    2010-12-01

    Microbial processes interact closely with abiotic geochemical reactions and mineralogical transformations in several hydrogeochemical systems. Reactive transport models are aimed to analyze these complex mechanisms integrating as well as the degradation of organic matter as the redox reactions involving successive terminal electron acceptors (TEAPs) mediated by microbes through the continuum of unsaturated zone (soil) - saturated zone (aquifer). The involvement of microbial processes in reactive transport in soil and subsurface geologic greatly complicates the mastery of the major mechanisms and the numerical modelling of these systems. The introduction of kinetic constraints of redox reactions in aqueous phase requires the decoupling of equilibrium reactions and the redefinition of mass balance of chemical elements including the concept of basis species and secondary species of thermodynamic databases used in geochemical modelling tools. An integrated methodology for modelling the reactive transport has been developed and implemented to simulate the transfer of arsenic, denitrification processes and the role of metastable aqueous sulfur species with pyrite and organic matter as electron donors entities. A mechanistic rate law of microbial respiration in various geochemical environments was used to simulate reactive transport of arsenic, nitrate and organic matter combined to the generalized rate law of mineral dissolution - precipitation reactions derived from the transition state theory was used for dissolution - precipitation of silica, aluminosilicate, carbonate, oxyhydroxide, and sulphide minerals. The kinetic parameters are compiled from the literature measurements based on laboratory constrained experiments and field observations. Numerical simulations, using the geochemical software PHREEQC, were performed aiming to identify the key reactions mediated by microbes in the framework of in the first hand the concept of the unsaturated - saturated zones of an

  20. Basin scale reactive-transport simulations of CO2 leakage and resulting metal transport in a shallow drinking water aquifer

    NASA Astrophysics Data System (ADS)

    Navarre-Sitchler, A.; Maxwell, R. M.; Hammond, G. E.; Lichtner, P. C.

    2011-12-01

    Leakage of CO2 from underground storage formations into overlying aquifers will decrease groundwater pH resulting in a geochemical response of the aquifer. If metal containing aquifer minerals dissolve as a part of this response, there is a risk of exceeding regulatory limits set by the EPA. Risk assessment methods require a realistic prediction of the maximum metal concentration at wells or other points of exposure. Currently, these predictions are based on numerical reactive transport simulations of CO2 leaks. While previous studies have simulated galena dissolution as a source of lead to explore the potential for contamination of drinking water aquifers, it may be more realistic to simulate lead release from more common minerals that are known to contain trace amounts of metals, e.g. calcite. Model domains for these previous studies are often sub-km in scale or have very coarse grid resolution, due to computation limitations. In this study we simulate CO2 leakage into a drinking water aquifer using the massively parallel subsurface flow and reactive transport code PFLOTRAN. The regional model domain is 4km x 1km x 0.1 km. Even with fairly coarse grid spacing (~ 9 m x 9 m x 0.9 m), the simulations have > 49 million degrees of freedom, requiring the use of High-Performance Computing (HPC). Our simulations are run on Jaguar at Oak Ridge National Laboratory. Lead concentrations in extraction wells 3 km down gradient from a CO2 leak increase above background concentrations due to kinetic mineral dissolution along the flow path. Increases in aqueous concentrations are less when lead is allowed to sorb onto mineral surfaces. Surprisingly, lead concentration increases are greater in simulations where lead is present as a trace constituent in calcite (5% by volume) relative to simulations with galena (0.001% by volume) as the lead source. It appears that galena becomes oversaturated and begins to precipitate, a result observed in previous modeling studies, and its low

  1. Murine Glut-1 transporter haploinsufficiency: postnatal deceleration of brain weight and reactive astrocytosis.

    PubMed

    Ullner, Paivi M; Di Nardo, Alessia; Goldman, James E; Schobel, Scott; Yang, Hong; Engelstad, Kristin; Wang, Dong; Sahin, Mustafa; De Vivo, Darryl C

    2009-10-01

    Glucose transporter type 1 (Glut-1) facilitates glucose flux across the blood-brain-barrier. In humans, Glut-1 deficiency causes acquired microcephaly, seizures and ataxia, which are recapitulated in our Glut-1 haploinsufficient mouse model. Postnatal brain weight deceleration and development of reactive astrogliosis were significant by P21 in Glut-1(+/-) mice. The brain weight differences remained constant after P21 whereas the reactive astrocytosis continued to increase and peaked at P90. Brain immunoblots showed increased phospho-mTOR and decreased phospho-GSK3-beta by P14. After fasting, the mature Glut-1(+/-) females showed a trend towards elevated phospho-GSK3-beta, a possible neuroprotective response. Lithium chloride treatment of human skin fibroblasts from control and Glut-1 DS patients produced a 45% increase in glucose uptake. Brain imaging of mature Glut-1(+/-) mice revealed a significantly decreased hippocampal volume. These subtle immunochemical changes reflect chronic nutrient deficiency during brain development and represent the experimental correlates to the human neurological phenotype associated with Glut-1 DS.

  2. 34S/32S fractionation during sulfate reduction in groundwater treatment systems: reactive transport modeling.

    PubMed

    Gibson, Blair D; Amos, Richard T; Blowes, David W

    2011-04-01

    Isotope ratio measurements provide a tool for indicating the relative significance of biogeochemical reactions and for constraining estimates of the extent and rate of reactions in passive treatment systems. In this paper, the reactive transport model MIN3P is used to evaluate sulfur isotope fractionation in column experiments designed to simulate treatment of contaminated water by microbially mediated sulfate reduction occurring within organic carbon-based and iron and carbon-based permeable reactive barriers. A mass dependent fractionation model was used to determine reaction rates for 32S and 34S compounds during reduction, precipitation, and dissolution reactions and to track isotope-dependent mass transfer during SO4 removal. The δ34S values obtained from the MIN3P model were similar to those obtained from the Rayleigh equation, indicating that there was not a significant difference between the conceptual models. Differences between the MIN3P derived α value and the Rayleigh equation derived value were attributed to minor changes in the dissolution and precipitation rate of gypsum and mathematical differences in the fitting models. The results indicated that the prediction of δ34S was fairly insensitive to differences in the fractionation factor at the concentration ranges measured in the current study. However, more significant differences would be expected at low sulfate conditions.

  3. Effects of Reactive Oxygen Species on Tubular Transport along the Nephron.

    PubMed

    Gonzalez-Vicente, Agustin; Garvin, Jeffrey L

    2017-03-23

    Reactive oxygen species (ROS) are oxygen-containing molecules naturally occurring in both inorganic and biological chemical systems. Due to their high reactivity and potentially damaging effects to biomolecules, cells express a battery of enzymes to rapidly metabolize them to innocuous intermediaries. Initially, ROS were considered by biologists as dangerous byproducts of respiration capable of causing oxidative stress, a condition in which overproduction of ROS leads to a reduction in protective molecules and enzymes and consequent damage to lipids, proteins, and DNA. In fact, ROS are used by immune systems to kill virus and bacteria, causing inflammation and local tissue damage. Today, we know that the functions of ROS are not so limited, and that they also act as signaling molecules mediating processes as diverse as gene expression, mechanosensation, and epithelial transport. In the kidney, ROS such as nitric oxide (NO), superoxide (O₂(-)), and their derivative molecules hydrogen peroxide (H₂O₂) and peroxynitrite (ONO₂(-)) regulate solute and water reabsorption, which is vital to maintain electrolyte homeostasis and extracellular fluid volume. This article reviews the effects of NO, O₂(-), ONO₂(-), and H₂O₂ on water and electrolyte reabsorption in proximal tubules, thick ascending limbs, and collecting ducts, and the effects of NO and O₂(-) in the macula densa on tubuloglomerular feedback.

  4. Reactive transport modeling of subsurface arsenic removal systems in rural Bangladesh.

    PubMed

    Rahman, M M; Bakker, M; Patty, C H L; Hassan, Z; Röling, W F M; Ahmed, K M; van Breukelen, B M

    2015-12-15

    Subsurface Arsenic Removal (SAR) is a technique for in-situ removal of arsenic from groundwater. Extracted groundwater is aerated and re-injected into an anoxic aquifer, where the oxygen in the injected water reacts with ferrous iron in the aquifer to form hydrous ferric oxide (HFO). Subsequent extraction of groundwater contains temporarily lower As concentrations, because As sorbs onto the HFO. Injection, storage, and extraction together is called a cycle. A reactive transport model (RTM) was developed in PHREEQC to determine the hydrogeochemical processes responsible for As (im)mobilization during experimental SAR operation performed in Bangladesh. Oxidation of Fe(II) and As(III) were modeled using kinetic-rate expressions. Cation exchange, precipitation of HFO, and surface complexation, were modeled as equilibrium processes. A best set of surface complexation reactions and corresponding equilibrium constants was adopted from previous studies to simulate all 20 cycles of a SAR experiment. The model gives a reasonable match with observed concentrations of different elements in the extracted water (e.g., the r(2) value of As was 0.59 or higher). As concentrations in the extracted water are governed by four major processes. First, As concentration decreases in response to the elevated pH of injection water and likewise increases when native neutral pH groundwater flows in. Second, the sorption capacity for As increases due to the gradual buildup of HFO. Third, As sorption is enhanced by preferential removal of As(V). Fourth, competitive sorption of Si limits the capacity of freshly precipitated HFO for As sorption. Transferability of the developed reactive transport model was demonstrated through successful application of the model, without further calibration, to two additional SAR sites in Bangladesh. This gives confidence that the model could be useful to assess potential SAR performance at locations in Bangladesh based on local hydrogeochemical conditions.

  5. Three-dimensional model for multi-component reactive transport with variable density groundwater flow

    USGS Publications Warehouse

    Mao, X.; Prommer, H.; Barry, D.A.; Langevin, C.D.; Panteleit, B.; Li, L.

    2006-01-01

    PHWAT is a new model that couples a geochemical reaction model (PHREEQC-2) with a density-dependent groundwater flow and solute transport model (SEAWAT) using the split-operator approach. PHWAT was developed to simulate multi-component reactive transport in variable density groundwater flow. Fluid density in PHWAT depends not on only the concentration of a single species as in SEAWAT, but also the concentrations of other dissolved chemicals that can be subject to reactive processes. Simulation results of PHWAT and PHREEQC-2 were compared in their predictions of effluent concentration from a column experiment. Both models produced identical results, showing that PHWAT has correctly coupled the sub-packages. PHWAT was then applied to the simulation of a tank experiment in which seawater intrusion was accompanied by cation exchange. The density dependence of the intrusion and the snow-plough effect in the breakthrough curves were reflected in the model simulations, which were in good agreement with the measured breakthrough data. Comparison simulations that, in turn, excluded density effects and reactions allowed us to quantify the marked effect of ignoring these processes. Next, we explored numerical issues involved in the practical application of PHWAT using the example of a dense plume flowing into a tank containing fresh water. It was shown that PHWAT could model physically unstable flow and that numerical instabilities were suppressed. Physical instability developed in the model in accordance with the increase of the modified Rayleigh number for density-dependent flow, in agreement with previous research. ?? 2004 Elsevier Ltd. All rights reserved.

  6. Pore-scale modeling of multiphase reactive transport with phase transitions and dissolution-precipitation processes in closed systems.

    PubMed

    Chen, Li; Kang, Qinjun; Robinson, Bruce A; He, Ya-Ling; Tao, Wen-Quan

    2013-04-01

    A pore-scale model based on the lattice Boltzmann (LB) method is developed for multiphase reactive transport with phase transitions and dissolution-precipitation processes. The model combines the single-component multiphase Shan-Chen LB model [X. Shan and H. Chen, Phys. Rev. E 47, 1815 (1993)], the mass transport LB model [S. P. Sullivan et al., Chem. Eng. Sci. 60, 3405 (2005)], and the dissolution-precipitation model [Q. Kang et al., J. Geophys. Res. 111, B05203 (2006)]. Care is taken to handle information on computational nodes undergoing solid-liquid or liquid-vapor phase changes to guarantee mass and momentum conservation. A general LB concentration boundary condition is proposed that can handle various concentration boundaries including reactive and moving boundaries with complex geometries. The pore-scale model can capture coupled nonlinear multiple physicochemical processes including multiphase flow with phase separations, mass transport, chemical reactions, dissolution-precipitation processes, and dynamic evolution of the pore geometries. The model is validated using several multiphase flow and reactive transport problems and then used to study the thermal migration of a brine inclusion in a salt crystal. Multiphase reactive transport phenomena with phase transitions between liquid-vapor phases and dissolution-precipitation processes of the salt in the closed inclusion are simulated and the effects of the initial inclusion size and temperature gradient on the thermal migration are investigated.

  7. Technical Basis for Peak Reactivity Burnup Credit for BWR Spent Nuclear Fuel in Storage and Transportation Systems

    SciTech Connect

    Marshall, William BJ J; Ade, Brian J; Bowman, Stephen M; Gauld, Ian C; Ilas, Germina; Mertyurek, Ugur; Radulescu, Georgeta

    2015-01-01

    Oak Ridge National Laboratory and the United States Nuclear Regulatory Commission have initiated a multiyear project to investigate application of burnup credit for boiling-water reactor (BWR) fuel in storage and transportation casks. This project includes two phases. The first phase (1) investigates applicability of peak reactivity methods currently used in spent fuel pools (SFPs) to storage and transportation systems and (2) evaluates validation of both reactivity (keff) calculations and burnup credit nuclide concentrations within these methods. The second phase will focus on extending burnup credit beyond peak reactivity. This paper documents the first phase, including an analysis of lattice design parameters and depletion effects, as well as both validation components. Initial efforts related to extended burnup credit are discussed in a companion paper. Peak reactivity analyses have been used in criticality analyses for licensing of BWR fuel in SFPs over the last 20 years. These analyses typically combine credit for the gadolinium burnable absorber present in the fuel with a modest amount of burnup credit. Gadolinium burnable absorbers are used in BWR assemblies to control core reactivity. The burnable absorber significantly reduces assembly reactivity at beginning of life, potentially leading to significant increases in assembly reactivity for burnups less than 15–20 GWd/MTU. The reactivity of each fuel lattice is dependent on gadolinium loading. The number of gadolinium-bearing fuel pins lowers initial lattice reactivity, but it has a small impact on the burnup and reactivity of the peak. The gadolinium concentration in each pin has a small impact on initial lattice reactivity but a significant effect on the reactivity of the peak and the burnup at which the peak occurs. The importance of the lattice parameters and depletion conditions are primarily determined by their impact on the gadolinium depletion. Criticality code validation for BWR burnup

  8. Exposure-time based modeling of nonlinear reactive transport in porous media subject to physical and geochemical heterogeneity.

    PubMed

    Sanz-Prat, Alicia; Lu, Chuanhe; Amos, Richard T; Finkel, Michael; Blowes, David W; Cirpka, Olaf A

    2016-09-01

    Transport of reactive solutes in groundwater is affected by physical and chemical heterogeneity of the porous medium, leading to complex spatio-temporal patterns of concentrations and reaction rates. For certain cases of bioreactive transport, it could be shown that the concentrations of reactive constituents in multi-dimensional domains are approximately aligned with isochrones, that is, lines of identical travel time, provided that the chemical properties of the matrix are uniform. We extend this concept to combined physical and chemical heterogeneity by additionally considering the time that a water parcel has been exposed to reactive materials, the so-called exposure time. We simulate bioreactive transport in a one-dimensional domain as function of time and exposure time, rather than space. Subsequently, we map the concentrations to multi-dimensional heterogeneous domains by means of the mean exposure time at each location in the multi-dimensional domain. Differences in travel and exposure time at a given location are accounted for as time difference. This approximation simplifies reactive-transport simulations significantly under conditions of steady-state flow when reactions are restricted to specific locations. It is not expected to be exact in realistic applications because the underlying assumption, such as neglecting transverse mixing altogether, may not hold. We quantify the error introduced by the approximation for the hypothetical case of a two-dimensional, binary aquifer made of highly-permeable, non-reactive and low-permeable, reactive materials releasing dissolved organic matter acting as electron donor for aerobic respiration and denitrification. The kinetically controlled reactions are catalyzed by two non-competitive bacteria populations, enabling microbial growth. Even though the initial biomass concentrations were uniform, the interplay between transport, non-uniform electron-donor supply, and bio-reactions led to distinct spatial patterns of

  9. Exposure-time based modeling of nonlinear reactive transport in porous media subject to physical and geochemical heterogeneity

    NASA Astrophysics Data System (ADS)

    Sanz-Prat, Alicia; Lu, Chuanhe; Amos, Richard T.; Finkel, Michael; Blowes, David W.; Cirpka, Olaf A.

    2016-09-01

    Transport of reactive solutes in groundwater is affected by physical and chemical heterogeneity of the porous medium, leading to complex spatio-temporal patterns of concentrations and reaction rates. For certain cases of bioreactive transport, it could be shown that the concentrations of reactive constituents in multi-dimensional domains are approximately aligned with isochrones, that is, lines of identical travel time, provided that the chemical properties of the matrix are uniform. We extend this concept to combined physical and chemical heterogeneity by additionally considering the time that a water parcel has been exposed to reactive materials, the so-called exposure time. We simulate bioreactive transport in a one-dimensional domain as function of time and exposure time, rather than space. Subsequently, we map the concentrations to multi-dimensional heterogeneous domains by means of the mean exposure time at each location in the multi-dimensional domain. Differences in travel and exposure time at a given location are accounted for as time difference. This approximation simplifies reactive-transport simulations significantly under conditions of steady-state flow when reactions are restricted to specific locations. It is not expected to be exact in realistic applications because the underlying assumption, such as neglecting transverse mixing altogether, may not hold. We quantify the error introduced by the approximation for the hypothetical case of a two-dimensional, binary aquifer made of highly-permeable, non-reactive and low-permeable, reactive materials releasing dissolved organic matter acting as electron donor for aerobic respiration and denitrification. The kinetically controlled reactions are catalyzed by two non-competitive bacteria populations, enabling microbial growth. Even though the initial biomass concentrations were uniform, the interplay between transport, non-uniform electron-donor supply, and bio-reactions led to distinct spatial patterns of

  10. Does the reactive surface area of sandstone depend on water saturation?—The role of reactive-transport in water film

    NASA Astrophysics Data System (ADS)

    Nishiyama, Naoki; Yokoyama, Tadashi

    2013-12-01

    To investigate how mineral-water reactive surface area changes depending on water saturation, flow-through dissolution experiments were performed using a sandstone core at various water saturations. Fontainebleau sandstone with an open porosity of 6.3%, consisting of ∼100% quartz, was used. The water saturation of the core was adjusted to 0%, 51%, or 100%, and at each saturation, water was infiltrated into the core at a constant pressure. The experimental results showed that the total amount of dissolved Si did not change with decreasing water saturation. It can be therefore concluded that virtually all of the mineral surfaces were wetted with water film and allowed the progression of dissolution; i.e., the reactive surface area was not affected by water saturation despite the presence of air in the pores. The results also suggested that the flushing rate of dissolved Si from the interior of the water film to the exterior was fast enough to keep the Si concentration in the film sufficiently lower than the equilibrium concentration of quartz. We derived a reactive-transport model describing dissolution and diffusion in water film. The model shows that the solute concentration in a film is a function of the film thickness, diffusion length, dissolution rate of the mineral, equilibrium concentration, and roughness factor. As for the Fontainebleau sandstone, film thicknesses of 7-18 nm and diffusion lengths of 300-600 μm were estimated. The reactive-transport calculation confirmed that the overall dissolution rate of our sandstone sample was almost unaffected by water saturation, owing to the high flushing efficiency of dissolved Si in water film, which agrees with the experimental result. Application of the model allows us to evaluate whether the reactive surface area and the dissolution rate change with water saturation for a given rock of interest.

  11. Release of aged contaminants from weathered sediments: Effects of sorbate speciation on scaling of reactive transport

    SciTech Connect

    Chorover, Jon; Perdrial, Nico; Mueller, Karl; Strepka, Caleb; O’Day, Peggy; Rivera, Nelson; Um, Wooyong; Chang, Hyun-Shik; Steefel, Carl; Thompson, Aaron

    2012-11-05

    Hanford sediments impacted by hyperalkaline high level radioactive waste have undergone incongruent silicate mineral weathering concurrent with contaminant uptake. In this project, we studied the impact of background pore water (BPW) on strontium, cesium and iodine desorption and transport in Hanford sediments that were experimentally weathered by contact with simulated hyperalkaline tank waste leachate (STWL) solutions. Using those lab-weathered Hanford sediments (HS) and model precipitates formed during nucleation from homogeneous STWL solutions (HN), we (i) provided thorough characterization of reaction products over a matrix of field-relevant gradients in contaminant concentration, partial pressure of carbon dioxide, and reaction time; (ii) improved molecular-scale understanding of how sorbate speciation controls contaminant desorption from weathered sediments upon removal of caustic sources; and (iii) developed a mechanistic, predictive model of meso- to field-scale contaminant reactive transport under these conditions. In this final report, we provide detailed descriptions of our results from this three-year study, completed in 2012 following a one-year no cost extension.

  12. Reactive chemical transport in ground-water hydrology: Challenges to mathematical modeling

    SciTech Connect

    Narasimhan, T.N.; Apps, J.A.

    1990-07-01

    For a long time, earth scientists have qualitatively recognized that mineral assemblages in soils and rocks conform to established principles of chemistry. In the early 1960's geochemists began systematizing this knowledge by developing quantitative thermodynamic models based on equilibrium considerations. These models have since been coupled with advective-dispersive-diffusive transport models, already developed by ground-water hydrologists. Spurred by a need for handling difficult environmental issues related to ground-water contamination, these models are being improved, refined and applied to realistic problems of interest. There is little doubt that these models will play an important role in solving important problems of engineering as well as science over the coming years. Even as these models are being used practically, there is scope for their improvement and many challenges lie ahead. In addition to improving the conceptual basis of the governing equations, much remains to be done to incorporate kinetic processes and biological mediation into extant chemical equilibrium models. Much also remains to be learned about the limits to which model predictability can be reasonably taken. The purpose of this paper is to broadly assess the current status of knowledge in modeling reactive chemical transport and to identify the challenges that lie ahead.

  13. Effects of autoregulation and CO2 reactivity on cerebral oxygen transport.

    PubMed

    Payne, S J; Selb, J; Boas, D A

    2009-11-01

    Both autoregulation and CO(2) reactivity are known to have significant effects on cerebral blood flow and thus on the transport of oxygen through the vasculature. In this paper, a previous model of the autoregulation of blood flow in the cerebral vasculature is expanded to include the dynamic behavior of oxygen transport through binding with hemoglobin. The model is used to predict the transfer functions for both oxyhemoglobin and deoxyhemoglobin in response to fluctuations in arterial blood pressure and arterial CO(2) concentration. It is shown that only six additional nondimensional groups are required in addition to the five that were previously found to characterize the cerebral blood flow response. A resonant frequency in the pressure-oxyhemoglobin transfer function is found to occur in the region of 0.1 Hz, which is a frequency of considerable physiological interest. The model predictions are compared with results from the published literature of phase angle at this frequency, showing that the effects of changes in breathing rate can significantly alter the inferred phase dynamics between blood pressure and hemoglobin. The question of whether dynamic cerebral autoregulation is affected under conditions of stenosis or stroke is then examined.

  14. PFLOTRAN: Reactive Flow & Transport Code for Use on Laptops to Leadership-Class Supercomputers

    SciTech Connect

    Hammond, Glenn E.; Lichtner, Peter C.; Lu, Chuan; Mills, Richard T.

    2012-04-18

    PFLOTRAN, a next-generation reactive flow and transport code for modeling subsurface processes, has been designed from the ground up to run efficiently on machines ranging from leadership-class supercomputers to laptops. Based on an object-oriented design, the code is easily extensible to incorporate additional processes. It can interface seamlessly with Fortran 9X, C and C++ codes. Domain decomposition parallelism is employed, with the PETSc parallel framework used to manage parallel solvers, data structures and communication. Features of the code include a modular input file, implementation of high-performance I/O using parallel HDF5, ability to perform multiple realization simulations with multiple processors per realization in a seamless manner, and multiple modes for multiphase flow and multicomponent geochemical transport. Chemical reactions currently implemented in the code include homogeneous aqueous complexing reactions and heterogeneous mineral precipitation/dissolution, ion exchange, surface complexation and a multirate kinetic sorption model. PFLOTRAN has demonstrated petascale performance using 2{sup 17} processor cores with over 2 billion degrees of freedom. Accomplishments achieved to date include applications to the Hanford 300 Area and modeling CO{sub 2} sequestration in deep geologic formations.

  15. Closed-flow column experiments: A numerical sensitivity analysis of reactive transport and parameter uncertainty

    NASA Astrophysics Data System (ADS)

    Ritschel, Thomas; Totsche, Kai Uwe

    2016-08-01

    The identification of transport parameters by inverse modeling often suffers from equifinality or parameter correlation when models are fitted to measurements of the solute breakthrough in column outflow experiments. This parameter uncertainty can be approached by performing multiple experiments with different sets of boundary conditions, each provoking observations that are uniquely attributable to the respective transport processes. A promising approach to further increase the information potential of the experimental outcome is the closed-flow column design. It is characterized by the recirculation of the column effluent into the solution supply vessel that feeds the inflow, which results in a damped sinusoidal oscillation in the breakthrough curve. In order to reveal the potential application of closed-flow experiments, we present a comprehensive sensitivity analysis using common models for adsorption and degradation. We show that the sensitivity of inverse parameter determination with respect to the apparent dispersion can be controlled by the experimenter. For optimal settings, a decrease in parameter uncertainty as compared to classical experiments by an order of magnitude is achieved. In addition, we show a reduced equifinality between rate-limited interactions and apparent dispersion. Furthermore, we illustrate the expected breakthrough curve for equilibrium and nonequilibrium adsorption, the latter showing strong similarities to the behavior found for completely mixed batch reactor experiments. Finally, breakthrough data from a reactive tracer experiment is evaluated using the proposed framework with excellent agreement of model and experimental results.

  16. Reactive transport modeling in the subsurface environment with OGS-IPhreeqc

    NASA Astrophysics Data System (ADS)

    He, Wenkui; Beyer, Christof; Fleckenstein, Jan; Jang, Eunseon; Kalbacher, Thomas; Naumov, Dimitri; Shao, Haibing; Wang, Wenqing; Kolditz, Olaf

    2015-04-01

    Worldwide, sustainable water resource management becomes an increasingly challenging task due to the growth of population and extensive applications of fertilizer in agriculture. Moreover, climate change causes further stresses to both water quantity and quality. Reactive transport modeling in the coupled soil-aquifer system is a viable approach to assess the impacts of different land use and groundwater exploitation scenarios on the water resources. However, the application of this approach is usually limited in spatial scale and to simplified geochemical systems due to the huge computational expense involved. Such computational expense is not only caused by solving the high non-linearity of the initial boundary value problems of water flow in the unsaturated zone numerically with rather fine spatial and temporal discretization for the correct mass balance and numerical stability, but also by the intensive computational task of quantifying geochemical reactions. In the present study, a flexible and efficient tool for large scale reactive transport modeling in variably saturated porous media and its applications are presented. The open source scientific software OpenGeoSys (OGS) is coupled with the IPhreeqc module of the geochemical solver PHREEQC. The new coupling approach makes full use of advantages from both codes: OGS provides a flexible choice of different numerical approaches for simulation of water flow in the vadose zone such as the pressure-based or mixed forms of Richards equation; whereas the IPhreeqc module leads to a simplification of data storage and its communication with OGS, which greatly facilitates the coupling and code updating. Moreover, a parallelization scheme with MPI (Message Passing Interface) is applied, in which the computational task of water flow and mass transport is partitioned through domain decomposition, whereas the efficient parallelization of geochemical reactions is achieved by smart allocation of computational workload over

  17. Reactive transport modeling in variably saturated porous media with OGS-IPhreeqc

    NASA Astrophysics Data System (ADS)

    He, W.; Beyer, C.; Fleckenstein, J. H.; Jang, E.; Kalbacher, T.; Shao, H.; Wang, W.; Kolditz, O.

    2014-12-01

    Worldwide, sustainable water resource management becomes an increasingly challenging task due to the growth of population and extensive applications of fertilizer in agriculture. Moreover, climate change causes further stresses to both water quantity and quality. Reactive transport modeling in the coupled soil-aquifer system is a viable approach to assess the impacts of different land use and groundwater exploitation scenarios on the water resources. However, the application of this approach is usually limited in spatial scale and to simplified geochemical systems due to the huge computational expense involved. Such computational expense is not only caused by solving the high non-linearity of the initial boundary value problems of water flow in the unsaturated zone numerically with rather fine spatial and temporal discretization for the correct mass balance and numerical stability, but also by the intensive computational task of quantifying geochemical reactions. In the present study, a flexible and efficient tool for large scale reactive transport modeling in variably saturated porous media and its applications are presented. The open source scientific software OpenGeoSys (OGS) is coupled with the IPhreeqc module of the geochemical solver PHREEQC. The new coupling approach makes full use of advantages from both codes: OGS provides a flexible choice of different numerical approaches for simulation of water flow in the vadose zone such as the pressure-based or mixed forms of Richards equation; whereas the IPhreeqc module leads to a simplification of data storage and its communication with OGS, which greatly facilitates the coupling and code updating. Moreover, a parallelization scheme with MPI (Message Passing Interface) is applied, in which the computational task of water flow and mass transport is partitioned through domain decomposition, whereas the efficient parallelization of geochemical reactions is achieved by smart allocation of computational workload over

  18. Uncertainty in the reactive transport model response to analkaline perturbation in a clay formation

    SciTech Connect

    Burnol, A.; Blanc, P.; Xu, T.; Spycher, N.; Gaucher, E.C.

    2006-03-15

    The mineral alteration in the concrete barrier and in the clay formation around long-lived intermediate-level radioactive waste in the French deep geological disposal concept is evaluated using numerical modeling. There are concerns that the mineralogical composition of the surrounded clay will not be stable under the high alkaline pore fluid conditions caused by concrete (pH {approx} 12). Conversely, the infiltration of CO{sub 2}-rich groundwater from the clay formation into initially unsaturated concrete, at the high temperature (T {approx} 70 C) produced from the decay of radionuclides, could cause carbonation, thereby potentially affecting critical performance functions of this barrier. This could also lead to significant changes in porosity, which would affect aqueous diffusive transport of long-lived radionuclides. All these processes are therefore intimately coupled and advanced reactive transport models are required for long-term performance assessment. The uncertainty in predictions of these models is one major question that must be answered. A mass-transfer model response to an alkaline perturbation in clay with standard model values is first simulated using the two-phase non-isothermal reactive transport code TOUGHREACT. The selection of input parameters is thereafter designed to sample uncertainties in a wide range of physico-chemical processes without making a priori assumptions about the relative importance of different feedbacks. This 'base-case' simulation is perturbed by setting a parameter to a minimum, intermediate or maximum value or by switching on/off a process. This sensitivity analysis is conducted using grid computing facilities of BRGM (http://iggi.imag.fr). Our evaluation of the preliminary results suggests that the resaturation and the heating of the near-field will be of long enough duration to cause a limited carbonation through all the width of the concrete barrier. Another prediction is the possibility of self-sealing at the concrete

  19. Reactive Transport of Nitrate in Northern California Groundwater basins: An Integrated Characterization and Modeling Approach

    NASA Astrophysics Data System (ADS)

    Esser, B. K.; Moran, J. E.; Hudson, G. B.; Carle, S. F.; McNab, W.; Tompson, A. F.; Moore, K.; Beller, H.; Kane, S.; Eaton, G.

    2003-12-01

    More than 1/3 of active public drinking water supply wells in California produce water with nitrate-N levels indicative of anthropogenic inputs (> 4 mg/L). Understanding how the distribution of nitrate in California groundwater basins will evolve is vital to water supply and infrastructure planning. To address this need, we are studying the basin-scale reactive transport of nitrate in the Livermore and Llagas basins of Northern California. Both basins have increasingly urban populations heavily reliant on groundwater. A distinct nitrate "plume" exists in the Livermore Basin (Alameda County) whereas pervasive nitrate contamination exists in shallow groundwaters of the Llagas Basin (Santa Clara County). The sources and timing of nitrate contamination in these basins are not definitively known; septic systems, irrigated agriculture and livestock operations exist or have existed in both areas. The role of denitrification in controlling nitrate distribution is also unknown; dissolved oxygen levels are sufficiently low in portions of each basin as to indicate the potential for denitrification. We have collected water from 60 wells, and are determining both groundwater age (by the 3H/3He method) and the extent of denitrification (by the excess N2 method). Excess nitrogen is being determined by both membrane-inlet and noble gas mass spectrometry, using Ar and Ne content to account for atmospheric N2. We are also analyzing for stable istotopes of nitrate and water, nitrate co-contaminants, and general water quality parameters. Preliminary analysis of archival water district data from both basins suggests positive correlations of nitrate with Ca+2, Mg+2 and bicarbonate and negative correlation with pH. In the Llagas Basin, a negative correlation also exists between nitrate and temperature. Flow path-oriented reactive transport modeling is being explored as a tool to aid in the identification of both the sources of nitrate and evidence for denitrification in both basins

  20. Reactive transport of gentisic acid in a hematite-coated sand column: Experimental study and modeling

    NASA Astrophysics Data System (ADS)

    Hanna, K.; Rusch, B.; Lassabatere, L.; Hofmann, A.; Humbert, B.

    2010-06-01

    The adsorption of gentisic acid (GA) by hematite nano-particles was examined under static and dynamic conditions by conducting batch and column tests. To simulate natural sediments, the iron oxide was deposited on 10 μm quartz particles. The GA adsorption was described by a surface complexation model fitted to pH-adsorption curves with GA concentrations of 0.1-1 mM in a pH range of 3-10. The surface was described with one type of site ( tbnd FeOH°), while gentisic acid at the surface was described by two surface complexes ( tbnd FeLH 2°, log Kint = 8.9 and tbnd FeLH -, log Kint = -8.2). Modeling was conducted with PHREEQC-2 using the MINTEQ database. From a kinetic point of view, the intrinsic chemical reactions were likely to be the rate-limiting step of sorption (˜10 -3 s -1) while external and internal mass transfer rates (˜10 2 s -1) were much faster. Under flow through conditions (column), adsorption of GA to hematite-coated sand was about 7-times lower than under turbulent mixing (batch). This difference could not be explained by chemical adsorption kinetics as shown by test calculations run with HYDRUS-1D software. Surface complexation model simulations however successfully described the data when the surface area was adjusted, suggesting that under flow conditions the accessibility to the reactive surface sites was reduced. The exact mechanism responsible for the increased mobility of GA could not be determined but some parameters suggested that decreased external mass transfer between solution and surface may play a significant role under flow through conditions.

  1. Pore network and pore scale modeling of reactive transport in porous media

    NASA Astrophysics Data System (ADS)

    Adler, P. M.; Vu, T. M.; Varloteaux, C.; Bekri, S.

    2012-12-01

    The study of the evolution of a porous medium where a reactive fluid flows is conditioned by the accurate determination of three macroscopic parameters governing the solute displacement, namely the solute velocity, dispersion and mean reaction rate. Of course, a possible application of such studies is CO2 sequestration. This presentation proposes to approach the determination of these parameters by two different ways and to compare them; both are on the pore scale. In the first one called PNM (for pore-network model), a pore-network is extracted from micro tomography images of a real porous medium. This network is composed of spherical pores joined by circular tubes; it is used to calculate transport macroscopic parameters and porosity-permeability evolution during the reactive transport flow as functions of dimensionless numbers representing the reaction and flow rate regimes. The flow is calculated by using Kirchhoff laws. Transport is determined in the asymptotic regime where the solute concentration undergoes an exponential evolution with time. In the second approach called PSM (for pore scale model), the pore-network model is used as a three dimensional medium which is discretized by the Level Set Method. The Stokes equations are solved in order to determine the local flow field and the corresponding permeability. The solute concentration is obtained by solving the local convection-diffusion equation in the 3D pore-network; numerical dispersion is reduced by a Flux Limiting Scheme. Two different geometries of porous media are addressed by both numerical codes. The first pore-network geometry is used to validate the PNM assumptions, whereas the second pore-network is defined for a better understanding of the dominant solute distribution. One of the main results obtained with the first pore-network is the dependence of the concentration profile on the Péclet number Pe in the pore-bodies. When this number increases, one has to switch from an assumption of

  2. Validating Mechanistic Sorption Model Parameters and Processes for Reactive Transport in Alluvium

    SciTech Connect

    Zavarin, M; Roberts, S K; Rose, T P; Phinney, D L

    2002-05-02

    The laboratory batch and flow-through experiments presented in this report provide a basis for validating the mechanistic surface complexation and ion exchange model we use in our hydrologic source term (HST) simulations. Batch sorption experiments were used to examine the effect of solution composition on sorption. Flow-through experiments provided for an analysis of the transport behavior of sorbing elements and tracers which includes dispersion and fluid accessibility effects. Analysis of downstream flow-through column fluids allowed for evaluation of weakly-sorbing element transport. Secondary Ion Mass Spectrometry (SIMS) analysis of the core after completion of the flow-through experiments permitted the evaluation of transport of strongly sorbing elements. A comparison between these data and model predictions provides additional constraints to our model and improves our confidence in near-field HST model parameters. In general, cesium, strontium, samarium, europium, neptunium, and uranium behavior could be accurately predicted using our mechanistic approach but only after some adjustment was made to the model parameters. The required adjustments included a reduction in strontium affinity for smectite, an increase in cesium affinity for smectite and illite, a reduction in iron oxide and calcite reactive surface area, and a change in clinoptilolite reaction constants to reflect a more recently published set of data. In general, these adjustments are justifiable because they fall within a range consistent with our understanding of the parameter uncertainties. These modeling results suggest that the uncertainty in the sorption model parameters must be accounted for to validate the mechanistic approach. The uncertainties in predicting the sorptive behavior of U-1a and UE-5n alluvium also suggest that these uncertainties must be propagated to nearfield HST and large-scale corrective action unit (CAU) models.

  3. Subsurface Multiphase Flow and Multicomponent Reactive Transport Modeling using High-Performance Computing

    SciTech Connect

    Hammond, Glenn E.; Lichtner, Peter C.; Lu, Chuan

    2007-08-01

    Numerical modeling has become a critical tool to the Department of Energy for evaluating the environmental impact of alternative energy sources and remediation strategies for legacy waste sites. Unfortunately, the physical and chemical complexity of many sites overwhelms the capabilities of even most “state of the art” groundwater models. Of particular concern are the representation of highly-heterogeneous stratified rock/soil layers in the subsurface and the biological and geochemical interactions of chemical species within multiple fluid phases. Clearly, there is a need for higher-resolution modeling (i.e. more spatial, temporal, and chemical degrees of freedom) and increasingly mechanistic descriptions of subsurface physicochemical processes. We present research being performed in the development of PFLOTRAN, a parallel multiphase flow and multicomponent reactive transport model. Written in Fortran90, PFLOTRAN is founded upon PETSc data structures and solvers and has exhibited impressive strong scalability on up to 4000 processors on the ORNL Cray XT3. We are employing PFLOTRAN in the simulation of uranium transport at the Hanford 300 Area, a contaminated site of major concern to the Department of Energy, the State of Washington, and other government agencies where overly-simplistic historical modeling erroneously predicted decade removal times for uranium by ambient groundwater flow. By leveraging the billions of degrees of freedom available through high-performance computation using tens of thousands of processors, we can better characterize the release of uranium into groundwater and its subsequent transport to the Columbia River, and thereby better understand and evaluate the effectiveness of various proposed remediation strategies.

  4. Effective grid-dependent dispersion coefficient for conservative and reactive transport simulations in heterogeneous porous media

    NASA Astrophysics Data System (ADS)

    Cortinez, J. M.; Valocchi, A. J.; Herrera, P. A.

    2013-12-01

    Because of the finite size of numerical grids, it is very difficult to correctly account for processes that occur at different spatial scales to accurately simulate the migration of conservative and reactive compounds dissolved in groundwater. In one hand, transport processes in heterogeneous porous media are controlled by local-scale dispersion associated to transport processes at the pore-scale. On the other hand, variations of velocity at the continuum- or Darcy-scale produce spreading of the contaminant plume, which is referred to as macro-dispersion. Furthermore, under some conditions both effects interact, so that spreading may enhance the action of local-scale dispersion resulting in higher mixing, dilution and reaction rates. Traditionally, transport processes at different spatial scales have been included in numerical simulations by using a single dispersion coefficient. This approach implicitly assumes that the separate effects of local-dispersion and macro-dispersion can be added and represented by a unique effective dispersion coefficient. Moreover, the selection of the effective dispersion coefficient for numerical simulations usually do not consider the filtering effect of the grid size over the small-scale flow features. We have developed a multi-scale Lagragian numerical method that allows using two different dispersion coefficients to represent local- and macro-scale dispersion. This technique considers fluid particles that carry solute mass and whose locations evolve according to a deterministic component given by the grid-scale velocity and a stochastic component that corresponds to a block-effective macro-dispersion coefficient. Mass transfer between particles due to local-scale dispersion is approximated by a meshless method. We use our model to test under which transport conditions the combined effect of local- and macro-dispersion are additive and can be represented by a single effective dispersion coefficient. We also demonstrate that for

  5. REACTIVE TRANSPORT MODELING USING A PARALLEL FULLY-COUPLED SIMULATOR BASED ON PRECONDITIONED JACOBIAN-FREE NEWTON-KRYLOV

    SciTech Connect

    Luanjing Guo; Chuan Lu; Hai Huang; Derek R. Gaston

    2012-06-01

    Systems of multicomponent reactive transport in porous media that are large, highly nonlinear, and tightly coupled due to complex nonlinear reactions and strong solution-media interactions are often described by a system of coupled nonlinear partial differential algebraic equations (PDAEs). A preconditioned Jacobian-Free Newton-Krylov (JFNK) solution approach is applied to solve the PDAEs in a fully coupled, fully implicit manner. The advantage of the JFNK method is that it avoids explicitly computing and storing the Jacobian matrix during Newton nonlinear iterations for computational efficiency considerations. This solution approach is also enhanced by physics-based blocking preconditioning and multigrid algorithm for efficient inversion of preconditioners. Based on the solution approach, we have developed a reactive transport simulator named RAT. Numerical results are presented to demonstrate the efficiency and massive scalability of the simulator for reactive transport problems involving strong solution-mineral interactions and fast kinetics. It has been applied to study the highly nonlinearly coupled reactive transport system of a promising in situ environmental remediation that involves urea hydrolysis and calcium carbonate precipitation.

  6. Reactive Transport Modeling and Geophysical Monitoring of Bioclogging at Reservoir Scale

    NASA Astrophysics Data System (ADS)

    Surasani, V.; Commer, M.; Ajo Franklin, J. B.; Li, L.; Hubbard, S. S.

    2012-12-01

    In Microbial-Enhanced-Hydrocarbon-Recovery (MEHR), preferential bioclogging targets the growth of the biofilms (def. immobilized biopolymers with active cells embodied in it) in highly permeable thief zones to enhance sweep efficiency in oil reservoirs. During MEHR, understanding and controlling bioclogging is hindered by the lack of advanced modeling and monitoring tools; these deficiencies contribute to suboptimal performance. Our focus in this study was on developing a systematic approach to understand and monitor bioclogging at the reservoir scale using a combination of reactive transport modeling and geophysical imaging tools (EM & seismic). In this study, we created a realistic reservoir model from a heterogeneous gas reservoir in the Southern Sacramento basin, California; the model well (Citizen Green #1) was characterized using sonic, electrical, nuclear, and NMR logs for hydrologic and geophysical properties. From the simplified 2D log data model, a strip of size 150m x75m with several high permeability streaks is identified for bioclogging simulation experiments. From the NMR log data it is observed that a good linear correlation exist between logarithmic permeability (0.55- 3.34 log (mD)) versus porosity (0.041-0.28). L. mesenteroides was chosen as the model bacteria. In the presence of sucrose, it enzymatically catalyzes the production of dextran, a useful bioclogging agent. Using microbial kinetics from our laboratory experiment and reservoir heterogeneity, a reactive transport model (RTM) is established for two kinds of bioclogging treatments based on whether microbes are present in situ or are supplied externally. In both cases, sucrose media (1.5 M) is injected at the rate of 1 liter/s for 20 days into the center of high permeable strip to stimulate microbes. Simulations show that the high dextran production was deep into the formation from the injection well. This phenomenon can be explained precisely with bacterial kinetics and injection rate. In

  7. Using a reactive transport model to elucidate differences between laboratory and field dissolution rates in regolith

    NASA Astrophysics Data System (ADS)

    Moore, Joel; Lichtner, Peter C.; White, Art F.; Brantley, Susan L.

    2012-09-01

    The reactive transport model FLOTRAN was used to forward-model weathering profiles developed on granitic outwash alluvium over 40-3000 ka from the Merced, California (USA) chronosequence as well as deep granitic regolith developed over 800 ka near Davis Run, Virginia (USA). Baseline model predictions that used laboratory rate constants (km), measured fluid flow velocities (v), and BET volumetric surface areas for the parent material (AB,mo) were not consistent with measured profiles of plagioclase, potassium feldspar, and quartz. Reaction fronts predicted by the baseline model are deeper and thinner than the observed, consistent with faster rates of reaction in the model. Reaction front depth in the model depended mostly upon saturated versus unsaturated hydrologic flow conditions, rate constants controlling precipitation of secondary minerals, and the average fluid flow velocity (va). Unsaturated hydrologic flow conditions (relatively open with respect to CO2(g)) resulted in the prediction of deeper reaction fronts and significant differences in the separation between plagioclase and potassium feldspar reaction fronts compared to saturated hydrologic flow (relatively closed with respect to CO2(g)). Under saturated or unsaturated flow conditions, the rate constant that controls precipitation rates of secondary minerals must be reduced relative to laboratory rate constants to match observed reaction front depths and measured pore water chemistry. Additionally, to match the observed reaction front depths, va was set lower than the measured value, v, for three of the four profiles. The reaction front gradients in mineralogy and pore fluid chemistry could only be modeled accurately by adjusting values of the product kmAB,mo. By assuming km values were constrained by laboratory data, field observations were modeled successfully with TST-like rate equations by dividing measured values of AB,mo by factors from 50 to 1700. Alternately, with sigmoidal or Al-inhibition rate

  8. Interplay between subsurface structural heterogeneity and multi-species reactive transport in human health risk predictions

    NASA Astrophysics Data System (ADS)

    Henri, C.; Fernandez-Garcia, D.; de Barros, F.

    2013-12-01

    The increasing presence of toxic chemicals released in the subsurface has led to a rapid growth of social concerns and to the need to develop and employ models that can predict the impact of groundwater contamination in human health under uncertainty. Monitored natural attenuation is a common remediation action in many contamination cases and represents an attractive decontamination method. However, natural attenuation can lead to the production of subspecies of distinct toxicity that may pose challenges in pollution management strategies. The actual threat that these contaminants pose to human health and ecosystems greatly depends on the interplay between the complexity of the geological system and the toxicity of the pollutants and their byproducts. In this work, we examine the interplay between multispecies reactive transport and the heterogeneous structure of the contaminated aquifer on human health risk predictions. The structure and organization of hydraulic properties of the aquifer can lead to preferential flow channels and fast contamination pathways. Early travel times, associated to channeling effects, are intuitively perceived as an indicator for high risk. However, in the case of multi-species systems, early travel times may also lead a limited production of daughter species that may contain higher toxicity as in the case of chlorinated compounds. In this work, we model a Perchloroethylene (PCE) contamination problem followed by the sequential first-order production/biodegradation of its daughter species Trichloroethylene (TCE), Dichloroethylene (DCE) and Vinyl Chlorine (VC). For this specific case, VC is known to be a highly toxic contaminant. By performing numerical experiments, we evaluate transport for two distinct three-dimensional aquifer structures. First, a multi-Gaussian hydraulic conductivity field and secondly, a geostatistically equivalent connected field. These two heterogeneity structures will provide two distinct ranges of mean travel

  9. Large-scale modeling of reactive solute transport in fracture zones of granitic bedrocks.

    PubMed

    Molinero, Jorge; Samper, Javier

    2006-01-10

    Final disposal of high-level radioactive waste in deep repositories located in fractured granite formations is being considered by several countries. The assessment of the safety of such repositories requires using numerical models of groundwater flow, solute transport and chemical processes. These models are being developed from data and knowledge gained from in situ experiments such as the Redox Zone Experiment carried out at the underground laboratory of Aspö in Sweden. This experiment aimed at evaluating the effects of the construction of the access tunnel on the hydrogeological and hydrochemical conditions of a fracture zone intersected by the tunnel. Most chemical species showed dilution trends except for bicarbonate and sulphate which unexpectedly increased with time. Molinero and Samper [Molinero, J. and Samper, J. Groundwater flow and solute transport in fracture zones: an improved model for a large-scale field experiment at Aspö (Sweden). J. Hydraul. Res., 42, Extra Issue, 157-172] presented a two-dimensional water flow and solute transport finite element model which reproduced measured drawdowns and dilution curves of conservative species. Here we extend their model by using a reactive transport which accounts for aqueous complexation, acid-base, redox processes, dissolution-precipitation of calcite, quartz, hematite and pyrite, and cation exchange between Na+ and Ca2+. The model provides field-scale estimates of cation exchange capacity of the fracture zone and redox potential of groundwater recharge. It serves also to identify the mineral phases controlling the solubility of iron. In addition, the model is useful to test the relevance of several geochemical processes. Model results rule out calcite dissolution as the process causing the increase in bicarbonate concentration and reject the following possible sources of sulphate: (1) pyrite dissolution, (2) leaching of alkaline sulphate-rich waters from a nearby rock landfill and (3) dissolution of

  10. Implementing fluid dynamics obtained from GeoPET in reactive transport models

    NASA Astrophysics Data System (ADS)

    Lippmann-Pipke, Johanna; Eichelbaum, Sebastian; Kulenkampff, Johannes

    2016-04-01

    Flow and transport simulations in geomaterials are commonly conducted on high-resolution tomograms (μCT) of the pore structure or stochastic models that are calibrated with measured integral quantities, like break through curves (BTC). Yet, there existed virtually no method for experimental verification of the simulated velocity distribution results. Positron emission tomography (PET) has unrivaled sensitivity and robustness for non-destructive, quantitative, spatio-temporal measurement of tracer concentrations in body tissue. In the past decade, we empowered PET for its applicability in opaque/geological media - GeoPET (Kulenkampff et al.; Kulenkampff et al., 2008; Zakhnini et al., 2013) and have developed detailed correction schemes to bring the images into sharp focus. Thereby it is the appropriate method for experimental verification and calibration of computer simulations of pore-scale transport by means of the observed propagation of a tracer pulse, c_PET(x,y,z,t). In parallel, we aimed at deriving velocity and porosity distributions directly from our concentration time series of fluid flow processes in geomaterials. This would allow us to directly benefit from lab scale observations and to parameterize respective numerical transport models. For this we have developed a robust spatiotemporal (3D+t) parameter extraction algorithm. Here, we will present its functionality, and demonstrate the use of obtained velocity distributions in finite element simulations of reactive transport processes on drill core scale. Kulenkampff, J., Gruendig, M., Zakhnini, A., Gerasch, R., and Lippmann-Pipke, J.: Process tomography of diffusion with PET for evaluating anisotropy and heterogeneity, Clay Minerals, in press. Kulenkampff, J., Gründig, M., Richter, M., and Enzmann, F.: Evaluation of positron emission tomography for visualisation of migration processes in geomaterials, Physics and Chemistry of the Earth, 33, 937-942, 2008. Zakhnini, A., Kulenkampff, J., Sauerzapf, S

  11. Interactions of corrosion products and bentonite: An extended multicomponent reactive transport model

    NASA Astrophysics Data System (ADS)

    Lu, Chuanhe; Samper, Javier; Fritz, Bertrand; Clement, Alain; Montenegro, Luis

    Radioactive waste disposal in deep geological repositories envisages various engineered barriers such as carbon-steel canisters and compacted bentonite. Canister corrosion and the chemical interactions of corrosion products with bentonite are key reactions for the long term performance of a repository. Samper, Lu, and Montenegro (Physics and Chemistry of the Earth 2008; 33S: S306-S316) reported numerical models to simulate canister corrosion and the interactions of corrosion products with bentonite for the near field of a repository in granite. Here we present an updated version of their reactive transport model which accounts for: (1) Three types of sorption sites in the bentonite; (2) Kinetically-controlled canister corrosion, (3) Kinetically-controlled magnetite precipitation; and (4) The competition effect of Ni 2+ for sorbing sites. Accounting for kinetically-controlled canister corrosion leads to a significant reduction in the corrosion rate. Uncertainties in the surface complexation reactions play a minor role in the time evolution of the computed pH in the bentonite and the granite. Computed iron concentrations, however, are very sensitive to changes in the surface complexation reactions. The apparent distribution coefficient of Fe computed with the three-site model is 10 times larger than that obtained with a single-site model. The concentration of dissolved Fe computed with kinetic magnetite precipitation is smaller than that obtained with magnetite precipitation at local equilibrium. The largest difference in the concentration of dissolved Fe occurs after 3 × 10 4 years. The competition of Ni 2+ for sorption sites affects significantly the chemical evolution of the bentonite porewater. The sorption of Ni 2+ on bentonite releases protons and therefore the pH in the bentonite is smaller than that computed without Ni 2+ transport. The sorption of Ni 2+ leads to a decrease of the concentration of sorbed Fe and an increase of the concentration of dissolved

  12. Permeability evolution due to dissolution and precipitation of carbonates using reactive transport modeling in pore networks

    NASA Astrophysics Data System (ADS)

    Nogues, Juan P.; Fitts, Jeffrey P.; Celia, Michael A.; Peters, Catherine A.

    2013-09-01

    A reactive transport model was developed to simulate reaction of carbonates within a pore network for the high-pressure CO2-acidified conditions relevant to geological carbon sequestration. The pore network was based on a synthetic oolithic dolostone. Simulation results produced insights that can inform continuum-scale models regarding reaction-induced changes in permeability and porosity. As expected, permeability increased extensively with dissolution caused by high concentrations of carbonic acid, but neither pH nor calcite saturation state alone was a good predictor of the effects, as may sometimes be the case. Complex temporal evolutions of interstitial brine chemistry and network structure led to the counterintuitive finding that a far-from-equilibrium solution produced less permeability change than a nearer-to-equilibrium solution at the same pH. This was explained by the pH buffering that increased carbonate ion concentration and inhibited further reaction. Simulations of different flow conditions produced a nonunique set of permeability-porosity relationships. Diffusive-dominated systems caused dissolution to be localized near the inlet, leading to substantial porosity change but relatively small permeability change. For the same extent of porosity change caused from advective transport, the domain changed uniformly, leading to a large permeability change. Regarding precipitation, permeability changes happen much slower compared to dissolution-induced changes and small amounts of precipitation, even if located only near the inlet, can lead to large changes in permeability. Exponent values for a power law that relates changes in permeability and porosity ranged from 2 to 10, but a value of 6 held constant when conditions led to uniform changes throughout the domain.

  13. The Development and Application of Reactive Transport Modeling Techniques to Study Radionuclide Migration at Yucca Mountain, NV

    SciTech Connect

    Viswanathan, Hari Selvi

    1999-09-01

    Yucca Mountain, Nevada has been chosen as a possible site for the first high level radioactive waste repository in the United States. As part of the site investigation studies, we need to make scientifically rigorous estimations of radionuclide migration in the event of a repository breach. Performance assessment models used to make these estimations are computationally intensive. We have developed two reactive transport modeling techniques to simulate radionuclide transport at Yucca Mountain: (1) the selective coupling approach applied to the convection-dispersion-reaction (CDR) model and (2) a reactive stream tube approach (RST). These models were designed to capture the important processes that influence radionuclide migration while being computationally efficient. The conventional method of modeling reactive transport models is to solve a coupled set of multi-dimensional partial differential equations for the relevant chemical components in the system. We have developed an iterative solution technique, denoted the selective coupling method, that represents a versatile alternative to traditional uncoupled iterative techniques and the filly coupled global implicit method. We show that selective coupling results in computational and memory savings relative to these approaches. We develop RST as an alternative to the CDR method for solving large two- or three-dimensional reactive transport simulations for cases in which one is interested in predicting the flux across a specific control plane. In the RST method, the multidimensional problem is reduced to a series of one-dimensional transport simulations along streamlines. The key assumption with RST is that mixing at the control plane approximates the transverse dispersion between streamlines. We compare the CDR and RST approaches for several scenarios that are relevant to the Yucca Mountain Project. For example, we apply the CDR and RST approaches to model an ongoing field experiment called the Unsaturated Zone

  14. Generic reactive transport codes as flexible tools to integrate soil organic matter degradation models with water, transport and geochemistry in soils

    NASA Astrophysics Data System (ADS)

    Jacques, Diederik; Gérard, Fréderic; Mayer, Uli; Simunek, Jirka; Leterme, Bertrand

    2016-04-01

    A large number of organic matter degradation, CO2 transport and dissolved organic matter models have been developed during the last decades. However, organic matter degradation models are in many cases strictly hard-coded in terms of organic pools, degradation kinetics and dependency on environmental variables. The scientific input of the model user is typically limited to the adjustment of input parameters. In addition, the coupling with geochemical soil processes including aqueous speciation, pH-dependent sorption and colloid-facilitated transport are not incorporated in many of these models, strongly limiting the scope of their application. Furthermore, the most comprehensive organic matter degradation models are combined with simplified representations of flow and transport processes in the soil system. We illustrate the capability of generic reactive transport codes to overcome these shortcomings. The formulations of reactive transport codes include a physics-based continuum representation of flow and transport processes, while biogeochemical reactions can be described as equilibrium processes constrained by thermodynamic principles and/or kinetic reaction networks. The flexibility of these type of codes allows for straight-forward extension of reaction networks, permits the inclusion of new model components (e.g.: organic matter pools, rate equations, parameter dependency on environmental conditions) and in such a way facilitates an application-tailored implementation of organic matter degradation models and related processes. A numerical benchmark involving two reactive transport codes (HPx and MIN3P) demonstrates how the process-based simulation of transient variably saturated water flow (Richards equation), solute transport (advection-dispersion equation), heat transfer and diffusion in the gas phase can be combined with a flexible implementation of a soil organic matter degradation model. The benchmark includes the production of leachable organic matter

  15. Reactive Transport Model of Sulfur Cycling as Impacted by Perchlorate and Nitrate Treatments.

    PubMed

    Cheng, Yiwei; Hubbard, Christopher G; Li, Li; Bouskill, Nicholas; Molins, Sergi; Zheng, Liange; Sonnenthal, Eric; Conrad, Mark E; Engelbrektson, Anna; Coates, John D; Ajo-Franklin, Jonathan B

    2016-07-05

    Microbial souring in oil reservoirs produces toxic, corrosive hydrogen sulfide through microbial sulfate reduction, often accompanying (sea)water flooding during secondary oil recovery. With data from column experiments as constraints, we developed the first reactive-transport model of a new candidate inhibitor, perchlorate, and compared it with the commonly used inhibitor, nitrate. Our model provided a good fit to the data, which suggest that perchlorate is more effective than nitrate on a per mole of inhibitor basis. Critically, we used our model to gain insight into the underlying competing mechanisms controlling the action of each inhibitor. This analysis suggested that competition by heterotrophic perchlorate reducers and direct inhibition by nitrite produced from heterotrophic nitrate reduction were the most important mechanisms for the perchlorate and nitrate treatments, respectively, in the modeled column experiments. This work demonstrates modeling to be a powerful tool for increasing and testing our understanding of reservoir-souring generation, prevention, and remediation processes, allowing us to incorporate insights derived from laboratory experiments into a framework that can potentially be used to assess risk and design optimal treatment schemes.

  16. Interaction Between Hyperalkaline Fluids and Rocks Hosting Repositories for Radioactive Waste: Reactive Transport Simulations

    SciTech Connect

    Soler, Josep M.; Maeder, Urs K.

    2005-09-15

    Reactive transport calculations simulating the interaction between hyperalkaline solutions derived from the degradation of cement and potential host rocks for repositories for low- and intermediate-level radioactive waste have been performed. Two different cases are shown: (a) The example of the planned repository at Wellenberg and (b) the modeling of the GTS-HPF experiment at the Grimsel Test Site. The GIMRT code has been used for the simulations. Mineral reactions are described by kinetic rate laws. The reaction rates for the primary minerals are based on experimentally determined rates published in the literature and geometric considerations combined with measurements regarding mineral surface areas. Relatively fast rates for the secondary minerals have been used, so the results resemble the local equilibrium solution for these minerals. In both cases, the alteration of the rock and the precipitation of secondary phases cause a reduction in the permeability of the system, which would actually be beneficial for the performance of a repository. Mineral surface area controls, to a large extent, the amount of mineral alteration and the change in permeability.

  17. The addition of organic carbon and nitrate affects reactive transport of heavy metals in sandy aquifers.

    PubMed

    Satyawali, Yamini; Seuntjens, Piet; Van Roy, Sandra; Joris, Ingeborg; Vangeel, Silvia; Dejonghe, Winnie; Vanbroekhoven, Karolien

    2011-04-25

    Organic carbon introduction in the soil to initiate remedial measures, nitrate infiltration due to agricultural practices or sulphate intrusion owing to industrial usage can influence the redox conditions and pH, thus affecting the mobility of heavy metals in soil and groundwater. This study reports the fate of Zn and Cd in sandy aquifers under a variety of plausible in-situ redox conditions that were induced by introduction of carbon and various electron acceptors in column experiments. Up to 100% Zn and Cd removal (from the liquid phase) was observed in all the four columns, however the mechanisms were different. Metal removal in column K1 (containing sulphate), was attributed to biological sulphate reduction and subsequent metal precipitation (as sulphides). In the presence of both nitrate and sulphate (K2), the former dominated the process, precipitating the heavy metals as hydroxides and/or carbonates. In the presence of sulphate, nitrate and supplemental iron (Fe(OH)(3)) (K3), metal removal was also due to precipitation as hydroxides and/or carbonates. In abiotic column, K4, (with supplemental iron (Fe(OH)(3)), but no nitrate), cation exchange with soil led to metal removal. The results obtained were modeled using the reactive transport model PHREEQC-2 to elucidate governing processes and to evaluate scenarios of organic carbon, sulphate and nitrate inputs.

  18. Reactive transport modelling of groundwater chemistry in a chalk aquifer at the watershed scale

    NASA Astrophysics Data System (ADS)

    Mangeret, A.; De Windt, L.; Crançon, P.

    2012-09-01

    This study investigates thermodynamics and kinetics of water-rock interactions in a carbonate aquifer at the watershed scale. A reactive transport model is applied to the unconfined chalk aquifer of the Champagne Mounts (France), by considering both the chalk matrix and the interconnected fracture network. Major element concentrations and main chemical parameters calculated in groundwater and their evolution along flow lines are in fair agreement with field data. A relative homogeneity of the aquifer baseline chemistry is rapidly reached in terms of pH, alkalinity and Ca concentration since calcite equilibrium is achieved over the first metres of the vadose zone. However, incongruent chalk dissolution slowly releases Ba, Mg and Sr in groundwater. Introducing dilution effect by rainwater infiltration and a local occurrence of dolomite improves the agreement between modelling and field data. The dissolution of illite and opal-CT, controlling K and SiO2 concentrations in the model, can be approximately tackled by classical kinetic rate laws, but not the incongruent chalk dissolution. An apparent kinetic rate has therefore been fitted on field data by inverse modelling: 1.5 × 10- 5 molchalk L - 1water year - 1. Sensitivity analysis indicates that the CO2 partial pressure of the unsaturated zone is a critical parameter for modelling the baseline chemistry over the whole chalk aquifer.

  19. Reactive transport modelling of groundwater chemistry in a chalk aquifer at the watershed scale.

    PubMed

    Mangeret, A; De Windt, L; Crançon, P

    2012-09-01

    This study investigates thermodynamics and kinetics of water-rock interactions in a carbonate aquifer at the watershed scale. A reactive transport model is applied to the unconfined chalk aquifer of the Champagne Mounts (France), by considering both the chalk matrix and the interconnected fracture network. Major element concentrations and main chemical parameters calculated in groundwater and their evolution along flow lines are in fair agreement with field data. A relative homogeneity of the aquifer baseline chemistry is rapidly reached in terms of pH, alkalinity and Ca concentration since calcite equilibrium is achieved over the first metres of the vadose zone. However, incongruent chalk dissolution slowly releases Ba, Mg and Sr in groundwater. Introducing dilution effect by rainwater infiltration and a local occurrence of dolomite improves the agreement between modelling and field data. The dissolution of illite and opal-CT, controlling K and SiO(2) concentrations in the model, can be approximately tackled by classical kinetic rate laws, but not the incongruent chalk dissolution. An apparent kinetic rate has therefore been fitted on field data by inverse modelling: 1.5×10(-5) mol(chalk)L (-1) water year (-1). Sensitivity analysis indicates that the CO(2) partial pressure of the unsaturated zone is a critical parameter for modelling the baseline chemistry over the whole chalk aquifer.

  20. A reactive transport model for mercury fate in contaminated soil--sensitivity analysis.

    PubMed

    Leterme, Bertrand; Jacques, Diederik

    2015-11-01

    We present a sensitivity analysis of a reactive transport model of mercury (Hg) fate in contaminated soil systems. The one-dimensional model, presented in Leterme et al. (2014), couples water flow in variably saturated conditions with Hg physico-chemical reactions. The sensitivity of Hg leaching and volatilisation to parameter uncertainty is examined using the elementary effect method. A test case is built using a hypothetical 1-m depth sandy soil and a 50-year time series of daily precipitation and evapotranspiration. Hg anthropogenic contamination is simulated in the topsoil by separately considering three different sources: cinnabar, non-aqueous phase liquid and aqueous mercuric chloride. The model sensitivity to a set of 13 input parameters is assessed, using three different model outputs (volatilized Hg, leached Hg, Hg still present in the contaminated soil horizon). Results show that dissolved organic matter (DOM) concentration in soil solution and the binding constant to DOM thiol groups are critical parameters, as well as parameters related to Hg sorption to humic and fulvic acids in solid organic matter. Initial Hg concentration is also identified as a sensitive parameter. The sensitivity analysis also brings out non-monotonic model behaviour for certain parameters.

  1. A field, laboratory and modeling study of reactive transport of groundwater arsenic in a coastal aquifer

    PubMed Central

    Jung, Hun Bok; Charette, Matthew A.; Zheng, Yan

    2009-01-01

    A field, laboratory, and modeling study of As in groundwater discharging to Waquoit Bay, MA, shed light on coupled control of chemistry and hydrology on reactive transport of As in a coastal aquifer. Dissolved Fe(II) and As(III) in a reducing groundwater plume bracketed by an upper and a lower redox interface are oxidized as water flows towards the bay. This results in precipitation of Fe(III) oxides, along with oxidation and adsorption of As to sediment at the redox interfaces where concentrations of sedimentary HCl-leachable Fe (80~90% Fe(III)) are 734±232 mg kg-1, sedimentary phosphate extractable As (90~100% As(V)) are 316±111 μg kg-1, and are linearly correlated. Batch adsorption of As(III) onto orange, brown and gray sediments follows Langmuir isotherms, and can be fitted by a surface complexation model (SCM) assuming a diffuse layer for ferrihydrite. The sorption capacity and distribution coefficient for As increase with decreasing sediment Fe(II)/Fe. To allow accumulation of the amount of sediment As, similar hydrogeochemical conditions would have been operating for thousands of years at Waquoit Bay. The SCM simulated the observed dissolved As concentration better than a parametric approach based on Kd. Site specific isotherms should be established for Kd or SCM based models. PMID:19708362

  2. Reactive transport modeling of concrete-clay interaction: The DM borehole at Tournemire.

    NASA Astrophysics Data System (ADS)

    Soler, J. M.

    2012-04-01

    Concrete and cement paste were in contact with a clay-rich rock during 15 years in a borehole at the Tournemire Underground Rock Laboratory in France. Overcoring of the borehole and mineralogical analyses have shown a reduction of porosity at the interface due to the precipitation of ettringite, C-S-H/C-A-S-H and calcium carbonate, together with dissolution of portlandite in the cement (De Windt et al., 2008; Gaboreau et al., 2011). In the framework of the GTS-LCS project (POSIVA, Finland; JAEA, Japan; NDA, UK; SKB, Sweden; NAGRA, Switzerland), new reactive transport modeling (solute diffusion + mineral reaction) has been performed. Results using the CrunchFlow code (Steefel, 2008) show sealing of porosity at the rock side of the interface (mm scale) due to the precipitation of C-A-S-H (calcium aluminum silicate hydrate), calcite and ettringite, together with some clay dissolution. The location of sealing is influenced by cation exchange. Inclusion of cation exchange results in sealing at the rock side of the interface. Without cation exchange, sealing is at the concrete side of the interface. Recent results (Gaboreau et al., 2011) confirm the sealing on the rock side of the interface and the increase in porosity on the concrete side (portlandite dissolution).

  3. Reactive transport modelling of a remediation measure at a former gasworks site in Southern Germany

    NASA Astrophysics Data System (ADS)

    Ptak, T.; Herold, M.; Greskowiak, J.; Prommer, H.

    2009-12-01

    The aquifer beneath a former manufactured gas plant site is contaminated with polycyclic and heterocyclic aromatic hydrocarbons that form large plumes and are only slowly degraded under natural conditions. This leaves active remediation as the only viable option to eliminate the risks of toxic substances to reach potential receptors. The aims of the study presented here were to verify the proposed conceptual model of interacting physical and biogeochemical processes and to assess the effectiveness of a proposed in-situ remediation approach with the help of multi-component reactive transport modelling, focusing on the situations (i) prior to the implementation of the in-situ remediation scheme and (ii) following the operation of a circulation well with O2 and H2O2 injection to aid aerobic microbial degradation of the contaminants in the otherwise anoxic surroundings. The model incorporates microbially mediated redox reactions, mineral precipitation/dissolution reactions as well as subsequent changes in the chemical composition of the aquifer. The degradation pathways proposed in the conceptual model could be verified. The model was then used (i) to explore two possible remediation scenarios where the results highlighted the importance of source remediation and (ii) to study the uncertainty regarding the presence of another electron donor in the form of pyrite.

  4. Reactive transport modelling of the interaction of fission product ground contamination with alkaline and cementitious leachates

    SciTech Connect

    Kwong, S.; Small, J.

    2007-07-01

    The fission products Cs-137 and Sr-90 are amongst the most common radionuclides occurring in ground contamination at the UK civil nuclear sites. Such contamination is often associated with alkaline liquids and the mobility of these fission products may be affected by these chemical conditions. Similar geochemical effects may also result from cementitious leachate associated with building foundations and the use of grouts to remediate ground contamination. The behaviour of fission products in these scenarios is a complex interaction of hydrogeological and geochemical processes. A suite of modelling tools have been developed to investigate the behaviour of a radioactive plume containing Cs and Sr. Firstly the effects of sorption due to cementitious groundwater is modelled using PHREEQC. This chemical model is then incorporated into PHAST for the 3-D reactive solute transport modeling. Results are presented for a generic scenario including features and processes that are likely to be relevant to a number of civil UK nuclear sites. Initial results show that modelling can be a very cost-effective means to study the complex hydrogeological and geochemical processes involved. Modelling can help predict the mobility of contaminants in a range of site end point scenarios, and in assessing the consequences of decommissioning activities. (authors)

  5. Glutamate Transporter EAAT2 Expression is Up-Regulated in Reactive Astrocytes in Human Periventricular Leukomalacia

    PubMed Central

    DESILVA, TARA M.; BILLIARDS, SARAID S.; BORENSTEIN, NATALIA S.; TRACHTENBERG, FELICIA L.; VOLPE, JOSEPH J.; KINNEY, HANNAH C.; ROSENBERG, PAUL A.

    2010-01-01

    The major neuropathological correlate of cerebral palsy in premature infants is periventricular leukomalacia (PVL), a disorder of the immature cerebral white matter. Cerebral ischemia leading to excitotoxicity is thought to be important in the pathogenesis of this disorder, implying a critical role for glutamate transporters, the major determinants of extracellular glutamate concentration. Previously, we found that EAAT2 expression is limited primarily to premyelinating oligodendrocytes early in development and is rarely observed in astrocytes until >40 weeks. In this study, we analyzed the expression of EAAT2 in cerebral white matter from PVL and control cases. Western blot analysis suggested an up-regulation of EAAT2 in PVL compared with control cases. Single- and double-label immunocytochemistry showed a significantly higher percentage of EAAT2-immunopositive astrocytes in PVL (51.8% ± 5.6%) compared with control white matter (21.4% ± 5.6%; P = 0.004). Macrophages in the necrotic foci in PVL also expressed EAAT2. Premyelinating oligodendrocytes in both PVL and control cases expressed EAAT2, without qualitative difference in expression. The previously unrecognized up-regulation of EAAT2 in reactive astrocytes and its presence in macrophages in PVL reported here may reflect a response to either hypoxic-ischemic injury or inflammation. PMID:18314905

  6. Reactive transport of metal contaminants in alluvium - Model comparison and column simulation

    USGS Publications Warehouse

    Brown, J.G.; Bassett, R.L.; Glynn, P.D.

    2000-01-01

    A comparative assessment of two reactive-transport models, PHREEQC and HYDROGEOCHEM (HGC), was done to determine the suitability of each for simulating the movement of acidic contamination in alluvium. For simulations that accounted for aqueous complexation, precipitation and dissolution, the breakthrough and rinseout curves generated by each model were similar. The differences in simulated equilibrium concentrations between models were minor and were related to (1) different units in model output, (2) different activity coefficients, and (3) ionic-strength calculations. When adsorption processes were added to the models, the rinseout pH simulated by PHREEQC using the diffuse double-layer adsorption model rose to a pH of 6 after pore volume 15, about 1 pore volume later than the pH simulated by HGC using the constant-capacitance model. In PHREEQC simulation of a laboratory column experiment, the inability of the model to match measured outflow concentrations of selected constituents was related to the evident lack of local geochemical equilibrium in the column. The difference in timing and size of measured and simulated breakthrough of selected constituents indicated that the redox and adsorption reactions in the column occurred slowly when compared with the modeled reactions. MINTEQA2 and PHREEQC simulations of the column experiment indicated that the number of surface sites that took part in adsorption reactions was less than that estimated from the measured concentration of Fe hydroxide in the alluvium.

  7. Integrated Microbial Trait Based-Reactive Transport Modeling Approach Towards Understanding Microbial Reservoir Souring and Desouring

    NASA Astrophysics Data System (ADS)

    Li, L.; Cheng, Y.; Bouskill, N.; Hubbard, C. G.; Engelbrektson, A. L.; Coates, J. D.; Ajo Franklin, J. B.

    2014-12-01

    Microbially mediated sulfate reduction is the major metabolic process that leads to the production of hydrogen sulfide (H2S) in oil reservoirs. Biogenesis of H2S (souring) has detrimental impacts on oil production operations and can cause significant environmental and health problems. Understanding the processes that control the rates and patterns of sulfate reduction is a crucial step in developing a predictive understanding of reservoir souring and associated mitigation processes. In this study, we describe the development of a microbial trait-based model that is coupled to a reactive transport model. The model represents several anaerobic microbial functional guilds with different resource acquisition (e.g., electron donor, sulfate) traits. The integrated model was used to simulate the temporal and spatial evolution of the primary chemical species (e.g. sulfate, sulfide, nitrate, chlorate and perchlorate) and the microbial community dynamics involved in the souring and desouring processes as revealed in a recent laboratory column experiment comparing the effectiveness of nitrate, chlorate and perchlorate treatments as souring control strategies. Simulation of the laboratory experimental results shows that the model captured the spatio-temporal trend of the chemical species and microbial guilds during both souring and desouring. Model parameters derived through modeling of the column data are utilized in subsequent field-scale model simulations across a set of reservoir relevant environmental conditions. This integrated model demonstrates that interactions between SRBs and other heterotrophs can significantly impact the occurrence and extent of H2S production.

  8. Influence of permeability anisotropy on mixing controlled reactive transport simulations in porous media

    NASA Astrophysics Data System (ADS)

    Chiogna, Gabriele; Herrera, Paulo

    2015-04-01

    Several studies have demonstrated how plume deformation induced by flow heterogeneity in porous media can enhance mixing of reactants. This enhancement can have important impact on mixing controlled reactions such a biodegradation of plumes of organic compounds. On the other hand, recent studies have indicated the possibility of observing complex flow topology on groundwater flow that occurs in anisotropic yet homogenous porous media. Moreover, it has been demonstrated that those complex flow topologies can also enhance solute mixing. We study the effect of medium anisotropy on reactive solute transport for the case of a chemical reactor composed of two homogeneous anisotropic layers. We simulate different injection strategies for different chemical reactions that involve two reactants. We demonstrate the effect of the medium anisotropy by analyzing the results of the simulations and identify best strategies for the operation and design of the system to maximize reaction rates. These findings could have potential application in the design of new remediation systems for contaminated groundwater, chemical reactors and other engineering problems that involve flow through porous media.

  9. Reactive transport of uranium in fractured crystalline rock: Upscaling in time and distance

    SciTech Connect

    Dittrich, Timothy M.; Reimus, Paul W.

    2015-09-29

    In this study, batch adsorption and breakthrough column experiments were conducted to evaluate uranium transport through altered material that fills fractures in a granite rock system at the Grimsel Test Site in Switzerland at pH 6.9 and 7.9. The role of adsorption and desorption kinetics was evaluated with reactive transport modeling by comparing one-, two-, and three-site models. Emphasis was placed on describing long desorption tails that are important for upscaling in time and distance. The effect of increasing pH in injection solutions was also evaluated. For pH 6.9, a three-site model with forward rate constants between 0.07 and 0.8 ml g–1 h–1, reverse rate constants between 0.001 and 0.06 h–1, and site densities of 1.3, 0.104, and 0.026 μmol g–1 for ‘weak/fast’, ‘strong/slow’, and ‘very strong/very slow’ sites provided the best fits. For pH 7.9, a three-site model with forward rate constants between 0.05 and 0.8 mL g–1 h–1, reverse rate constants between 0.001 and 0.6 h–1, and site densities of 1.3, 0.039, and 0.013 μmol g–1 for a ‘weak/fast’, ‘strong/slow’, and ‘very strong/very slow’ sites provided the best fits. Column retardation coefficients (Rd) were 80 for pH 6.9 and 10.3 for pH 7.9. Model parameters determined from the batch and column experiments were used in 50 year large-scale simulations for continuous and pulse injections and indicated that a three-site model is necessary at pH 6.9, although a Kd-type equilibrium partition model with one-site was adequate for large scale predictions at pH 7.9. Batch experiments were useful for predicting early breakthrough times in the columns while column experiments helped differentiate the relative importance of sorption sites and desorption rate constants on transport.

  10. Reactive transport of uranium in fractured crystalline rock: Upscaling in time and distance

    DOE PAGES

    Dittrich, Timothy M.; Reimus, Paul W.

    2015-09-29

    In this study, batch adsorption and breakthrough column experiments were conducted to evaluate uranium transport through altered material that fills fractures in a granite rock system at the Grimsel Test Site in Switzerland at pH 6.9 and 7.9. The role of adsorption and desorption kinetics was evaluated with reactive transport modeling by comparing one-, two-, and three-site models. Emphasis was placed on describing long desorption tails that are important for upscaling in time and distance. The effect of increasing pH in injection solutions was also evaluated. For pH 6.9, a three-site model with forward rate constants between 0.07 and 0.8more » ml g–1 h–1, reverse rate constants between 0.001 and 0.06 h–1, and site densities of 1.3, 0.104, and 0.026 μmol g–1 for ‘weak/fast’, ‘strong/slow’, and ‘very strong/very slow’ sites provided the best fits. For pH 7.9, a three-site model with forward rate constants between 0.05 and 0.8 mL g–1 h–1, reverse rate constants between 0.001 and 0.6 h–1, and site densities of 1.3, 0.039, and 0.013 μmol g–1 for a ‘weak/fast’, ‘strong/slow’, and ‘very strong/very slow’ sites provided the best fits. Column retardation coefficients (Rd) were 80 for pH 6.9 and 10.3 for pH 7.9. Model parameters determined from the batch and column experiments were used in 50 year large-scale simulations for continuous and pulse injections and indicated that a three-site model is necessary at pH 6.9, although a Kd-type equilibrium partition model with one-site was adequate for large scale predictions at pH 7.9. Batch experiments were useful for predicting early breakthrough times in the columns while column experiments helped differentiate the relative importance of sorption sites and desorption rate constants on transport.« less

  11. Reactive transport modeling of CO2 injection in the Farnsworth, Texas hydrocarbon field

    NASA Astrophysics Data System (ADS)

    Ahmmed, B.; Appold, M. S.; McPherson, B. J. O. L.; Grigg, R.; White, M. D.

    2014-12-01

    The Farnsworth hydrocarbon field in northern Texas has been an experimental site for CO2 sequestration and enhanced oil recovery for the U.S. Department of Energy-sponsored Southwest Partnership (SWP) since April, 2013. CO2 is to be injected into the Pennsylvanian Morrow Sandstone at a rate of 200,000 tonnes per year for at least five years. The Morrow is a quartz-rich sandstone that lies at a depth of about 2400 m. Pore water in the Morrow has a total dissolved solids content of about 3600 mg/L dominated by Na, Cl, bicarbonate, and Ca. A reactive solute transport model was constructed for a 1700 × 1700 × 95 m volume using the TOUGHREACT software and the ECO2N equation of state for aqueous brine and CO2. Simulations were carried out to 100 years. The results showed immiscible CO2 gas to be concentrated in a lateral plume extending radially from the well screen, its ascent impeded by vigorous lateral groundwater flow in the more permeable upper Morrow. CO2 was much more widespread in aqueous solution, lowering pH throughout much of the model volume after 100 years, to a minimum of about 4.7. The low reactivity of the Morrow Sandstone due to its quartz-rich matrix and dilute pore fluid resulted in little mineral precipitation or dissolution, with net volume changes for any mineral no higher than order 10-4. The simulations predicted net dissolution of albite, calcite, and chlorite, and net precipitation of dawsonite, illite, and magnesite. The Morrow matrix was predicted to undergo slight net dissolution overall, resulting in porosity increases of up to 0.01%, suggesting that the Morrow would be resistant to significant changes in hydraulic properties as a result of the proposed amount of CO2 injection. For the 100 year simulation times calculated thus far, only a small fraction of the injected CO2 would be sequestered as carbonate minerals, with most of the injected CO2 dissolved in the aqueous phase.

  12. Reactive Transport Analysis of Fault 'Self-sealing' Associated with CO2 Storage

    NASA Astrophysics Data System (ADS)

    Patil, V.; McPherson, B. J. O. L.; Priewisch, A.; Franz, R. J.

    2014-12-01

    We present an extensive hydrologic and reactive transport analysis of the Little Grand Wash fault zone (LGWF), a natural analog of fault-associated leakage from an engineered CO2 repository. Injecting anthropogenic CO2 into the subsurface is suggested for climate change mitigation. However, leakage of CO2 from its target storage formation into unintended areas is considered as a major risk involved in CO2 sequestration. In the event of leakage, permeability in leakage pathways like faults may get sealed (reduced) due to precipitation or enhanced (increased) due to dissolution reactions induced by CO2-enriched water, thus influencing migration and fate of the CO2. We hypothesize that faults which act as leakage pathways can seal over time in presence of CO2-enriched waters. An example of such a fault 'self-sealing' is found in the LGWF near Green River, Utah in the Paradox basin, where fault outcrop shows surface and sub-surface fractures filled with calcium carbonate (CaCO3). The LGWF cuts through multiple reservoirs and seal layers piercing a reservoir of naturally occurring CO2, allowing it to leak into overlying aquifers. As the CO2-charged water from shallower aquifers migrates towards atmosphere, a decrease in pCO2 leads to supersaturation of water with respect to CaCO3, which precipitates in the fractures of the fault damage zone. In order to test the nature, extent and time-frame of the fault sealing, we developed reactive flow simulations of the LGWF. Model parameters were chosen based on hydrologic measurements from literature. Model geochemistry was constrained by water analysis of the adjacent Crystal Geyser and observations from a scientific drilling test conducted at the site. Precipitation of calcite in the top portion of the fault model led to a decrease in the porosity value of the damage zone, while clay precipitation led to a decrease in the porosity value of the fault core. We found that the results were sensitive to the fault architecture

  13. A comparison of results obtained with two subsurface non-isothermal multiphase reactive transport simulators, FADES-CORE and TOUGHREACT

    SciTech Connect

    Juncosa Rivera, Ricardo; Xu, Tianfu; Pruess, Karsten

    2001-01-01

    FADES-CORE and TOUGHREACT are codes used to model the non-isothermal multiphase flow with multicomponent reactive transport in porous media. Different flow and reactive transport problems were used to compare the FADES-CORE and TOUGHREACT codes. These problems take into account the different cases of multiphase flow with and without heat transport, conservative transport, and reactive transport. Consistent results were obtained from both codes, which use different numerical methods to solve the differential equations resulting from the various physicochemical processes. Here we present the results obtained from both codes for various cases. Some results are slightly different with minor discrepancies, which have been remedied, so that both codes would be able to reproduce the same processes using the same parameters. One of the discrepancies found is related to the different calculation for thermal conductivity in heat transport, which affects the calculation of the temperatures, as well as the pH of the reaction of calcite dissolution problem modeled. Therefore it is possible to affirm that the pH is highly sensitive to temperature. Generally speaking, the comparison was concluded to be highly satisfactory, leading to the complete verification of the FADES-CORE code. However, we must keep in mind that, as there are no analytical solutions available with which to verify the codes, the TOUGHREACT code has been thoroughly corroborated, given that the only possible way to prove that the code simulation is correct, is by comparing the results obtained with both codes for the identical problems, or to validate the simulation results with actual measured data.

  14. CRITIQUE OF DUAL CONTINUUM FORMULATIONS OF MULTICOMPONENT REACTIVE TRANSPORT IN FRACTURED POROUS MEDIA

    SciTech Connect

    Lichtner, P.C.

    2000-02-01

    Subsurface flow processes may take place at many different scales. The different scales refer to rock pore structure, micro-fractures, distinct fracture networks ranging from small to large fracture spacing, and even faults. Presently, there is no satisfactory methodology for describing quantitatively flow and reactive transport in multi-scale media. Approaches commonly applied to model fractured systems include single continuum models (SCM), equivalent continuum models (ECM), discrete fracture models (DFM), and various forms of dual continuum models (DCM). The SCM describes flow in the fracture network only and is valid in the absence of fracture-matrix interaction. The ECM, on the other hand, requires pervasive interaction between fracture and matrix and is based on averaging their properties. The ECM is characterized by equal fracture and matrix solute concentrations, but generally different mineral concentrations. The DFM is perhaps the most rigorous, but would require inordinate computational resources for a highly fractured rock mass. The DCM represents a fractured porous medium as two interacting continua with one continuum corresponding to the fracture network and the other the matrix. A coupling term provides mass transfer between the two continua. Vidues for mineral and solute concentrations and other properties such as liquid saturation state maybe assigned individually to fracture and matrix. Two forms of the DCM are considered characterized by connected and disconnected matrix blocks. The former is referred to as the DCCM (dual continuum connected matrix) model and the latter as the DCDM (dual continuum disconnected matrix) model. In contrast to the DCCM model in which concentration gradients in the matrix are allowed only parallel to the fracture, the DFM provides for matrix concentration gradients perpendicular to the fracture. The DFM and DCCM models can agree with each other only in the case where both reduce to the ECM. The DCCM model exhibits the

  15. Reactive Transport at Aquifer - River Interfaces - Panacea for River Restoration or Ticking Time Bomb?

    NASA Astrophysics Data System (ADS)

    Naden, E.; Angermann, L.; Cassidy, N. J.; Kaeser, D.; Binley, A. M.; Heathwaite, L.; Krause, S.

    2009-12-01

    The ‘hyporheic zone’ or ‘interstitial’ characterises an area of intensive groundwater and surface water mixing within streambed sediments. Its physical conditions, as for instance the hydraulic conductivity and residence time, control fluxes and exchange rates between groundwater and surface water. Because of its often steep and dynamic redox gradients, the hyporheic zone can represent an area of high chemical activity. Previous studies described how the transport and redox processes in the hyporheic zone can cause effective nutrient attenuation, e.g. by denitrification. Hence, regulatory bodies and catchment management plans hope for the hyporheic zone to delimit the negative impact, polluted groundwater can have for the stream ecological health. In this study we investigate spatial and temporal patterns of physical streambed characteristics and redox chemical conditions and its controls on the reactive transport and transformation of nitrogen in the streambeds of two UK upland and lowland rivers. For the streambed sediments of several stream reaches, pore water nitrate/nitrite and ammonia concentrations were monitored together with common anions, redox conditions, dissolved oxygen and organic carbon and rates of groundwater up-welling and surface water mixing in a dense system of nested piezometer over several baseflow periods. Spatial patterns of aquifer - river exchange were furthermore investigated by active and passive heat tracer experiments using fibre optic distributed temperature sensor networks at reach and heat pulse injection experiments at local scales. The results of this study indicate that hyporheic nutrient transformation can well exceed the usually assumed streambed depths of a few cm and may occur in depths of > 1m. Our investigations furthermore detected, that within the research area the hyporheic passage has a spatially very variable impact on the exchange fluxes and nitrogen concentrations and transformation rates in the streambed

  16. Critique of dual continuum formulations of multicomponent reactive transport in fractured porous media

    NASA Astrophysics Data System (ADS)

    Lichtner, Peter C.

    Subsurface flow processes may take place at many different scales. The different scales refer to rock pore structure, microfractures, distinct fracture networks (ranging from small to large fracture spacing), and even faults. Presently, there is no satisfactory methodology for quantitatively describing flow and reactive transport in multiscale media. Approaches commonly applied to model fractured systems include single continuum models (SCM), equivalent continuum models (ECM), discrete fracture models (DFM), and various forms of dual continuum models (DCM). The SCM describes flow in the fracture network only and is valid in the absence of fracture-matrix interaction. The ECM, on the other hand, requires pervasive interaction between fracture and matrix and is based on averaging their properties. The ECM is characterized by equal fracture and matrix solute concentrations, but generally different mineral concentrations. The DFM is perhaps the most rigorous, but would require inordinate computational resources for a highly fractured rock mass. The DCM represents a fractured porous medium as two interacting continuums with one continuum corresponding to the fracture network and the other the matrix. A coupling term provides mass transfer between the two continuums. Values for mineral and solute concentrations and other properties such as liquid saturation state may be assigned individually to fracture and matrix. Two forms of the DCM are considered, characterized by connected and disconnected matrix blocks. The former is referred to as the dual continuum connected matrix (DCCM) model and the latter as the dual continuum disconnected matrix (DCDM) model. In contrast to the DCCM model, in which concentration gradients in the matrix are allowed only parallel to the fracture, the DFM provides for matrix concentration gradients perpendicular to the fracture. The DFM and DCCM models can agree with each other only in the case where both reduce to the ECM. The DCCM model

  17. Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling

    NASA Astrophysics Data System (ADS)

    Amos, Richard T.; Ulrich Mayer, K.

    2006-09-01

    In many natural and contaminated aquifers, geochemical processes result in the production or consumption of dissolved gases. In cases where methanogenesis or denitrification occurs, the production of gases may result in the formation and growth of gas bubbles below the water table. Near the water table, entrapment of atmospheric gases during water table rise may provide a significant source of O 2 to waters otherwise depleted in O 2. Furthermore, the presence of bubbles will affect the hydraulic conductivity of an aquifer, resulting in changes to the groundwater flow regime. The interactions between physical transport, biogeochemical processes, and gas bubble formation, entrapment and release is complex and requires suitable analysis tools. The objective of the present work is the development of a numerical model capable of quantitatively assessing these processes. The multicomponent reactive transport code MIN3P has been enhanced to simulate bubble growth and contraction due to in-situ gas production or consumption, bubble entrapment due to water table rise and subsequent re-equilibration of the bubble with ambient groundwater, and permeability changes due to trapped gas phase saturation. The resulting formulation allows for the investigation of complex geochemical systems where microbially mediated redox reactions both produce and consume gases as well as affect solution chemistry, alkalinity, and pH. The enhanced model has been used to simulate processes in a petroleum hydrocarbon contaminated aquifer where methanogenesis is an important redox process. The simulations are constrained by data from a crude oil spill site near Bemidji, MN. Our results suggest that permeability reduction in the methanogenic zone due to in-situ formation of gas bubbles, and dissolution of entrapped atmospheric bubbles near the water table, both work to attenuate the dissolved gas plume emanating from the source zone. Furthermore, the simulations demonstrate that under the given

  18. Pareto optimal calibration of highly nonlinear reactive transport groundwater models using particle swarm optimization

    NASA Astrophysics Data System (ADS)

    Siade, A. J.; Prommer, H.; Welter, D.

    2014-12-01

    Groundwater management and remediation requires the implementation of numerical models in order to evaluate the potential anthropogenic impacts on aquifer systems. In many situations, the numerical model must, not only be able to simulate groundwater flow and transport, but also geochemical and biological processes. Each process being simulated carries with it a set of parameters that must be identified, along with differing potential sources of model-structure error. Various data types are often collected in the field and then used to calibrate the numerical model; however, these data types can represent very different processes and can subsequently be sensitive to the model parameters in extremely complex ways. Therefore, developing an appropriate weighting strategy to address the contributions of each data type to the overall least-squares objective function is not straightforward. This is further compounded by the presence of potential sources of model-structure errors that manifest themselves differently for each observation data type. Finally, reactive transport models are highly nonlinear, which can lead to convergence failure for algorithms operating on the assumption of local linearity. In this study, we propose a variation of the popular, particle swarm optimization algorithm to address trade-offs associated with the calibration of one data type over another. This method removes the need to specify weights between observation groups and instead, produces a multi-dimensional Pareto front that illustrates the trade-offs between data types. We use the PEST++ run manager, along with the standard PEST input/output structure, to implement parallel programming across multiple desktop computers using TCP/IP communications. This allows for very large swarms of particles without the need of a supercomputing facility. The method was applied to a case study in which modeling was used to gain insight into the mobilization of arsenic at a deepwell injection site

  19. Investigating the role of gas bubble formation and entrapment in contaminated aquifers: Reactive transport modelling

    USGS Publications Warehouse

    Amos, Richard T.; Mayer, K. Ulrich

    2006-01-01

    In many natural and contaminated aquifers, geochemical processes result in the production or consumption of dissolved gases. In cases where methanogenesis or denitrification occurs, the production of gases may result in the formation and growth of gas bubbles below the water table. Near the water table, entrapment of atmospheric gases during water table rise may provide a significant source of O2 to waters otherwise depleted in O2. Furthermore, the presence of bubbles will affect the hydraulic conductivity of an aquifer, resulting in changes to the groundwater flow regime. The interactions between physical transport, biogeochemical processes, and gas bubble formation, entrapment and release is complex and requires suitable analysis tools. The objective of the present work is the development of a numerical model capable of quantitatively assessing these processes. The multicomponent reactive transport code MIN3P has been enhanced to simulate bubble growth and contraction due to in-situ gas production or consumption, bubble entrapment due to water table rise and subsequent re-equilibration of the bubble with ambient groundwater, and permeability changes due to trapped gas phase saturation. The resulting formulation allows for the investigation of complex geochemical systems where microbially mediated redox reactions both produce and consume gases as well as affect solution chemistry, alkalinity, and pH. The enhanced model has been used to simulate processes in a petroleum hydrocarbon contaminated aquifer where methanogenesis is an important redox process. The simulations are constrained by data from a crude oil spill site near Bemidji, MN. Our results suggest that permeability reduction in the methanogenic zone due to in-situ formation of gas bubbles, and dissolution of entrapped atmospheric bubbles near the water table, both work to attenuate the dissolved gas plume emanating from the source zone. Furthermore, the simulations demonstrate that under the given

  20. Open-Source Development of the Petascale Reactive Flow and Transport Code PFLOTRAN

    NASA Astrophysics Data System (ADS)

    Hammond, G. E.; Andre, B.; Bisht, G.; Johnson, T.; Karra, S.; Lichtner, P. C.; Mills, R. T.

    2013-12-01

    Open-source software development has become increasingly popular in recent years. Open-source encourages collaborative and transparent software development and promotes unlimited free redistribution of source code to the public. Open-source development is good for science as it reveals implementation details that are critical to scientific reproducibility, but generally excluded from journal publications. In addition, research funds that would have been spent on licensing fees can be redirected to code development that benefits more scientists. In 2006, the developers of PFLOTRAN open-sourced their code under the U.S. Department of Energy SciDAC-II program. Since that time, the code has gained popularity among code developers and users from around the world seeking to employ PFLOTRAN to simulate thermal, hydraulic, mechanical and biogeochemical processes in the Earth's surface/subsurface environment. PFLOTRAN is a massively-parallel subsurface reactive multiphase flow and transport simulator designed from the ground up to run efficiently on computing platforms ranging from the laptop to leadership-class supercomputers, all from a single code base. The code employs domain decomposition for parallelism and is founded upon the well-established and open-source parallel PETSc and HDF5 frameworks. PFLOTRAN leverages modern Fortran (i.e. Fortran 2003-2008) in its extensible object-oriented design. The use of this progressive, yet domain-friendly programming language has greatly facilitated collaboration in the code's software development. Over the past year, PFLOTRAN's top-level data structures were refactored as Fortran classes (i.e. extendible derived types) to improve the flexibility of the code, ease the addition of new process models, and enable coupling to external simulators. For instance, PFLOTRAN has been coupled to the parallel electrical resistivity tomography code E4D to enable hydrogeophysical inversion while the same code base can be used as a third

  1. Reactive sputter deposition of pyrite structure transition metal disulfide thin films: Microstructure, transport, and magnetism

    SciTech Connect

    Baruth, A.; Manno, M.; Narasimhan, D.; Shankar, A.; Zhang, X.; Johnson, M.; Aydil, E. S.; Leighton, C.

    2012-09-01

    Transition metal disulfides crystallizing in the pyrite structure (e.g., TMS{sub 2}, with TM = Fe, Co, Ni, and Cu) are a class of materials that display a remarkably diverse array of functional properties. These properties include highly spin-polarized ferromagnetism (in Co{sub 1-x}Fe{sub x}S{sub 2}), superconductivity (in CuS{sub 2}), an antiferromagnetic Mott insulating ground state (in NiS{sub 2}), and semiconduction with close to optimal parameters for solar absorber applications (in FeS{sub 2}). Exploitation of these properties in heterostructured devices requires the development of reliable and reproducible methods for the deposition of high quality pyrite structure thin films. In this manuscript, we report on the suitability of reactive sputter deposition from metallic targets in an Ar/H{sub 2}S environment as a method to achieve exactly this. Optimization of deposition temperature, Ar/H{sub 2}S pressure ratio, and total working gas pressure, assisted by plasma optical emission spectroscopy, reveals significant windows over which deposition of single-phase, polycrystalline, low roughness pyrite films can be achieved. This is illustrated for the test cases of the ferromagnetic metal CoS{sub 2} and the diamagnetic semiconductor FeS{sub 2}, for which detailed magnetic and transport characterization are provided. The results indicate significant improvements over alternative deposition techniques such as ex situ sulfidation of metal films, opening up exciting possibilities for all-sulfide heterostructured devices. In particular, in the FeS{sub 2} case it is suggested that fine-tuning of the sputtering conditions provides a potential means to manipulate doping levels and conduction mechanisms, critical issues in solar cell applications. Parenthetically, we note that conditions for synthesis of phase-pure monosulfides and thiospinels are also identified.

  2. Expanding the role of reactive transport models in critical zone processes

    USGS Publications Warehouse

    Li, Li; Maher, Kate; Navarre-Sitchler, Alexis; Druhan, Jennifer; Meile, Christof; Lawrence, Corey; Moore, Joel; Perdrial, Julia; Sullivan, Pamela; Thompson, Aaron; Jin, Lixin; Bolton, Edward W.; Brantley, Susan L.; Dietrich, William E.; Mayer, K. Ulrich; Steefel, Carl; Valocchi, Albert J.; Zachara, John M.; Kocar, Benjamin D.; McIntosh, Jennifer; Tutolo, Benjamin M.; Kumar, Mukesh; Sonnenthal, Eric; Bao, Chen; Beisman, Joe

    2017-01-01

    Models test our understanding of processes and can reach beyond the spatial and temporal scales of measurements. Multi-component Reactive Transport Models (RTMs), initially developed more than three decades ago, have been used extensively to explore the interactions of geothermal, hydrologic, geochemical, and geobiological processes in subsurface systems. Driven by extensive data sets now available from intensive measurement efforts, there is a pressing need to couple RTMs with other community models to explore non-linear interactions among the atmosphere, hydrosphere, biosphere, and geosphere. Here we briefly review the history of RTM development, summarize the current state of RTM approaches, and identify new research directions, opportunities, and infrastructure needs to broaden the use of RTMs. In particular, we envision the expanded use of RTMs in advancing process understanding in the Critical Zone, the veneer of the Earth that extends from the top of vegetation to the bottom of groundwater. We argue that, although parsimonious models are essential at larger scales, process-based models offer tools to explore the highly nonlinear coupling that characterizes natural systems. We present seven testable hypotheses that emphasize the unique capabilities of process-based RTMs for (1) elucidating chemical weathering and its physical and biogeochemical drivers; (2) understanding the interactions among roots, micro-organisms, carbon, water, and minerals in the rhizosphere; (3) assessing the effects of heterogeneity across spatial and temporal scales; and (4) integrating the vast quantity of novel data, including “omics” data (genomics, transcriptomics, proteomics, metabolomics), elemental concentration and speciation data, and isotope data into our understanding of complex earth surface systems. With strong support from data-driven sciences, we are now in an exciting era where integration of RTM framework into other community models will facilitate process

  3. Hierarchical Testing with Automated Document Generation for Amanzi, ASCEM's Subsurface Flow and Reactive Transport Simulator

    NASA Astrophysics Data System (ADS)

    Moulton, J. D.; Steefel, C. I.; Yabusaki, S.; Castleton, K.; Scheibe, T. D.; Keating, E. H.; Freedman, V. L.

    2013-12-01

    The Advanced Simulation Capabililty for Environmental Management (ASCEM) program is developing an approach and open-source tool suite for standardized risk and performance assessments at legacy nuclear waste sites. These assessments use a graded and iterative approach, beginning with simplified highly abstracted models, and adding geometric and geologic complexity as understanding is gained. To build confidence in this assessment capability, extensive testing of the underlying tools is needed. Since the tools themselves, such as the subsurface flow and reactive-transport simulator, Amanzi, are under active development, testing must be both hierarchical and highly automated. In this presentation we show how we have met these requirements, by leveraging the python-based open-source documentation system called Sphinx with several other open-source tools. Sphinx builds on the reStructured text tool docutils, with important extensions that include high-quality formatting of equations, and integrated plotting through matplotlib. This allows the documentation, as well as the input files for tests, benchmark and tutorial problems, to be maintained with the source code under a version control system. In addition, it enables developers to build documentation in several different formats (e.g., html and pdf) from a single source. We will highlight these features, and discuss important benefits of this approach for Amanzi. In addition, we'll show that some of ASCEM's other tools, such as the sampling provided by the Uncertainty Quantification toolset, are naturally leveraged to enable more comprehensive testing. Finally, we will highlight the integration of this hiearchical testing and documentation framework with our build system and tools (CMake, CTest, and CDash).

  4. Using Reactive Transport Modeling to Evaluate the Source Term at Yucca Mountain

    SciTech Connect

    Y. Chen

    2001-12-19

    The conventional approach of source-term evaluation for performance assessment of nuclear waste repositories uses speciation-solubility modeling tools and assumes pure phases of radioelements control their solubility. This assumption may not reflect reality, as most radioelements (except for U) may not form their own pure phases. As a result, solubility limits predicted using the conventional approach are several orders of magnitude higher then the concentrations of radioelements measured in spent fuel dissolution experiments. This paper presents the author's attempt of using a non-conventional approach to evaluate source term of radionuclide release for Yucca Mountain. Based on the general reactive-transport code AREST-CT, a model for spent fuel dissolution and secondary phase precipitation has been constructed. The model accounts for both equilibrium and kinetic reactions. Its predictions have been compared against laboratory experiments and natural analogues. It is found that without calibrations, the simulated results match laboratory and field observations very well in many aspects. More important is the fact that no contradictions between them have been found. This provides confidence in the predictive power of the model. Based on the concept of Np incorporated into uranyl minerals, the model not only predicts a lower Np source-term than that given by conventional Np solubility models, but also produces results which are consistent with laboratory measurements and observations. Moreover, two hypotheses, whether Np enters tertiary uranyl minerals or not, have been tested by comparing model predictions against laboratory observations, the results favor the former. It is concluded that this non-conventional approach of source term evaluation not only eliminates over-conservatism in conventional solubility approach to some extent, but also gives a realistic representation of the system of interest, which is a prerequisite for truly understanding the long

  5. Analysis of acidity production during enhanced reductive dechlorination using a simplified reactive transport model

    NASA Astrophysics Data System (ADS)

    Brovelli, A.; Barry, D. A.; Robinson, C.; Gerhard, J. I.

    2012-07-01

    Build-up of fermentation products and hydrochloric acid at a contaminated site undergoing enhanced reductive dechlorination can result in groundwater acidification. Sub-optimal pH conditions can inhibit microbial activity and lead to reduced dechlorination rates. The extent of acidification likely to occur is site-specific and depends primarily on the extent of fermentation and dechlorination, the geochemical composition of soil and groundwater, and the pH-sensitivity of the active microbial populations. Here, the key chemical and physical mechanisms that control the extent of groundwater acidification in a contaminated site were examined, and the extent to which the remediation efficiency was affected by variations in groundwater pH was evaluated using a simplified process-based reactive-transport model. This model was applied successfully to a well-documented field site and was then employed in a sensitivity analysis to identify the processes likely to significantly influence acidity production and subsequent microbial inhibition. The accumulation of organic acids produced from the fermentation of the injected substrate was the main cause of the pH change. The concentration of dissolved sulphates controlled substrate utilisation efficiency because sulphate-reducing biomass competed with halo-respiring biomass for the fermentation products. It was shown further that increased groundwater velocity increases dilution and reduces the accumulation of acidic products. As a consequence, the flow rate corresponding to the highest remediation efficiency depends on the fermentation and dechlorination rates. The model enables investigation and forecasting of the extent and areal distribution of pH change, providing a means to optimise the application of reductive dechlorination for site remediation.

  6. Numerical modeling of coupled thermal chemical reactive transport: simulation of a heat storage system

    NASA Astrophysics Data System (ADS)

    Shao, H.; Watanabe, N.; Singh, A. K.; Nagel, T.; Linder, M.; Woerner, A.; Kolditz, O.

    2012-12-01

    As a carbon-free energy supply technology, the operation time and final energy output of thermal solar power plants can be greatly extended if efficient thermal storage systems are applied. One of the proposed design of such system is to utilize reversible thermochemical reactions and its embedded reaction enthalpy, e.g. the Ca(OH)2/CaO hydration circle, in a fixed-bed gas-solid reactor (Schaube et al. 2011) The modeling of such a storage system involves multiple strongly-coupled physical and chemical processes. Seepage velocity is calculated by the nonlinear Forchheimer law. Gas phase density and viscosity are temperature, pressure and composition dependent. Also, heat transfer between gas and solid phases is largely influenced by the exothermal heat produced by the hydration of calcium oxide. Numerical solution of four governing PDEs include the mass balance, reactive transport, heat balance equations for gas and solid phases, which are implemented into the open source scientific software OpenGeoSys in a monolithic way. Based on it, a 2D numerical model, considering the boundary heat loss of the system, was set up to simulate the energy-storage and release circle. The high performance computing techniques were employed in two stages. First, the dynamic behavior of the heat storage system is simulated on a parallel platform. Second, a large number of processors are employed to perform sensitivity analysis, whereas the reaction rates and efficiency factor of heat transfer are parameterized so that the measured and simulated temperature profile fit with each other. The model showed that heat transfer coefficient between solid and gas phase, grain size of the filling material will influence the final performance greatly. By varying these factors, the calibrated model will be further applied to optimize the design of such energy storage system.

  7. Reactive Transport Modeling of Subsurface Arsenic Removal Systems in Rural Bangladesh

    NASA Astrophysics Data System (ADS)

    Bakker, M.; Rahman, M. M.; van Breukelen, B. M.; Ahmed, K. M.

    2014-12-01

    Elevated concentrations of arsenic (As) in the groundwater of the shallow aquifers of Bangladesh are a major public health concern. Subsurface Arsenic Removal (SAR) is a relatively new treatment option that can potentially be a cost effective method for arsenic removal for community-based drinking water supplies. The basic idea of SAR is to extract water, aerate it, and re-inject it, after which groundwater with reduced arsenic concentrations may be extracted. The main process for As reduction is sorption to Hydrous Ferric Oxides (HFO) that forms after injection of the aerated water. The purpose of this poster is to investigate the major geochemical processes responsible for the (im)mobilization of As during SAR operation. SAR was applied at a test site in Muradnagar upazila in Comilla district about 100 km southeast of Dhaka in Bangladesh. Multiple extraction/aeration/re-injection cycles were performed and water samples were analyzed. A PHREEQC reactive transport model (RTM) was used in a radial flow setting to try to reproduce the measurements. Kinetic oxidation/dissolution reactions, cation exchange, and surface complexation were simulated. The simulation of different reactions enables the possibility to discern the reaction parameters involved in the im(mobilization) of As. The model fit has reasonable agreement with the observed data for major ions and trace elements. The model suggests an increasing sorption capacity due to the gradual development of HFO precipitates resulting from the injection phases. Modeled breakthrough curves of As, Fe(II), and Mn, match the measured increase of As, Fe(II), and Mn removal with successive cycles. The model illustrates that the pH of groundwater during SAR operation has a great impact on As sorption in the subsurface. The surface complexation modeling suggests that competitive displacement of As by H4SiO4 is an important factor limiting As removal during SAR operation.

  8. Influence of biofilm accumulation on flow and reactive transport through porous media

    NASA Astrophysics Data System (ADS)

    Sharp, R.; Adgie, M.; Cunningham, A.

    2003-04-01

    A series of continuous flow, porous media reactor studies were performed to characterize the development of thick biofilms in porous media and the subsequent effects on flow and reactive transport. The bioluminescent organism Vibrio fischeri was used to produce various degrees of biofilm growth within the porous media system. V. fischeri biofilm growth, distribution, and activity in the porous media reactors was evaluated using bioluminescent imaging. Bulk fluid flow and flow channel dynamics in the porous media were monitored by imaging pulses of nigrosine bulk fluid dye. Hydrodynamics of the porous media/biofilm systems were analyzed using fluorescein break through curves and head loss across the system. Bioluminescent and bulk-fluid dye imaging, along with fluoroscein break through curve analysis, provided quantitative information on the transient distribution of biofilm within the reactor and the dynamic relationship between biofilm development and porous media hydraulics. Bioluminescent and bulk-fluid dye images showed continuous creation and closure of flow channels in the biofilm/porous media matrix. Flow channel size and distribution changed with increasing degrees of biofilm growth. Bioluminescence showed not only the density and distribution of biofilm growth in the porous media, but also the rate of oxygen uptake across the flow field. Results from the breakthrough curves suggest that thin biofilms transform the well-defined plug flow regime of clean porous media to a flow with severe axial and longitudinal dispersion. As the biofilm thickens, the flow regime is transformed to dispersed plug flow with an accelerated residence time. These studies provide a better quantitative understanding of the fundamental relationship between biofilm development and bulk fluid hydrodynamics in porous media. Results demonstrate the simultaneous visualization of biofilm growth and bulk fluid flow in porous media at the meso-scale. The studies also establish a novel

  9. Evolution of carbon isotope signatures during reactive transport of hydrocarbons in heterogeneous aquifers

    NASA Astrophysics Data System (ADS)

    Höyng, Dominik; Prommer, Henning; Blum, Philipp; Grathwohl, Peter; Mazo D'Affonseca, Fernando

    2015-03-01

    Compound-specific isotope analysis (CSIA) of organic pollutants has become a well-established tool for assessing the occurrence and extent of biodegradation processes in contaminated aquifers. However, the precision of CSIA is influenced by the degree to which assumptions underlying CSIA data interpretation hold under realistic field-scale conditions. For the first time this study demonstrates how aquifer analogs combined with reactive transport models offer an underexplored way to develop generic process understanding, evaluate monitoring and quantification strategies in highly heterogeneous subsurface settings. Data from high-resolution aquifer analogs were used in numerical experiments to track the propagation of a representative oxidizable organic compound (toluene) within a variety of realistic heterogeneous aquifers and to investigate its detailed fate. The simulations were used to analyze (1) the effects of physical aquifer heterogeneities on spatiotemporal patterns of contaminant concentrations and isotope signatures, (2) the performance of the commonly applied Rayleigh equation and (3) the applicability of an extension of the Rayleigh equation for complex hydrogeological conditions. The results indicate that if field-derived enrichment factors are applied without corrections for dilution, the conventional Rayleigh equation is inaccurate and estimates for biodegradation are typically overestimated and unreliable in heterogeneous aquifers. Underestimations can occur due to the partial source zone depletion. In contrast, if dilution can be accurately accounted for, field-derived enrichment factors comprise a suitable alternative to laboratory-derived and redox-specific enrichment factors. The study also examines to what extent variations in monitoring/sampling strategies influence the obtained results. Especially measurements from long-screened wells (> 1 m) reveal to be inappropriate for the application of the Rayleigh equation in the investigated aquifer

  10. A reactive transport model to simulate uranium immobilization through pH manipulation

    SciTech Connect

    Zhang, Fan; Luo, Wensui; Watson, David B; Peterson, Mark J; Gu, Baohua; Spalding, Brian Patrick; Jardine, Philip M

    2008-07-01

    Saprolite cores collected from around the former S-3 Ponds waste disposal site on the Oak Ridge Reservation in east Tennessee, USA, exhibit low pH and high concentrations of Al, Ca, Mg, Mn, various trace metals such as Ni and Co, and radionuclides such as U and Tc. Because uranium is one of the major contaminants of concern at the site, its behavior was of particular interest. The mobility of uranium depends highly on pH. Groundwater titration experiments showed that when pH was increased from 3.87 to 5.45 with addition of dissolved sodium hydroxide, concentration of aqueous uranium decreased from 50 ppm to less than 5 ppm. However, base additions to the sediments to increase pH are strongly buffered by various precipitation and sorption reactions. This study was undertaken to investigate the geochemical processes that control contaminant mobility and to develop a practical model to predict uranium immobilization under conditions where pH is manipulated for remediation of geochemically complex sites. The method of Spalding and Spalding was utilized to model soil buffer capacity by treating aquifer solids as a polyprotic acid. Aluminum precipitation and dissolution kinetics was included in HydroGeoChem v5.0 in addition to an equilibrium reaction model that considers aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange capacity. The HydroGeoChem model was successfully utilized to simulate batch titration experiments and comparison of reactive transport model results with pH manipulation column experiments were in close agreement. The model was also calibrated to simulate acidic groundwater percolating through carbonate gravel at the site.

  11. Hybrid finite-volume/transported PDF method for the simulation of turbulent reactive flows

    NASA Astrophysics Data System (ADS)

    Raman, Venkatramanan

    A novel computational scheme is formulated for simulating turbulent reactive flows in complex geometries with detailed chemical kinetics. A Probability Density Function (PDF) based method that handles the scalar transport equation is coupled with an existing Finite Volume (FV) Reynolds-Averaged Navier-Stokes (RANS) flow solver. The PDF formulation leads to closed chemical source terms and facilitates the use of detailed chemical mechanisms without approximations. The particle-based PDF scheme is modified to handle complex geometries and grid structures. Grid-independent particle evolution schemes that scale linearly with the problem size are implemented in the Monte-Carlo PDF solver. A novel algorithm, in situ adaptive tabulation (ISAT) is employed to ensure tractability of complex chemistry involving a multitude of species. Several non-reacting test cases are performed to ascertain the efficiency and accuracy of the method. Simulation results from a turbulent jet-diffusion flame case are compared against experimental data. The effect of micromixing model, turbulence model and reaction scheme on flame predictions are discussed extensively. Finally, the method is used to analyze the Dow Chlorination Reactor. Detailed kinetics involving 37 species and 158 reactions as well as a reduced form with 16 species and 21 reactions are used. The effect of inlet configuration on reactor behavior and product distribution is analyzed. Plant-scale reactors exhibit quenching phenomena that cannot be reproduced by conventional simulation methods. The FV-PDF method predicts quenching accurately and provides insight into the dynamics of the reactor near extinction. The accuracy of the fractional time-stepping technique in discussed in the context of apparent multiple-steady states observed in a non-premixed feed configuration of the chlorination reactor.

  12. The Effect of Variable Geochemical Conditions on the Reactive Transport of U(VI) in Small Scale Tracer Tests

    NASA Astrophysics Data System (ADS)

    Curtis, G. P.; Fox, P.; Kohler, M.; Davis, J. A.

    2005-12-01

    Small-scale tracer tests were conducted to evaluate the effect of variable geochemical conditions on the reactive transport of U(VI). The tracer tests were conducted in a shallow alluvial aquifer downgradient from a former uranium mill and a tailings disposal area near Naturita, CO. The U(VI) concentration in the groundwater at the tracer test site was approximately 5 μM, the alkalinity was 8.5 meq/L and the pH was approximately 7.1. Previous studies at the site demonstrated the U(VI) was most sensitive to the alkalinity and least sensitive to the pH values relative to the range of measured values. Uranium migration tests were conducted on a scale of 1-2.5 m and considered variable U(VI) and alkalinity and included Br as an inert tracer. The tracer tests demonstrated that the sediment readily released U(VI) even after many years of contact with the contaminated groundwater suggesting the U(VI) migration is controlled by adsorption reactions. Reactive transport simulations used a surface complexation model developed independently from laboratory bench scale studies to simulate adsorption. The reactive transport simulations gave good predictions of the observed breakthrough of U(VI) when the advection and dispersion parameters were fitted to Br breakthrough. Field studies also included several single well push-pull tests that were conducted at increased and decreased U(VI) and alkalinity values. Reactive transport simulations of these experiments will be presented and compared with the tracer tests simulations.

  13. Summary of Radionuclide Reactive Transport Experiments in Fractured Tuff and Carbonate Rocks from Yucca Flat, Nevada Test Site

    SciTech Connect

    Zavarin, M; Roberts, S; Reimus, P; Johnson, M

    2006-10-11

    In the Yucca Flat basin of the Nevada Test Site (NTS), 747 shaft and tunnel nuclear detonations were conducted primarily within the tuff confining unit (TCU) or the overlying alluvium. The TCU in the Yucca Flat basin is hypothesized to inhibit radionuclide migration to the highly transmissive and regionally extensive lower carbonate aquifer (LCA) due to its wide-spread aerial extent, low permeability, and chemical reactivity. However, fast transport pathways through the TCU by way of fractures may provide a migration path for radionuclides to the LCA. Radionuclide transport in both TCU and the LCA fractures is likely to determine the location of the contaminant boundary for the Yucca Flat/Climax Mine Corrective Action Unit (CAU). Radionuclide transport through the TCU may involve both matrix and fracture flow. However, radionuclide migration over significant distances is likely to be dominated by fracture transport. Transport through the LCA will almost certainly be dominated by fracture flow, as the LCA has a very dense, low porosity matrix with very low permeability. Because of the complex nature of reactive transport in fractures, a stepwise approach to identifying mechanisms controlling radionuclide transport was used. The simplest LLNL experiments included radionuclide transport through synthetic parallel-plate fractured tuff and carbonate cores. These simplified fracture transport experiments isolated matrix diffusion and sorption effects from all other fracture transport processes (fracture lining mineral sorption, heterogeneous flow, etc.). Additional fracture transport complexity was added by performing induced fractured LCA flowthrough experiments (effect of aperture heterogeneity) or iron oxide coated parallel plate TCU flowthrough experiments (effect of fracture lining minerals). Finally naturally fractured tuff and carbonate cores were examined at LLNL and LANL. All tuff and carbonate core used in the experiments was obtained from the USGS Core Library

  14. The importance of conceptual models in the reactive transport simulation of oxygen ingress in sparsely fractured crystalline rock.

    PubMed

    Macquarrie, K T B; Mayer, K U; Jin, B; Spiessl, S M

    2010-03-01

    Redox evolution in sparsely fractured crystalline rocks is a key, and largely unresolved, issue when assessing the geochemical suitability of deep geological repositories for nuclear waste. Redox zonation created by the influx of oxygenated waters has previously been simulated using reactive transport models that have incorporated a variety of processes, resulting in predictions for the depth of oxygen penetration that may vary greatly. An assessment and direct comparison of the various underlying conceptual models are therefore needed. In this work a reactive transport model that considers multiple processes in an integrated manner is used to investigate the ingress of oxygen for both single fracture and fracture zone scenarios. It is shown that the depth of dissolved oxygen migration is greatly influenced by the a priori assumptions that are made in the conceptual models. For example, the ability of oxygen to access and react with minerals in the rock matrix may be of paramount importance for single fracture conceptual models. For fracture zone systems, the abundance and reactivity of minerals within the fractures and thin matrix slabs between the fractures appear to provide key controls on O(2) attenuation. The findings point to the need for improved understanding of the coupling between the key transport-reaction feedbacks to determine which conceptual models are most suitable and to provide guidance for which parameters should be targeted in field and laboratory investigations.

  15. Chemical weathering rates in deep-sea sediments: Comparison of multicomponent reactive transport models and estimates based on 234U

    NASA Astrophysics Data System (ADS)

    Maher, K.; Steefel, C. I.; Depaolo, D. J.

    2004-12-01

    Chemical weathering rates in natural systems are typically much slower than expected based on experiments and theory. There are several possible explanations. However, because it has been difficult to determine what effects in particular reduce the rates in specific settings, natural rates remain difficult to predict. Silicate-rich deep-sea sediments provide an ideal in-situ laboratory for investigating weathering rates because certain potentially important factors, such as advective transport through heterogeneous media, limitations on the availability of reactive surface area due to low porosity and/or cementation, unsaturated flow conditions, and seasonal variations in fluid flux and temperature, do not occur in this setting. Geochemical profiles from Site 984 in the North Atlantic are modeled using a multi-component reactive transport model (CRUNCH) to determine in-situ rates of plagioclase dissolution and other diagenetic processes, including sulfate reduction and anaerobic methane oxidation. Various possible processes which might contribute to slower rates in the field are considered, including the effect of mineral saturation state, secondary precipitation of clays, inhibition by dissolved aluminum, and the availability of reactive surface area. The reactive transport model includes an isotopic solid-solution formulation that tracks the isotopic composition of precipitating (calcite) and dissolving (plagioclase and calcite) phases, thus allowing the determination of plagioclase dissolution rates. The rate constants for plagioclase determined by geochemical transport modeling of major element profiles are within the same range determined from U-series calculations and suggest that natural weathering rates for this system are on the order of 10-17.5 to 10-17.7 mol/m2/sec assuming estimates of reactive surface area are correct, several orders of magnitude slower than laboratory-derived rates. The slow plagioclase rates are most likely due to the fact that

  16. Investigating Uranium Mobility Using Stable Isotope Partitioning of 238U/235U and a Reactive Transport Model

    NASA Astrophysics Data System (ADS)

    Bizjack, M.; Johnson, T. M.; Druhan, J. L.; Shiel, A. E.

    2015-12-01

    We report a numerical reactive transport model which explicitly incorporates the effectively stable isotopes of uranium (U) and the factors that influence their partitioning in bioactive systems. The model reproduces trends observed in U isotope ratios and concentration measurements from a field experiment, thereby improving interpretations of U isotope ratios as a tracer for U reactive transport. A major factor contributing to U storage and transport is its redox state, which is commonly influenced by the availability of organic carbon to support metal-reducing microbial communities. Both laboratory and field experiments have demonstrated that biogenic reduction of U(VI) fractionates the stable isotope ratio 238U/235U, producing an isotopically heavy solid U(IV) product. It has also been shown that other common reactive transport processes involving U do not fractionate isotopes to a consistently measurable level, which suggests the capacity to quantify the extent of bioreduction occurring in groundwater containing U using 238U/235U ratios. A recent study of a U bioremediation experiment at the Rifle IFRC site (Colorado, USA) applied Rayleigh distillation models to quantify U stable isotope fractionation observed during acetate amendment. The application of these simplified models were fit to the observations only by invoking a "memory-effect," or a constant source of low-concentration, unfractionated U(VI). In order to more accurately interpret the measured U isotope ratios, we present a multi-component reactive transport model using the CrunchTope software. This approach is capable of quantifying the cycling and partitioning of individual U isotopes through a realistic network of transport and reaction pathways including reduction, oxidation, and microbial growth. The model incorporates physical heterogeneity of the aquifer sediments through zones of decreased permeability, which replicate the observed bromide tracer, major ion chemistry, U concentration, and U

  17. Nonideal transport of reactive solutes in heterogeneous porous media--4, Analysis of the Cape Cod natural-gradient field experiment

    USGS Publications Warehouse

    Brusseau, Mark L.; Srivastava, Rajesh

    1999-01-01

    One of the largest field studies of reactive-solute transport is the natural-gradient experiment conducted at Cape Cod from 1985 to 1988. Major findings regarding the transport behavior of the reactive solute (lithium) were that the rate of plume displacement decreased with time (temporal increase in effective retardation), the degree of longitudinal spreading was much greater than that observed for bromide for an equivalent travel distance, and the plume was asymmetric, with maximum concentrations located near the leading edges. The objective of our work was to quantitatively analyze the transport of lithium and to attempt to identify the factor or factors that contributed significantly to its observed nonideal transport. We used a mathematical model that accounted for several transport factors, including spatially variable hydraulic conductivity and spatially variable, nonlinear, rate-limited sorption, with all parameter values obtained independently. The transport behavior observed during the first 250 days, corresponding to a transport distance of 60 m, was predicted reasonably well by the simulation that incorporated spatially variable hydraulic conductivity; nonlinear, rate-limited, spatially variable sorption; and uniform water chemistry. However, the larger degree of deceleration observed during the latter stage of the experiment (the filial 20 m) was not. The larger deceleration was successfully simulated by increasing 3-fold the mean sorption capacity of the latter portion of the transport domain. Such a change in sorption capacity is consistent with the potential impact on lithium sorption of measured changes in water chemistry (e.g.,pH increase, reduction in resident Zn)at occur in the zone through which the lithium plume traversed. The results of the analyses suggest that nonlinear sorption and variable water chemistry may have btors responsible for the nonuniform displacement of the lithium plume, with rate-limited sorption/desorption having minimal

  18. Direct coupling of a genome-scale microbial in silico model and a groundwater reactive transport model

    NASA Astrophysics Data System (ADS)

    Fang, Yilin; Scheibe, Timothy D.; Mahadevan, Radhakrishnan; Garg, Srinath; Long, Philip E.; Lovley, Derek R.

    2011-03-01

    The activity of microorganisms often plays an important role in dynamic natural attenuation or engineered bioremediation of subsurface contaminants, such as chlorinated solvents, metals, and radionuclides. To evaluate and/or design bioremediated systems, quantitative reactive transport models are needed. State-of-the-art reactive transport models often ignore the microbial effects or simulate the microbial effects with static growth yield and constant reaction rate parameters over simulated conditions, while in reality microorganisms can dynamically modify their functionality (such as utilization of alternative respiratory pathways) in response to spatial and temporal variations in environmental conditions. Constraint-based genome-scale microbial in silico models, using genomic data and multiple-pathway reaction networks, have been shown to be able to simulate transient metabolism of some well studied microorganisms and identify growth rate, substrate uptake rates, and byproduct rates under different growth conditions. These rates can be identified and used to replace specific microbially-mediated reaction rates in a reactive transport model using local geochemical conditions as constraints. We previously demonstrated the potential utility of integrating a constraint-based microbial metabolism model with a reactive transport simulator as applied to bioremediation of uranium in groundwater. However, that work relied on an indirect coupling approach that was effective for initial demonstration but may not be extensible to more complex problems that are of significant interest (e.g., communities of microbial species and multiple constraining variables). Here, we extend that work by presenting and demonstrating a method of directly integrating a reactive transport model (FORTRAN code) with constraint-based in silico models solved with IBM ILOG CPLEX linear optimizer base system (C library). The models were integrated with BABEL, a language interoperability tool. The

  19. Direct coupling of a genome-scale microbial in silico model and a groundwater reactive transport model

    SciTech Connect

    Fang, Yilin; Scheibe, Timothy D.; Mahadevan, Radhakrishnan; Garg, Srinath; Long, Philip E.; Lovley, Derek R.

    2011-02-28

    The activity of microorganisms often plays an important role in dynamic natural attenuation or engineered bioremediation of subsurface contaminants, such as chlorinated solvents, metals, and radionuclides. To evaluate and/or design bioremediated systems, quantitative reactive transport models are needed. State-of-the-art reactive transport models often ignore the microbial effects or simulate the microbial effects with static growth yield and constant reaction rate parameters over simulated conditions, while in reality microorganisms can dynamically modify their functionality (such as utilization of alternative respiratory pathways) in response to spatial and temporal variations in environmental conditions. Constraint-based genome-scale microbial in silico models, using genomic data and multiple-pathway reaction networks, have been shown to be able to simulate transient metabolism of some well studied microorganisms and identify growth rate, substrate uptake rates, and byproduct rates under different growth conditions. These rates can be identified and used to replace specific microbially-mediated reaction rates in a reactive transport model using local geochemical conditions as constraints. We previously demonstrated the potential utility of integrating a constraint based microbial metabolism model with a reactive transport simulator as applied to bioremediation of uranium in groundwater. However, that work relied on an indirect coupling approach that was effective for initial demonstration but may not be extensible to more complex problems that are of significant interest (e.g., communities of microbial species, multiple constraining variables). Here, we extend that work by presenting and demonstrating a method of directly integrating a reactive transport model (FORTRAN code) with constraint-based in silico models solved with IBM ILOG CPLEX linear optimizer base system (C library). The models were integrated with BABEL, a language interoperability tool. The

  20. Reactive Transport Modeling of Cap Rock Integrity During Natural and Engineered CO2 Storage

    SciTech Connect

    Johnson, J W; Nitao, J J; Morris, J P

    2004-05-26

    Long-term cap rock integrity represents the single most important constraint on the long-term isolation performance of natural and engineered CO{sub 2} storage sites. CO{sub 2} influx that forms natural accumulations and CO{sub 2} injection for EOR/sequestration or saline-aquifer disposal both lead to concomitant geochemical alteration and geomechanical deformation of the cap rock, enhancing or degrading its seal integrity depending on the relative effectiveness of these interdependent processes. Using our reactive transport simulator (NUFT), supporting geochemical databases and software (GEMBOCHS, SUPCRT92), and distinct-element geomechanical model (LDEC), we have shown that influx-triggered mineral dissolution/precipitation reactions within typical shale cap rocks continuously reduce microfracture apertures, while pressure and effective-stress evolution first rapidly increase then slowly constrict them. For a given shale composition, the extent of geochemical enhancement is nearly independent of key reservoir properties (permeability and lateral continuity) that distinguish EOR/sequestration and saline-aquifer settings and CO{sub 2} influx parameters (rate, focality, and duration) that distinguish engineered disposal sites and natural accumulations, because these characteristics and parameters have negligible (indirect) impact on mineral dissolution/precipitation rates. In contrast, the extent of geomechanical degradation is highly dependent on these reservoir properties and influx parameters because they effectively dictate magnitude of the pressure perturbation; specifically, initial geomechanical degradation has been shown inversely proportional to reservoir permeability and lateral continuity and proportional to influx rate. Hence, while the extent of geochemical alteration is nearly independent of filling mode, that of geomechanical deformation is significantly more pronounced during engineered injection. This distinction limits the extent to which naturally

  1. Incorporating Geochemical And Microbial Kinetics In Reactive Transport Models For Generation Of Acid Rock Drainage

    NASA Astrophysics Data System (ADS)

    Andre, B. J.; Rajaram, H.; Silverstein, J.

    2010-12-01

    Acid mine drainage, AMD, results from the oxidation of metal sulfide minerals (e.g. pyrite), producing ferrous iron and sulfuric acid. Acidophilic autotrophic bacteria such as Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans obtain energy by oxidizing ferrous iron back to ferric iron, using oxygen as the electron acceptor. Most existing models of AMD do not account for microbial kinetics or iron geochemistry rigorously. Instead they assume that oxygen limitation controls pyrite oxidation and thus focus on oxygen transport. These models have been successfully used for simulating conditions where oxygen availability is a limiting factor (e.g. source prevention by capping), but have not been shown to effectively model acid generation and effluent chemistry under a wider range of conditions. The key reactions, oxidation of pyrite and oxidation of ferrous iron, are both slow kinetic processes. Despite being extensively studied for the last thirty years, there is still not a consensus in the literature about the basic mechanisms, limiting factors or rate expressions for microbially enhanced oxidation of metal sulfides. An indirect leaching mechanism (chemical oxidation of pyrite by ferric iron to produce ferrous iron, with regeneration of ferric iron by microbial oxidation of ferrous iron) is used as the foundation of a conceptual model for microbially enhanced oxidation of pyrite. Using literature data, a rate expression for microbial consumption of ferrous iron is developed that accounts for oxygen, ferrous iron and pH limitation. Reaction rate expressions for oxidation of pyrite and chemical oxidation of ferrous iron are selected from the literature. A completely mixed stirred tank reactor (CSTR) model is implemented coupling the kinetic rate expressions, speciation calculations and flow. The model simulates generation of AMD and effluent chemistry that qualitatively agrees with column reactor and single rock experiments. A one dimensional reaction

  2. Using a Mechanistic Reactive Transport Model to Represent Soil Organic Matter Dynamics and Climate Sensitivity

    NASA Astrophysics Data System (ADS)

    Guerry, N.; Riley, W. J.; Maggi, F.; Torn, M. S.; Kleber, M.

    2011-12-01

    The nature of long term Soil Organic Matter (SOM) dynamics is uncertain and the mechanisms involved are crudely represented in site, regional, and global models. Recent work challenging the paradigm that SOM is stabilized because of its sequential transformations to more intrinsically recalcitrant compounds motivated us to develop a mechanistic modeling framework that can be used to test hypotheses of SOM dynamics. We developed our C cycling model in TOUGHREACT, an established 3-dimensional reactive transport solver that accounts for multiple phases (aqueous, gaseous, sorbed), multiple species, advection and diffusion, and multiple microbial populations. Energy and mass exchange through the soil boundaries are accounted for via ground heat flux, rainfall, C sources (e.g., exudation, woody, leaf, root litter) and C losses (e.g., CO2 emissions and DOC deep percolation). SOM is categorized according to the various types of compounds commonly found in the above mentioned C sources and microbial byproducts, including poly- and monosaccharides, lignin, amino compounds, organic acids, nucleic acids, lipids, and phenols. Each of these compounds is accounted for by one or more representative species in the model. A reaction network was developed to describe the microbially-mediated processes and chemical interactions of these species, including depolymerization, microbial assimilation, respiration and deposition of byproducts, and incorporation of dead biomass into SOM stocks. Enzymatic reactions are characterized by Michaelis-Menten kinetics, with maximum reaction rates determined by the species' O/C ratio. Microbial activity is further regulated by soil moisture content, O2 availability, pH, and temperature. For the initial set of simulations, literature values were used to constrain microbial Monod parameters, Michaelis-Menten parameters, sorption parameters, physical protection, partitioning of microbial byproducts, and partitioning of litter inputs, although there is

  3. Modeling Np and Pu transport with a surface complexation model and spatially variant sorption capacities: Implications for reactive transport modeling and performance assessments of nuclear waste disposal sites

    USGS Publications Warehouse

    Glynn, P.D.

    2003-01-01

    One-dimensional (1D) geochemical transport modeling is used to demonstrate the effects of speciation and sorption reactions on the ground-water transport of Np and Pu, two redox-sensitive elements. Earlier 1D simulations (Reardon, 1981) considered the kinetically limited dissolution of calcite and its effect on ion-exchange reactions (involving 90Sr, Ca, Na, Mg and K), and documented the spatial variation of a 90Sr partition coefficient under both transient and steady-state chemical conditions. In contrast, the simulations presented here assume local equilibrium for all reactions, and consider sorption on constant potential, rather than constant charge, surfaces. Reardon's (1981) seminal findings on the spatial and temporal variability of partitioning (of 90Sr) are reexamined and found partially caused by his assumption of a kinetically limited reaction. In the present work, sorption is assumed the predominant retardation process controlling Pu and Np transport, and is simulated using a diffuse-double-layer-surface-complexation (DDLSC) model. Transport simulations consider the infiltration of Np- and Pu-contaminated waters into an initially uncontaminated environment, followed by the cleanup of the resultant contamination with uncontaminated water. Simulations are conducted using different spatial distributions of sorption capacities (with the same total potential sorption capacity, but with different variances and spatial correlation structures). Results obtained differ markedly from those that would be obtained in transport simulations using constant Kd, Langmuir or Freundlich sorption models. When possible, simulation results (breakthrough curves) are fitted to a constant K d advection-dispersion transport model and compared. Functional differences often are great enough that they prevent a meaningful fit of the simulation results with a constant K d (or even a Langmuir or Freundlich) model, even in the case of Np, a weakly sorbed radionuclide under the

  4. Reactive transport modeling of stable carbon isotope fractionation in a multi-phase multi-component system during carbon sequestration

    SciTech Connect

    Zhang, Shuo; DePaolo, Donald J.; Zheng, Liange; Mayer, Bernhard

    2014-12-31

    Carbon stable isotopes can be used in characterization and monitoring of CO2 sequestration sites to track the migration of the CO2 plume and identify leakage sources, and to evaluate the chemical reactions that take place in the CO2-water-rock system. However, there are few tools available to incorporate stable isotope information into flow and transport codes used for CO2 sequestration problems. We present a numerical tool for modeling the transport of stable carbon isotopes in multiphase reactive systems relevant to geologic carbon sequestration. The code is an extension of the reactive transport code TOUGHREACT. The transport module of TOUGHREACT was modified to include separate isotopic species of CO2 gas and dissolved inorganic carbon (CO2, CO32-, HCO3-,…). Any process of transport or reaction influencing a given carbon species also influences its isotopic ratio. Isotopic fractionation is thus fully integrated within the dynamic system. The chemical module and database have been expanded to include isotopic exchange and fractionation between the carbon species in both gas and aqueous phases. The performance of the code is verified by modeling ideal systems and comparing with theoretical results. Efforts are also made to fit field data from the Pembina CO2 injection project in Canada. We show that the exchange of carbon isotopes between dissolved and gaseous carbon species combined with fluid flow and transport, produce isotopic effects that are significantly different from simple two-component mixing. These effects are important for understanding the isotopic variations observed in field demonstrations.

  5. Reactive transport modeling of stable carbon isotope fractionation in a multi-phase multi-component system during carbon sequestration

    DOE PAGES

    Zhang, Shuo; DePaolo, Donald J.; Zheng, Liange; ...

    2014-12-31

    Carbon stable isotopes can be used in characterization and monitoring of CO2 sequestration sites to track the migration of the CO2 plume and identify leakage sources, and to evaluate the chemical reactions that take place in the CO2-water-rock system. However, there are few tools available to incorporate stable isotope information into flow and transport codes used for CO2 sequestration problems. We present a numerical tool for modeling the transport of stable carbon isotopes in multiphase reactive systems relevant to geologic carbon sequestration. The code is an extension of the reactive transport code TOUGHREACT. The transport module of TOUGHREACT was modifiedmore » to include separate isotopic species of CO2 gas and dissolved inorganic carbon (CO2, CO32-, HCO3-,…). Any process of transport or reaction influencing a given carbon species also influences its isotopic ratio. Isotopic fractionation is thus fully integrated within the dynamic system. The chemical module and database have been expanded to include isotopic exchange and fractionation between the carbon species in both gas and aqueous phases. The performance of the code is verified by modeling ideal systems and comparing with theoretical results. Efforts are also made to fit field data from the Pembina CO2 injection project in Canada. We show that the exchange of carbon isotopes between dissolved and gaseous carbon species combined with fluid flow and transport, produce isotopic effects that are significantly different from simple two-component mixing. These effects are important for understanding the isotopic variations observed in field demonstrations.« less

  6. Reactive transport in porous media for CO2 sequestration: Pore scale modeling using the lattice Boltzmann method

    NASA Astrophysics Data System (ADS)

    Gao, Jinfang; Xing, Huilin; Tian, Zhiwei; Pearce, Julie K.; Sedek, Mohamed; Golding, Suzanne D.; Rudolph, Victor

    2017-01-01

    Injection of CO2 subsurface may lead to chemical reactivity of rock where CO2 is dissolved in groundwater. This process can modify pore networks to increase or decrease porosity through mineral dissolution and precipitation. A lattice Boltzmann (LB) based computational model study on the pore scale reactive transport in three dimensional heterogeneous porous media (sandstone consisting of both reactive and non-reactive minerals) is described. This study examines how fluid transport in porous materials subject to reactive conditions is affected by unsteady state local reactions and unstable dissolution fronts. The reaction of a calcite cemented core sub-plug from the Hutton Sandstone of the Surat Basin, Australia, is used as a study case. In particular, the work studies the interaction of acidic fluid (an aqueous solution with an elevated concentration of carbonic acid) with reactive (e.g. calcite) and assumed non-reactive (e.g. quartz) mineral surfaces, mineral dissolution and mass transfer, and resultant porosity change. The proposed model is implemented in our custom LBM code and suitable for studies of multiple mineral reactions with disparate reaction rates. A model for carbonic acid reaction with calcite cemented sandstone in the CO2-water-rock system is verified through laboratory experimental data including micro-CT characterization before and after core reaction at reservoir conditions. The experimentally validated model shows: (1) the dissolution of calcite cement forms conductive channels at the pore scale, and enables the generation of pore throats and connectivity; (2) the model is able to simulate the reaction process until the reaction equilibrium status is achieved (around 1440 days); (3) calcite constituting a volume of around 9.6% of the whole core volume is dissolved and porosity is consequently increased from 1.1% to 10.7% on reaching equilibrium; (4) more than a third of the calcite (constituting 7.4% of the total core volume) is unaffected

  7. Investigation of Uranium Transport Utilizing Experimental Data and Reactive Numerical Modeling from a Heterogeneous Three-Dimensional Tank

    NASA Astrophysics Data System (ADS)

    Rodriguez, D.; Miller, A. W.; Honeyman, B.

    2009-12-01

    The study of the transport of contaminants in groundwater is required in order to reduce the associated risks to downstream receptors from sites where past releases of these contaminants has resulted in the degradation of the water quality of the underlying aquifer. The fate and transport of these contaminants usually occurs in a physically and chemically heterogeneous environment; thereby making the understanding of the ultimate fate of these contaminants difficult in a field setting. In order to better understand the fundamental processes that have the greatest effect on the transport of these contaminants, careful laboratory study must be completed in a controlled environment. An experiment was conducted in a three-dimensional tank (2.44 m x 0.61 m x 0.61 m) to generate data to quantify the processes of uranium transport in fully saturated conditions. The tank was designed so that liquid samples could be collected from 46 wells at varying depths across the length of the tank. Samples were also collected from the effluent end of the tank. The tank was packed into 500 cells, which contained varying percentages of the five fractions separated out from a <2mm fraction of a composite field material collected from the Naturita Uranium Mill Tailings Remedial Action site. The fractions included the following classes: 4 to 12 mm, < 2 mm composite, > 0.25 micron, < 0.25 micron and 125 to 250 micron. Various physical and chemical parameters were measured in the tank. A bromide tracer test was also conducted in the tank. This work presents the results from this tank study from a reactive transport perspective and also provides a discussion on the complexities that arise when conducting a large-scale experiment utilizing field materials in a laboratory. The uranium outflow and distribution within the tank were found to vary with the orientation of the macroscopic physical heterogeneities as well as local chemical characteristics. Correlations were found between calcium and

  8. Developing Sediment Transport and Dredging Prediction Model of Ohio River at Olmsted Locks and Dams Area using HEC-RAS (1D/2D)By Ganesh Raj Ghimire1 and Bruce A. Devantier 2

    NASA Astrophysics Data System (ADS)

    Ghimire, G. R.

    2015-12-01

    Sediment deposition is a serious issue in the construction and operation of large reservoir and inland navigation projects in the United States and around the world. Olmsted Locks and Dams in the Ohio River navigation system is facing similar challenges of huge sediment deposition during the ongoing in-wet construction methodology since 1993. HEC-RAS 5.0 integrated with ArcGIS, will be used to yield unsteady 2D hydrodynamic model of Ohio River at Olmsted area. Velocity, suspended sediment, bed sediment and hydrographic survey data acquired from public archives of USGS and USACE Louisville District will be input into the model. Calibration and validation of model will be performed against the measured stage, flow and velocity data. It will be subjected to completely unsteady 1D sediment transport modeling new to HEC-RAS 5.0 which incorporates sediment load and bed gradation via a DSS file, commercial dredging and BSTEM model. Sediment model will be calibrated to replicate the historical bed volume changes. Excavated cross-sections at Olmsted area will also be used to predict the sediment volume trapped inside the ditch over the period between excavations and placement of dam shells at site. Model will attempt to replicate historical dredging volume data and compare with the deposition volume from simulation model to formulate the dredging prediction model. Hence, the results of this research will generate a model that can form a basis for scheduling the dredging event prior to the placement of off-shore cast shells replacing the current as and when required approach of dredging plan. 1 Graduate Student, Department of Civil Engineering, Southern Illinois University Carbondale Carbondale, Illinois, 62901-6603 2 Professor, Department of Civil Engineering, Southern Illinois University Carbondale Carbondale, Illinois, 62901-6603

  9. Fringe-controlled biodegradation under dynamic conditions: quasi 2-D flow-through experiments and reactive-transport modeling.

    PubMed

    Eckert, Dominik; Kürzinger, Petra; Bauer, Robert; Griebler, Christian; Cirpka, Olaf A

    2015-01-01

    Biodegradation in contaminated aquifers has been shown to be most pronounced at the fringe of contaminant plumes, where mixing of contaminated water and ambient groundwater, containing dissolved electron acceptors, stimulates microbial activity. While physical mixing of contaminant and electron acceptor by transverse dispersion has been shown to be the major bottleneck for biodegradation in steady-state plumes, so far little is known on the effect of flow and transport dynamics (caused, e.g., by a seasonally fluctuating groundwater table) on biodegradation in these systems. Towards this end we performed experiments in quasi-two-dimensional flow-through microcosms on aerobic toluene degradation by Pseudomonas putida F1. Plume dynamics were simulated by vertical alteration of the toluene plume position and experimental results were analyzed by reactive-transport modeling. We found that, even after disappearance of the toluene plume for two weeks, the majority of microorganisms stayed attached to the sediment and regained their full biodegradation potential within two days after reappearance of the toluene plume. Our results underline that besides microbial growth, also maintenance and dormancy are important processes that affect biodegradation performance under transient environmental conditions and therefore deserve increased consideration in future reactive-transport modeling.

  10. Development of Modeling Methods and Tools for Predicting Coupled Reactive Transport Processes in Porous Media at Multiple Scales

    SciTech Connect

    Clement, T Prabhakar; Barnett, Mark O; Zheng, Chunmiao; Jones, Norman L

    2010-05-05

    DE-FG02-06ER64213: Development of Modeling Methods and Tools for Predicting Coupled Reactive Transport Processes in Porous Media at Multiple Scales Investigators: T. Prabhakar Clement (PD/PI) and Mark O. Barnett (Auburn), Chunmiao Zheng (Univ. of Alabama), and Norman L. Jones (BYU). The objective of this project was to develop scalable modeling approaches for predicting the reactive transport of metal contaminants. We studied two contaminants, a radioactive cation [U(VI)] and a metal(loid) oxyanion system [As(III/V)], and investigated their interactions with two types of subsurface materials, iron and manganese oxyhydroxides. We also developed modeling methods for describing the experimental results. Overall, the project supported 25 researchers at three universities. Produced 15 journal articles, 3 book chapters, 6 PhD dissertations and 6 MS theses. Three key journal articles are: 1) Jeppu et al., A scalable surface complexation modeling framework for predicting arsenate adsorption on goethite-coated sands, Environ. Eng. Sci., 27(2): 147-158, 2010. 2) Loganathan et al., Scaling of adsorption reactions: U(VI) experiments and modeling, Applied Geochemistry, 24 (11), 2051-2060, 2009. 3) Phillippi, et al., Theoretical solid/solution ratio effects on adsorption and transport: uranium (VI) and carbonate, Soil Sci. Soci. of America, 71:329-335, 2007

  11. Quinone-reactive proteins devoid of haem b form widespread membrane-bound electron transport modules in bacterial respiration.

    PubMed

    Simon, Jörg; Kern, Melanie

    2008-10-01

    Many quinone-reactive enzyme complexes that are part of membrane-integral eukaryotic or prokaryotic respiratory electron transport chains contain one or more haem b molecules embedded in the membrane. In recent years, various novel proteins have emerged that are devoid of haem b but are thought to fulfil a similar function in bacterial anaerobic respiratory systems. These proteins are encoded by genes organized in various genomic arrangements and are thought to form widespread membrane-bound quinone-reactive electron transport modules that exchange electrons with redox partner proteins located at the outer side of the cytoplasmic membrane. Prototypic representatives are the multihaem c-type cytochromes NapC, NrfH and TorC (NapC/NrfH family), the putative iron-sulfur protein NapH and representatives of the NrfD/PsrC family. Members of these protein families vary in the number of their predicted transmembrane segments and, consequently, diverse quinone-binding sites are expected. Only a few of these enzymes have been isolated and characterized biochemically and high-resolution structures are limited. This mini-review briefly summarizes predicted and experimentally demonstrated properties of the proteins in question and discusses their role in electron transport and bioenergetics of anaerobic respiration.

  12. Coupling a genome‐scale metabolic model with a reactive transport model to describe in situ uranium bioremediation

    PubMed Central

    Scheibe, Timothy D.; Mahadevan, Radhakrishnan; Fang, Yilin; Garg, Srinath; Long, Philip E.; Lovley, Derek R.

    2009-01-01

    Summary The increasing availability of the genome sequences of microorganisms involved in important bioremediation processes makes it feasible to consider developing genome‐scale models that can aid in predicting the likely outcome of potential subsurface bioremediation strategies. Previous studies of the in situ bioremediation of uranium‐contaminated groundwater have demonstrated that Geobacter species are often the dominant members of the groundwater community during active bioremediation and the primary organisms catalysing U(VI) reduction. Therefore, a genome‐scale, constraint‐based model of the metabolism of Geobacter sulfurreducens was coupled with the reactive transport model HYDROGEOCHEM in an attempt to model in situ uranium bioremediation. In order to simplify the modelling, the influence of only three growth factors was considered: acetate, the electron donor added to stimulate U(VI) reduction; Fe(III), the electron acceptor primarily supporting growth of Geobacter; and ammonium, a key nutrient. The constraint‐based model predicted that growth yields of Geobacter varied significantly based on the availability of these three growth factors and that there are minimum thresholds of acetate and Fe(III) below which growth and activity are not possible. This contrasts with typical, empirical microbial models that assume fixed growth yields and the possibility for complete metabolism of the substrates. The coupled genome‐scale and reactive transport model predicted acetate concentrations and U(VI) reduction rates in a field trial of in situ uranium bioremediation that were comparable to the predictions of a calibrated conventional model, but without the need for empirical calibration, other than specifying the initial biomass of Geobacter. These results suggest that coupling genome‐scale metabolic models with reactive transport models may be a good approach to developing models that can be truly predictive, without empirical calibration, for

  13. Analyzing the impact of reactive transport on the repository performance of TRISO fuel

    NASA Astrophysics Data System (ADS)

    Schmidt, Gregory

    graphite surrounding the spent HTGR fuel will impact the release of aqueous uranium from the TRISO fuel. In order to answer this question, the sorption and partitioning behavior of uranium to graphite under a variety of conditions was investigated. Key systematic variables that were analyzed include solution pH, dissolved carbonate concentration, uranium metal concentration and ionic strength. The kinetics and desorption characteristics of uranium/graphite partitioning were studied as well. The graphite used in these experiments was also characterized by a variety of techniques and conclusions are drawn about the relevant surface chemistry of graphite. This data was then used to generate a model for the reactive transport of uranium in a graphite matrix. This model was implemented with the software code CXTFIT and validated through the use of column studies mirroring the predicted system.

  14. Dynamic Pore-Scale Imaging of Reactive Transport in Heterogeneous Carbonates at Reservior Conditions

    NASA Astrophysics Data System (ADS)

    Menke, Hannah; Bijeljic, Branko; Andrew, Matthew; Blunt, Martin

    2014-05-01

    minor dissolution rate differences between the pores and pore throats. This was not true for the heterogeneous carbonates, Estalliades and Portland Basebed, which formed wormholes. Pore-scale modelling of flow directly on the voxels showed the differences in the evolution of complex flow fields with changes in dissolution regime. The PDFs of normalized velocity for uniform dissolution showed that the maximum pore velocity within the system decreased as dissolution occurred. This is due to dissolution enlarging pores and pore throats. However, in the wormholing regime, there was a large increase in maximum velocity once the wormhole broke through the length of the core and a preferential flow path was created. Additionally, this study serves as a unique benchmark for pore-scale reactive transport modelling directly on the binarized Micro-CT images. This dynamic pore-scale imaging method offers advantages in helping fully explain the dominant physical and chemical processes at the pore scale so that they may be up-scaled to the reservoir scale for increased accuracy in model prediction.

  15. Study of Uranium Transport Utilizing Reactive Numerical Modeling and Experimental Data from Heterogeneous Intermediate-Scale Tanks

    NASA Astrophysics Data System (ADS)

    Rodriguez, D.; Miller, A.; Honeyman, B.

    2007-12-01

    The study of the transport of contaminants in groundwater is critical in order to mitigate risks to downstream receptors from sites where past releases of these contaminants has resulted in the degradation of the water quality of the underlying aquifer. In most cases, the fate and transport of these contaminants occurs in a chemically and physically heterogeneous environment; thereby making the prediction of the ultimate fate of these contaminants difficult. In order to better understand the fundamental processes that have the greatest effect on the transport of these contaminants, careful laboratory study must be completed in a controlled environment. Once the experimental data has been generated, the validation of numerical models may then be achieved. Questions on the management of contaminated sites may center on the long-term release (e.g., desorption, dissolution) behavior of contaminated geomedia. Data on the release of contaminants is often derived from bench-scale experiments or, in rare cases, through field-scale experiments. A central question, however, is how molecular-scale processes (e.g., bond breaking) are expressed at the macroscale. This presentation describes part of a collaborative study between the Colorado School of Mines, the USGS and Lawrence Berkeley National Lab on upscaling pore-scale processes to understanding field-scale observations. In the work described here, two experiments were conducted in two intermediate-scale tanks (2.44 m x 1.22 m x 7.6 cm and 2.44 m x 0.61 m x 7.6 cm) to generate data to quantify the processes of uranium dissolution and transport in fully saturated conditions, and to evaluate the ability of two reactive transport models to capture the relevant processes and predict U behavior at the intermediate scale. Each tank was designed so that spatial samples could be collected from the side of the tank, as well as samples from the effluent end of the tank. The larger tank was packed with a less than 2mm fraction of a

  16. Multi-component reactive transport modeling of natural attenuation of an acid groundwater plume at a uranium mill tailings site

    NASA Astrophysics Data System (ADS)

    Zhu, Chen; Hu, Fang Q.; Burden, David S.

    2001-11-01

    Natural attenuation of an acidic plume in the aquifer underneath a uranium mill tailings pond in Wyoming, USA was simulated using the multi-component reactive transport code PHREEQC. A one-dimensional model was constructed for the site and the model included advective-dispersive transport, aqueous speciation of 11 components, and precipitation-dissolution of six minerals. Transport simulation was performed for a reclamation scenario in which the source of acidic seepage will be terminated after 5 years and the plume will then be flushed by uncontaminated upgradient groundwater. Simulations show that successive pH buffer reactions with calcite, Al(OH) 3(a), and Fe(OH) 3(a) create distinct geochemical zones and most reactions occur at the boundaries of geochemical zones. The complex interplay of physical transport processes and chemical reactions produce multiple concentration waves. For SO 42- transport, the concentration waves are related to advection-dispersion, and gypsum precipitation and dissolution. Wave speeds from numerical simulations compare well to an analytical solution for wave propagation.

  17. Multi-component reactive transport modeling of natural attenuation of an acid groundwater plume at a uranium mill tailings site.

    PubMed

    Zhu, C; Hu, F Q; Burden, D S

    2001-11-01

    Natural attenuation of an acidic plume in the aquifer underneath a uranium mill tailings pond in Wyoming, USA was simulated using the multi-component reactive transport code PHREEQC. A one-dimensional model was constructed for the site and the model included advective-dispersive transport, aqueous speciation of 11 components, and precipitation-dissolution of six minerals. Transport simulation was performed for a reclamation scenario in which the source of acidic seepage will be terminated after 5 years and the plume will then be flushed by uncontaminated upgradient groundwater. Simulations show that successive pH buffer reactions with calcite, Al(OH)3(a), and Fe(OH)3(a) create distinct geochemical zones and most reactions occur at the boundaries of geochemical zones. The complex interplay of physical transport processes and chemical reactions produce multiple concentration waves. For SO4(2-) transport, the concentration waves are related to advection-dispersion, and gypsum precipitation and dissolution. Wave speeds from numerical simulations compare well to an analytical solution for wave propagation.

  18. Numerical methods for improving sensitivity analysis and parameter estimation of virus transport simulated using sorptive-reactive processes

    USGS Publications Warehouse

    Barth, G.; Hill, M.C.

    2005-01-01

    Using one- and two-dimensional homogeneous simulations, this paper addresses challenges associated with sensitivity analysis and parameter estimation for virus transport simulated using sorptive-reactive processes. Head, flow, and conservative- and virus-transport observations are considered. The paper examines the use of (1) observed-value weighting, (2) breakthrough-curve temporal moment observations, and (3) the significance of changes in the transport time-step size. The results suggest that (1) sensitivities using observed-value weighting are more susceptible to numerical solution variability, (2) temporal moments of the breakthrough curve are a more robust measure of sensitivity than individual conservative-transport observations, and (3) the transport-simulation time step size is more important than the inactivation rate in solution and about as important as at least two other parameters, reflecting the ease with which results can be influenced by numerical issues. The approach presented allows more accurate evaluation of the information provided by observations for estimation of parameters and generally improves the potential for reasonable parameter-estimation results. ?? 2004 Elsevier B.V. All rights reserved.

  19. Uranium and strontium fate in waste-weathered sediments: Scaling of molecular processes to predict reactive transport

    SciTech Connect

    Chorover, Jon; Mueller, Karl; O'Day, Peggy; Steefel, Carl; Um, Wooyong; Zachara, John; Perdrial, Nico; Kanematsu, Msakazu; Reinoso-Maset, Estela; Poweleit, Eric; Vazquez-Ortega, Angelica; Wang, Guohui

    2016-04-02

    Objectives of the project: 1. Determine the process coupling that occurs between mineral transformation and contaminant (U and Sr) speciation in acid-uranium waste weathered Hanford sediments. 2. Establish linkages between molecular-scale contaminant speciation and meso-scale contaminant lability, release and reactive transport. 3. Make conjunctive use of molecular- to bench-scale data to constrain the development of a mechanistic, reactive transport model that includes coupling of contaminant sorption-desorption and mineral transformation reactions. Hypotheses tested: - Uranium and strontium speciation in legacy sediments from the U-8 and U-12 Crib sites can be reproduced in bench-scale weathering experiments conducted on unimpacted Hanford sediments from the same formations. - Reactive transport modeling of future uranium and strontium releases from the vadose zone of acid-waste weathered sediments can be effectively constrained by combining molecular-scale information on contaminant bonding environment with grain-scale information on contaminant phase partitioning, and meso-scale kinetic data on contaminant release from the waste-weathered porous media. - Although field contamination and laboratory experiments differ in their diagenetic time scales (decades for field vs. months to years for lab), sediment dissolution, neophase nucleation, and crystal growth reactions that occur during the initial disequilibrium induced by waste-sediment interaction leave a strong imprint that persists over subsequent longer-term equilibration time scales and, therefore, give rise to long-term memory effects. Enabling capabilities developed: Our team developed an iterative measure-model approach that is broadly applicable to elucidate the mechanistic underpinnings of reactive contaminant transport in geomedia subject to active weathering. Experimental design: Hypotheses were tested by comparing (with a similar set of techniques) the geochemical transformations and transport

  20. The mineral dissolution rate conundrum: Insights from reactive transport modeling of U isotopes and pore fluid chemistry in marine sediments

    NASA Astrophysics Data System (ADS)

    Maher, Kate; Steefel, Carl I.; DePaolo, Donald J.; Viani, Brian E.

    2006-01-01

    Pore water chemistry and 234U/ 238U activity ratios from fine-grained sediment cored by the Ocean Drilling Project at Site 984 in the North Atlantic were used as constraints in modeling in situ rates of plagioclase dissolution with the multicomponent reactive transport code Crunch. The reactive transport model includes a solid-solution formulation to enable the use of the 234U/ 238U activity ratios in the solid and fluid as a tracer of mineral dissolution. The isotopic profiles are combined with profiles of the major element chemistry (especially alkalinity and calcium) to determine whether the apparent discrepancy between laboratory and field dissolution rates still exists when a mechanistic reactive transport model is used to interpret rates in a natural system. A suite of reactions, including sulfate reduction and methane production, anaerobic methane oxidation, CaCO 3 precipitation, dissolution of plagioclase, and precipitation of secondary clay minerals, along with diffusive transport and fluid and solid burial, control the pore fluid chemistry in Site 984 sediments. The surface area of plagioclase in intimate contact with the pore fluid is estimated to be 6.9 m 2/g based on both grain geometry and on the depletion of 234U/ 238U in the sediment via α-recoil loss. Various rate laws for plagioclase dissolution are considered in the modeling, including those based on (1) a linear transition state theory (TST) model, (2) a nonlinear dependence on the undersaturation of the pore water with respect to plagioclase, and (3) the effect of inhibition by dissolved aluminum. The major element and isotopic methods predict similar dissolution rate constants if additional lowering of the pore water 234U/ 238U activity ratio is attributed to isotopic exchange via recrystallization of marine calcite, which makes up about 10-20% of the Site 984 sediment. The calculated dissolution rate for plagioclase corresponds to a rate constant that is about 10 2 to 10 5 times smaller than

  1. Final Project Report: Release of aged contaminants from weathered sediments: Effects of sorbate speciation on scaling of reactive transport

    SciTech Connect

    Jon Chorover, University of Arizona; Peggy O'€™Day, University of California, Merced; Karl Mueller, Penn State University; Wooyong Um, Pacific Northwest National Laboratory; Carl Steefel, Lawrence Berkeley National Laboratory

    2012-10-01

    Hanford sediments impacted by hyperalkaline high level radioactive waste have undergone incongruent silicate mineral weathering concurrent with contaminant uptake. In this project, we studied the impact of background pore water (BPW) on strontium, cesium and iodine desorption and transport in Hanford sediments that were experimentally weathered by contact with simulated hyperalkaline tank waste leachate (STWL) solutions. Using those lab-weathered Hanford sediments (HS) and model precipitates formed during nucleation from homogeneous STWL solutions (HN), we (i) provided detailed characterization of reaction products over a matrix of field-relevant gradients in contaminant concentration, PCO2, and reaction time; (ii) improved molecular-scale understanding of how sorbate speciation controls contaminant desorption from weathered sediments upon removal of caustic sources; and (iii) developed a mechanistic, predictive model of meso- to field-scale contaminant reactive transport under these conditions.

  2. Coupling Sorption to Soil Weathering During Reactive Transport: Impacts of Mineral Transformation and Sorbate Aging on Contaminant Speciation and Mobility

    SciTech Connect

    Chorover, Jon; Mueller, Karl T.; O'Day, Peggy; Serne, R. Jeff; Um, Wooyong; Steefel, Carl

    2006-06-01

    Our work is aimed at developing a predictive-mechanistic understanding of the coupling between mineral weathering from caustic waste release and contaminant (Cs, Sr, I) fate and transport in waste-impacted sediments across space, time and geochemical gradients that encompass the process-level heterogeneity observed at the Hanford DOE site. Our specific objectives are: (1) to assess the molecular-scale mechanisms responsible for time-dependent sequestration of contaminants (Cs, Sr and I) during penetration of waste-induced weathering fronts through sedimentary media; (2) to determine the rate and extent of contaminant release from the sorbed state; (3) to develop a reactive transport model based on molecular mechanisms and macroscopic flow experiments (from (1) and (2)) that accurately simulates adsorption, aging, and desorption at the bench-scale, and that can be applied to--and validated at--field sites such as Hanford.

  3. Interaction of reactive fronts during transport in a homogeneous porous medium with initial small non-uniformity.

    PubMed

    Chen, Jui-Sheng; Liu, Chen-Wuing

    2004-08-01

    A reactive fluid circulating within a porous medium can dissolve minerals with which it is out of equilibrium and modify the porosity and permeability. The positive feedback between fluid transport and mineral dissolution causes complex reaction front morphologies such as fingers or wormholes. This study presents a numerical model to investigate reaction front instability, temporal aquifer porosity, and species concentration evolution during reactive transport in a homogeneous porous medium with two small, initially local non-uniformities. Simulation results indicate that a stable planar front develops for a small upstream pressure gradient while the growth of two non-uniformities becomes unstable for a large upstream pressure gradient. Moreover, the unstable reaction front may be either double- or single-finger in shape. Reaction front shape selection depends on the spacing of the two local non-uniformities and the upstream pressure gradients. A behavior diagram is constructed to identify a planar, single- or double-front morphology. The critical non-uniformities spacing at which a reaction front begins to merge into a single-finger decreases with increasing upstream pressure gradient.

  4. A Reactive-Transport Model Describing Methanogen Growth and Methane Production in Diffuse Flow Vents at Axial Seamount

    NASA Astrophysics Data System (ADS)

    Algar, C. K.

    2015-12-01

    Hydrogenotrophic methanogenesis is an important mode of metabolism in deep-sea hydrothermal vents. Diffuse vent fluids often show a depletion in hydrogen with a corresponding increase in methane relative to pure-mixing of end member fluid and seawater, and genomic surveys show an enrichment in genetic sequences associated with known methanogens. However, because we cannot directly sample the subseafloor habitat where these organisms are living, constraining the size and activity of these populations remains a challenge and limits our ability to quantify the role they play in vent biogeochemistry. Reactive-transport modeling may provide a useful tool for approaching this problem. Here we present a reactive-transport model describing methane production along the flow-path of hydrothermal fluid from its high temperature end-member to diffuse venting at the seafloor. The model is set up to reflect conditions at several diffuse vents in the Axial Seamount. The model describes the growth of the two dominant thermophilic methanogens, Methanothermococcus and Methanocaldococcus, observed at Axial seamount. Monod and Arrhenius constants for Methanothermococcus thermolithotrophicus and Methanocaldococcus jannaschii were obtained for the model using chemostat and bottle experiments at varying temperatures. The model is used to investigate the influence of different mixing regimes on the subseafloor populations of these methanogens. By varying the model flow path length and subseafloor cell concentrations, and fitting to observed hydrogen and methane concentrations in the venting fluid, the subseafloor biomass, fluid residence time, and methane production rate can be constrained.

  5. A versatile pore-scale multicomponent reactive transport approach based on lattice Boltzmann method: Application to portlandite dissolution

    NASA Astrophysics Data System (ADS)

    Patel, Ravi A.; Perko, Janez; Jacques, Diederik; De Schutter, Geert; Van Breugel, Klaas; Ye, Guang

    A versatile lattice Boltzmann (LB) based pore-scale multicomponent reactive transport approach is presented in this paper. This approach is intended to capture mineral phase and pore structure evolution resulting from geochemical interactions applicable, for example to model microstructural evolution of hardened cement paste during chemical degradation. In the proposed approach heterogeneous reactions are conceptualized as pseudo-homogenous (volumetric) reactions by introducing an additional source term in the fluid node located at the interface adjacent to a solid node, and not as flux boundaries as used in previously proposed approaches. This allows a complete decoupling of transport and reaction computations, thus different reaction systems can be introduced within the LB framework through coupling with external geochemical codes. A systematic framework for coupling an external geochemical code with the LB including pore geometry evolution is presented, with the generic geochemical code PHREEQC as an example. The developed approach is validated with a set of benchmarks. A first example demonstrates the ability of the developed approach to capture the influence of pH on average portlandite dissolution rate and surface evolution. This example is further extended to illustrate the influence of reactive surface area and spatial arrangement of mineral grains on average dissolution rate. It was demonstrated that both location of mineral grains and surface area play a crucial role in determining average dissolution rate and pore structure evolution.

  6. Comparative assessment of continuum-scale models of bimolecular reactive transport in porous media under pre-asymptotic conditions

    NASA Astrophysics Data System (ADS)

    Porta, G. M.; Ceriotti, G.; Thovert, J.-F.

    2016-02-01

    We compare the ability of various continuum-scale models to reproduce the key features of a transport setting associated with a bimolecular reaction taking place in the fluid phase and numerically simulated at the pore-scale level in a disordered porous medium. We start by considering a continuum-scale formulation which results from formal upscaling of this reactive transport process by means of volume averaging. The resulting (upscaled) continuum-scale system of equations includes nonlocal integro-differential terms and the effective parameters embedded in the model are quantified directly through computed pore-scale fluid velocity and pore space geometry attributes. The results obtained through this predictive model formulation are then compared against those provided by available effective continuum models which require calibration through parameter estimation. Our analysis considers two models recently proposed in the literature which are designed to embed incomplete mixing arising from the presence of fast reactions under advection-dominated transport conditions. We show that best estimates of the parameters of these two models heavily depend on the type of data employed for model calibration. Our upscaled nonlocal formulation enables us to reproduce most of the critical features observed through pore-scale simulation without any model calibration. As such, our results clearly show that embedding into a continuum-scale model the information content associated with pore-scale geometrical features and fluid velocity yields improved interpretation of typically available continuum-scale transport observations.

  7. Water transport in the nano-pore of the calcium silicate phase: reactivity, structure and dynamics.

    PubMed

    Hou, Dongshuai; Li, Zongjin; Zhao, Tiejun; Zhang, Peng

    2015-01-14

    Reactive force field molecular dynamics was utilized to simulate the reactivity, structure and dynamics of water molecules confined in calcium-silicate-hydrate (C-S-H) nano-pores of 4.5 nm width. Due to the highly reactive C-S-H surface, hydrolytic reactions occur in the solid-liquid interfacial zone, and partially surface adsorbed water molecules transforming into the Si-OH and Ca-OH groups are strongly embedded in the C-S-H structure. Due to the electronic charge difference, the silicate and calcium hydroxyl groups have binomial distributions of the dipolar moment and water orientation. While Ca-OH contributes to the Ow-downward orientation, the ONB atoms in the silicate chains prefer to accept H-bonds from the surface water molecules. Furthermore, the defective silicate chains and solvated Caw atoms near the surface contribute to the glassy nature of the surface water molecules, with large packing density, pronounced orientation preference, and distorted organization. The stable H-bonds connected with the Ca-OH and Si-OH groups also restrict the mobility of the surface water molecules. The significant reduction of the diffusion coefficient matches well with the experimental results obtained by NMR, QENS and PCFR techniques. Upon increasing the distance from the channel, the structural and dynamic behavior of the water molecules varies and gradually translates into bulk water properties at distances of 10-15 Å from the liquid-solid interface.

  8. RESEARCH ACTIVITIES AT U.S. GOVERNMENT AGENCIES IN SUBSURFACE REACTIVE TRANSPORT MODELING

    EPA Science Inventory

    The fate of contaminants in the environment is controlled by both chemical reactions and transport phenomena in the subsurface. Our ability to understand the significance of these processes over time requires an accurate conceptual model that incorporates the various mechanisms ...

  9. Reactive Solute Transport in Streams: 1. Development of an Equilibrium-Based Model

    NASA Astrophysics Data System (ADS)

    Runkel, Robert L.; Bencala, Kenneth E.; Broshears, Robert E.; Chapra, Steven C.

    1996-02-01

    An equilibrium-based solute transport model is developed for the simulation of trace metal fate and transport in streams. The model is formed by coupling a solute transport model with a chemical equilibrium submodel based on MINTEQ. The solute transport model considers the physical processes of advection, dispersion, lateral inflow, and transient storage, while the equilibrium submodel considers the speciation and complexation of aqueous species, precipitation/dissolution and sorption. Within the model, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (water-borne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach.

  10. Reactive solute transport in streams. 1. Development of an equilibrium- based model

    USGS Publications Warehouse

    Runkel, R.L.; Bencala, K.E.; Broshears, R.E.; Chapra, S.C.

    1996-01-01

    An equilibrium-based solute transport model is developed for the simulation of trace metal fate and transport in streams. The model is formed by coupling a solute transport model with a chemical equilibrium submodel based on MINTEQ. The solute transport model considers the physical processes of advection, dispersion, lateral inflow, and transient storage, while the equilibrium submodel considers the speciation and complexation of aqueous species, precipitation/dissolution and sorption. Within the model, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (water-borne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach.

  11. Reactive transport modeling to study changes in water chemistry induced by CO2 injection at the Frio-I brine pilot

    SciTech Connect

    Kharaka, Y.K; Doughty, C.; Freifeld, B.M.; Daley, T.M.; Xu, T.

    2009-11-01

    To demonstrate the potential for geologic storage of CO{sub 2} in saline aquifers, the Frio-I Brine Pilot was conducted, during which 1600 tons of CO{sub 2} were injected into a high-permeability sandstone and the resulting subsurface plume of CO{sub 2} was monitored using a variety of hydrogeological, geophysical, and geochemical techniques. Fluid samples were obtained before CO{sub 2} injection for baseline geochemical characterization, during the CO{sub 2} injection to track its breakthrough at a nearby observation well, and after injection to investigate changes in fluid composition and potential leakage into an overlying zone. Following CO{sub 2} breakthrough at the observation well, brine samples showed sharp drops in pH, pronounced increases in HCO{sub 3}{sup -} and aqueous Fe, and significant shifts in the isotopic compositions of H{sub 2}O and dissolved inorganic carbon. Based on a calibrated 1-D radial flow model, reactive transport modeling was performed for the Frio-I Brine Pilot. A simple kinetic model of Fe release from the solid to aqueous phase was developed, which can reproduce the observed increases in aqueous Fe concentration. Brine samples collected after half a year had lower Fe concentrations due to carbonate precipitation, and this trend can be also captured by our modeling. The paper provides a method for estimating potential mobile Fe inventory, and its bounding concentration in the storage formation from limited observation data. Long-term simulations show that the CO{sub 2} plume gradually spreads outward due to capillary forces, and the gas saturation gradually decreases due to its dissolution and precipitation of carbonates. The gas phase is predicted to disappear after 500 years. Elevated aqueous CO{sub 2} concentrations remain for a longer time, but eventually decrease due to carbonate precipitation. For the Frio-I Brine Pilot, all injected CO{sub 2} could ultimately be sequestered as carbonate minerals.

  12. Simulations of Carbon Dioxide Storage and Methane Production from Guest Molecule Exchange of Hydrates Using Reactive Transport Modeling and Gibbs Energy Minimization

    NASA Astrophysics Data System (ADS)

    Darnell, K.; Flemings, P. B.

    2015-12-01

    We investigate guest molecule exchange of hydrates as a method for simultaneous carbon dioxide storage and methane production. We simulate N2/CO2 binary gas mixture injection into marine and terrestrial methane hydrate bearing sediments. Different compositions of the injected gas can lead to four possible outcomes: 1) Injected gas flows downstream past methane hydrate and does not alter the methane hydrate, 2) Injected gas causes complete dissociation of methane hydrate, which creates a gas mixture of methane and injected gas that flows downstream, 3) Injected gas causes complete dissociation of methane hydrate with flow of methane gas downstream and all injected gas replaces methane in the hydrate cage, 4) Injected gas causes partial dissociation of methane hydrate with some replacement of methane in the hydrate cage and downstream flow of a methane and injected gas mixture. We focus on how composition of injected gas affects the outcome of the injection process, and then determine the optimal injection mixture of N2/CO2 for carbon dioxide storage and methane production. Our simulations combine dynamic flash calculations using the Gibbs energy minimization of Ballard and Sloan (2004) with 1-d reactive transport modeling. This work provides insight into the efficiency of the guest molecule exchange process in methane hydrate systems. Our results can be directly incorporated into simulations of more complex geometries and field settings such as the Ignik Sikumi Gas Hydrate Field Trial. ReferencesBallard, A. L., and Sloan, E. D. (2004). The next generation of hydrate prediction: Part III. Gibbs energy minimization formalism. Fluid phase equilibria, 218(1), 15-31.

  13. Reactive transport modeling to study changes in water chemistry induced by CO2 injection at the Frio-I Brine Pilot

    USGS Publications Warehouse

    Xu, T.; Kharaka, Y.K.; Doughty, C.; Freifeld, B.M.; Daley, T.M.

    2010-01-01

    To demonstrate the potential for geologic storage of CO2 in saline aquifers, the Frio-I Brine Pilot was conducted, during which 1600 tons of CO2 were injected into a high-permeability sandstone and the resulting subsurface plume of CO2 was monitored using a variety of hydrogeological, geophysical, and geochemical techniques. Fluid samples were obtained before CO2 injection for baseline geochemical characterization, during the CO2 injection to track its breakthrough at a nearby observation well, and after injection to investigate changes in fluid composition and potential leakage into an overlying zone. Following CO2 breakthrough at the observation well, brine samples showed sharp drops in pH, pronounced increases in HCO3- and aqueous Fe, and significant shifts in the isotopic compositions of H2O and dissolved inorganic carbon. Based on a calibrated 1-D radial flow model, reactive transport modeling was performed for the Frio-I Brine Pilot. A simple kinetic model of Fe release from the solid to aqueous phase was developed, which can reproduce the observed increases in aqueous Fe concentration. Brine samples collected after half a year had lower Fe concentrations due to carbonate precipitation, and this trend can be also captured by our modeling. The paper provides a method for estimating potential mobile Fe inventory, and its bounding concentration in the storage formation from limited observation data. Long-term simulations show that the CO2 plume gradually spreads outward due to capillary forces, and the gas saturation gradually decreases due to its dissolution and precipitation of carbonates. The gas phase is predicted to disappear after 500 years. Elevated aqueous CO2 concentrations remain for a longer time, but eventually decrease due to carbonate precipitation. For the Frio-I Brine Pilot, all injected CO2 could ultimately be sequestered as carbonate minerals. ?? 2010 Elsevier B.V.

  14. Reactive-transport simulation of phosphorus in the sewage plume at the Massachusetts Military Reservation, Cape Cod, Massachusetts

    USGS Publications Warehouse

    Parkhurst, David L.; Stollenwerk, Kenneth G.; Colman, John A.

    2003-01-01

    The subsurface transport of phosphorus introduced by the disposal of treated sewage effluent to ground-infiltration disposal beds at the Massachusetts Military Reservation on western Cape Cod was simulated with a three-dimensional reactive-transport model. The simulations were used to estimate the load of phosphorus transported to Ashumet Pond during operation of the sewage-treatment plant?from 1936 to 1995?and for 60 years following cessation of sewage disposal. The model accounted for spatial and temporal changes in water discharge from the sewage-treatment plant, ground-water flow, transport of associated chemical constituents, and a set of chemical reactions, including phosphorus sorption on aquifer materials, dissolution and precipitation of iron- and manganese-oxyhydroxide and iron phosphate minerals, organic carbon sorption and decomposition, cation sorption, and irreversible denitrification. The flow and transport in the aquifer were simulated by using parameters consistent with those used in previous flow models of this area of Cape Cod, except that numerical dispersion was much larger than the physical dispersion estimated in previous studies. Sorption parameters were fit to data derived from phosphorus sorption and desorption laboratory column experiments. Rates of organic carbon decomposition were adjusted to match the location of iron concentrations in an anoxic iron zone within the sewage plume. The sensitivity of the simulated load of phosphorus transported to Ashumet Pond was calculated for a variety of processes and input parameters. Model limitations included large uncertainties associated with the loading of the sewage beds, the flow system, and the chemistry and sorption characteristics in the aquifer. The results of current model simulations indicate a small load of phosphorus transported to Ashumet Pond during 1965?85, but this small load was particularly sensitive to model parameters that specify flow conditions and the chemical process by

  15. Inverse Reactive Transport Simulator (Inverts): An Inverse Model for Contaminant Transport with Nonlinear Adsorption and Source Terms

    SciTech Connect

    McGrail, B. Peter

    2001-10-31

    A numerically based simulator was developed to assist in the interpretation of complex laboratory experiments examining transport processes of chemical and biological contaminants subject to nonlinear adsorption and/or source terms. The inversion is performed with any of three nonlinear regression methods, Marquardt-Levenberg, conjugate gradient, or quasi-Newton. The governing equations for the problem are solved by the method of finite-differences including any combination of three boundary conditions: (1) Dirichlet, (2) Neumann, and (3) Cauchy. The dispersive terms in the transport equations were solved using the second-order accurate in time and space Crank-Nicolson scheme, while the advective terms were handled using a third-order in time and space, total variation diminishing (TVD) scheme that damps spurious oscillations around sharp concentration fronts. The numerical algorithms were implemented in the computer code INVERTS, which runs on any standard personal computer. Apart from a comprehensive set of test problems, INVERTS was also used to model the elution of a nonradioactive tracer, {sup 185}Re, in a pressurized unsaturated flow (PUF) experiment with a simulated waste glass for low-activity waste immobilization. Interpretation of the elution profile was best described with a nonlinear kinetic model for adsorption.

  16. Integration of Genome-Scale Metabolic Nodels of Iron-Reducing Bacteria With Subsurface Flow and Geochemical Reactive Transport Models

    NASA Astrophysics Data System (ADS)

    Scheibe, T. D.; Mahadevan, R.; Fang, Y.; Garg, S.; Long, P. E.; Lovley, D. M.

    2008-12-01

    Several field and laboratory experiments have demonstrated that the growth and activity of iron-reducing bacteria can be stimulated in many subsurface environments by amendment of groundwater with a soluble electron donor. Under strong iron-reducing conditions, these organisms mediate reactions that can impact a wide range of subsurface contaminants including chlorinated hydrocarbons, metals, and radionuclides. Therefore there is strong interest in in-situ bioremediation as a potential technology for cleanup of contaminated aquifers. To evaluate and design bioremediation systems, as well as to evaluate the viability of monitored natural attenuation as an alternative, quantitative models of biogeochemically reactive transport are needed. To date, most such models represent microbial activity in terms of kinetic rate (e.g., Monod- type) formulations. Such models do not account for fundamental changes in microbial functionality (such as utilization of alternative respiratory pathways) that occur as the result of spatial and temporal variations in the geochemical environment experienced by microorganisms. Constraint-based genome-scale in silico models of microbial metabolism present an alternative to simplified rate formulations that provide flexibility to account for changes in microbial function in response to local geochemical conditions. We have developed and applied a methodology for coupling a constraint-based in silico model of Geobacter sulfurreducens with a conventional model of groundwater flow, transport, and geochemical reaction. Two uses of the in silico model are tested: 1) incorporation of modified microbial growth yield coefficients based on the in silico model, and 2) variation of reaction rates in a reactive transport model based on in silico modeling of a range of local geochemical conditions. Preliminary results from this integrated model will be presented.

  17. Multicomponent reactive transport modeling in variably saturated porous media using a generalized formulation for kinetically controlled reactions

    NASA Astrophysics Data System (ADS)

    Mayer, K. Ulrich; Frind, Emil O.; Blowes, David W.

    2002-09-01

    A generalized formulation for kinetically controlled reactions has been developed and incorporated into a multicomponent reactive transport model to facilitate the investigation of a large variety of problems involving inorganic and organic chemicals in variably saturated media. The general kinetic formulation includes intra-aqueous and dissolution-precipitation reactions in addition to geochemical equilibrium expressions for hydrolysis, aqueous complexation, oxidation-reduction, ion exchange, surface complexation, and gas dissolution-exsolution reactions. The generalized approach allows consideration of fractional order terms with respect to any dissolved species in terms of species activities or in terms of total concentrations, which facilitates the incorporation of a variety of experimentally derived rate expressions. Monod and inhibition terms can be used to describe microbially mediated reactions or to limit the reaction progress of inorganic reactions. Dissolution-precipitation reactions can be described as surface-controlled or transport-controlled reactions. The formulation also facilitates the consideration of any number of parallel reaction pathways, and reactions can be treated as irreversible or reversible processes. Two groundwater contamination scenarios, both set in variably saturated media but with significantly different geochemical reaction networks, are investigated and demonstrate the advantage of the generalized approach. The first problem focuses on a hypothetical case study of the natural attenuation of organic contaminants undergoing dissolution, volatilization, and biodegradation in an unconfined aquifer overlaid by unsaturated sediments. The second problem addresses the generation of acid mine drainage in the unsaturated zone of a tailings impoundment at the Nickel Rim Mine Site near Sudbury, Ontario, and subsequent reactive transport in the saturated portion of the tailings.

  18. Kinetic dissolution of carbonates and Mn oxides in acidic water: Measurement of in situ field rates and reactive transport modeling

    USGS Publications Warehouse

    Brown, J.G.; Glynn, P.D.

    2003-01-01

    The kinetics of carbonate and Mn oxide dissolution under acidic conditions were examined through the in situ exposure of pure phase samples to acidic ground water in Pinal Creek Basin, Arizona. The average long-term calculated in situ dissolution rates for calcite and dolomite were 1.65??10-7 and 3.64??10-10 mmol/(cm2 s), respectively, which were about 3 orders of magnitude slower than rates derived in laboratory experiments by other investigators. Application of both in situ and lab-derived calcite and dolomite dissolution rates to equilibrium reactive transport simulations of a column experiment did not improve the fit to measured outflow chemistry: at the spatial and temporal scales of the column experiment, the use of an equilibrium model adequately simulated carbonate dissolution in the column. Pyrolusite (MnO2) exposed to acidic ground water for 595 days increased slightly in weight despite thermodynamic conditions that favored dissolution. This result might be related to a recent finding by another investigator that the reductive dissolution of pyrolusite is accompanied by the precipitation of a mixed Mn-Fe oxide species. In PHREEQC reactive transport simulations, the incorporation of Mn kinetics improved the fit between observed and simulated behavior at the column and field scales, although the column-fitted rate for Mn-oxide dissolution was about 4 orders of magnitude greater than the field-fitted rate. Remaining differences between observed and simulated contaminant transport trends at the Pinal Creek site were likely related to factors other than the Mn oxide dissolution rate, such as the concentration of Fe oxide surface sites available for adsorption, the effects of competition among dissolved species for available surface sites, or reactions not included in the model.

  19. HYDROGEOCHEM: A coupled model of HYDROlogic transport and GEOCHEMical equilibria in reactive multicomponent systems

    SciTech Connect

    Yeh, G.T.; Tripathi, V.S.

    1990-11-01

    This report presents the development of a hydrogeochemical transport model for multicomponent systems. The model is designed for applications to proper hydrological setting, accommodation of complete suite of geochemical equilibrium processes, easy extension to deal with chemical kinetics, and least constraints of computer resources. The hydrological environment to which the model can be applied is the heterogeneous, anisotropic, saturated-unsaturated subsurface media under either transient or steady state flow conditions. The geochemical equilibrium processes included in the model are aqueous complexation, adsorption-desorption, ion exchange, precipitation-dissolution, redox, and acid-base reactions. To achieve the inclusion of the full complement of these geochemical processes, total analytical concentrations of all chemical components are chosen as the primary dependent variables in the hydrological transport equations. Attendant benefits of this choice are to make the extension of the model to deal with kinetics of adsorption-desorption, ion exchange, precipitation-dissolution, and redox relatively easy. To make the negative concentrations during the iteration between the hydrological transport and geochemical equilibrium least likely, an implicit form of transport equations are proposed. To alleviate severe constraints of computer resources in terms of central processing unit (CPU) time and CPU memory, various optional numerical schemes are incorporated in the model. The model consists of a hydrological transport module and geochemical equilibrium module. Both modules were thoroughly tested in code consistency and were found to yield plausible results. The model is verified with ten examples. 79 refs., 21 figs., 17 tabs.

  20. Preliminary characterization of materials for a reactive transport model validation experiment

    SciTech Connect

    Siegel, M.D.; Ward, D.B.; Cheng, W.C.; Bryant, C.; Chocas, C.S.; Reynolds, C.G.

    1993-03-01

    The geochemical properties of a porous sand and several tracers (Ni, Br, and Li) have been characterized for use in a caisson experiment designed to validate sorption models used in models of inactive transport. The surfaces of the sand grains have been examined by a combination of techniques including potentiometric titration, acid leaching, optical microscopy, and scanning electron microscopy with energy-dispersive spectroscopy. The surface studies indicate the presence of small amounts of carbonate, kaolinite and iron-oxyhydroxides. Adsorption of nickel, lithium and bromide by the sand was measured using batch techniques. Bromide was not sorbed by the sand. A linear (K{sub d}) or an isotherm sorption model may adequately describe transport of Li; however, a model describing the changes of pH and the concentrations of other solution species as a function of time and position within the caisson and the concomitant effects on Ni sorption may be required for accurate predictions of nickel transport.

  1. The effects of gas-fluid-rock interactions on CO2 injection and storage: Insights from reactive transport modeling

    SciTech Connect

    Xiao, Y.; Xu, T.; Pruess, K.

    2008-10-15

    Possible means of reducing atmospheric CO{sub 2} emissions include injecting CO{sub 2} in petroleum reservoirs for Enhanced Oil Recovery or storing CO{sub 2} in deep saline aquifers. Large-scale injection of CO{sub 2} into subsurface reservoirs would induce a complex interplay of multiphase flow, capillary trapping, dissolution, diffusion, convection, and chemical reactions that may have significant impacts on both short-term injection performance and long-term fate of CO{sub 2} storage. Reactive Transport Modeling is a promising approach that can be used to predict the spatial and temporal evolution of injected CO{sub 2} and associated gas-fluid-rock interactions. This presentation will summarize recent advances in reactive transport modeling of CO{sub 2} storage and review key technical issues on (1) the short- and long-term behavior of injected CO{sub 2} in geological formations; (2) the role of reservoir mineral heterogeneity on injection performance and storage security; (3) the effect of gas mixtures (e.g., H{sub 2}S and SO{sub 2}) on CO{sub 2} storage; and (4) the physical and chemical processes during potential leakage of CO{sub 2} from the primary storage reservoir. Simulation results suggest that CO{sub 2} trapping capacity, rate, and impact on reservoir rocks depend on primary mineral composition and injecting gas mixtures. For example, models predict that the injection of CO{sub 2} alone or co-injection with H{sub 2}S in both sandstone and carbonate reservoirs lead to acidified zones and mineral dissolution adjacent to the injection well, and carbonate precipitation and mineral trapping away from the well. Co-injection of CO{sub 2} with H{sub 2}S and in particular with SO{sub 2} causes greater formation alteration and complex sulfur mineral (alunite, anhydrite, and pyrite) trapping, sometimes at a much faster rate than previously thought. The results from Reactive Transport Modeling provide valuable insights for analyzing and assessing the dynamic

  2. Transport and Reactivity of Engineered Nanoparticles in Partially Saturated Porous Media

    NASA Astrophysics Data System (ADS)

    Dror, I.; Yecheskel, Y.; Berkowitz, B.

    2015-12-01

    Engineered nanoparticles (ENPs) are being produced in increasing amounts and have numerous applications in a variety of products and industrial processes. The same properties that make these substances so appealing may also cause them to act as persistent and toxic pollutants. The post-use release of ENPs to the environment is inevitable and soil appears to be one of the largest sinks of these potential contaminants. To date, despite the significant attention that ENP behavior in the environment has received, only a few studies have considered the fate and transport of ENPs in partially saturated systems. Here, we report measurements on the transport and fate of three commonly used ENPs - silver (Ag), gold (Au) and zinc oxide (ZnO) - in partially saturated porous media. The results show that ENP interactions with the solid matrix and solution components affect the fate of the ENPs and their transport. The negatively charged ENPs (AgNPs and AuNPs) are shown to be mobile in sand (which is also negatively charged) under various conditions, including water saturation levels and inlet concentration, with transport behavior resembling conservative tracer movement. Various aging scenarios were considered and the interaction of AgNPs with sulfides, chlorides, and calcium ions, all of which are known to interact and change AgNP properties, are shown to affect AgNP fate; however, in some cases, the changed particles remained suspended in solution and mobile. The positively charged ZnO showed very low mobility, but when humic acid was present in the inlet solution, interactions leading to enhanced mobility were observed. The presence of humic acid also changes ENP size and surface charge, transforming them to negatively charged larger aggregates that can be transported through the sand. Finally, remobilization of particles that were retained in the porous media was also demonstrated for ZnO ENPs, indicating possible release of entrapped ENPs upon changes in solution chemistry.

  3. Reactive solute transport in streams: A surface complexation approach for trace metal sorption

    USGS Publications Warehouse

    Runkel, R.L.; Kimball, B.A.; McKnight, Diane M.; Bencala, K.E.

    1999-01-01

    A model for trace metals that considers in-stream transport, metal oxide precipitation-dissolution, and pH-dependent sorption is presented. Linkage between a surface complexation submodel and the stream transport equations provides a framework for modeling sorption onto static and/or dynamic surfaces. A static surface (e.g., an iron-oxide-coated streambed) is defined as a surface with a temporally constant solid concentration. Limited contact between solutes in the water column and the static surface is considered using a pseudokinetic approach. A dynamic surface (e.g., freshly precipitated metal oxides) has a temporally variable solid concentration and is in equilibrium with the water column. Transport and deposition of solute mass sorbed to the dynamic surface is represented in the stream transport equations that include precipitate settling. The model is applied to a pH-modification experiment in an acid mine drainage stream. Dissolved copper concentrations were depressed for a 3 hour period in response to the experimentally elevated pH. After passage of the pH front, copper was desorbed, and dissolved concentrations returned to ambient levels. Copper sorption is modeled by considering sorption to aged hydrous ferric oxide (HFO) on the streambed (static surface) and freshly precipitated HFO in the water column (dynamic surface). Comparison of parameter estimates with reported values suggests that naturally formed iron oxides may be more effective in removing trace metals than synthetic oxides used in laboratory studies. The model's ability to simulate pH, metal oxide precipitation-dissolution, and pH-dependent sorption provides a means of evaluating the complex interactions between trace metal chemistry and hydrologic transport at the field scale.

  4. Modeling of Calcite Precipitation Driven by Bacteria-facilitated Urea Hydrolysis in A Flow Column Using A Fully Coupled, Fully Implicit Parallel Reactive Transport Simulator

    NASA Astrophysics Data System (ADS)

    Guo, L.; Huang, H.; Gaston, D.; Redden, G. D.

    2009-12-01

    One approach for immobilizing subsurface metal contaminants involves stimulating the in situ production of mineral phases that sequester or isolate contaminants. One example is using calcium carbonate to immobilize strontium. The success of such approaches depends on understanding how various processes of flow, transport, reaction and resulting porosity-permeability change couple in subsurface systems. Reactive transport models are often used for such purpose. Current subsurface reactive transport simulators typically involve a de-coupled solution approach, such as operator-splitting, that solves the transport equations for components and batch chemistry sequentially, which has limited applicability for many biogeochemical processes with fast kinetics and strong medium property-reaction interactions. A massively parallel, fully coupled, fully implicit reactive transport simulator has been developed based on a parallel multi-physics object oriented software environment computing framework (MOOSE) developed at the Idaho National Laboratory. Within this simulator, the system of transport and reaction equations is solved simultaneously in a fully coupled manner using the Jacobian Free Newton-Krylov (JFNK) method with preconditioning. The simulator was applied to model reactive transport in a one-dimensional column where conditions that favor calcium carbonate precipitation are generated by urea hydrolysis that is catalyzed by urease enzyme. Simulation results are compared to both laboratory column experiments and those obtained using the reactive transport simulator STOMP in terms of: the spatial and temporal distributions of precipitates and reaction rates and other major species in the reaction system; the changes in porosity and permeability; and the computing efficiency based on wall clock simulation time.

  5. Transport Properties of Amine/Carbon Dioxide Reactive Mixtures and Implications to Carbon Capture Technologies.

    PubMed

    Turgman-Cohen, Salomon; Giannelis, Emmanuel P; Escobedo, Fernando A

    2015-08-19

    The structure and transport properties of physisorbed and chemisorbed CO2 in model polyamine liquids (hexamethylenediamine and diethylenetriamine) are studied via molecular dynamics simulations. Such systems are relevant to CO2 absorption processes where nonaqueous amines are used as absorbents (e.g., when impregnated or grafted onto mesoporous media or misted in the gas phase). It is shown that accounting for the ionic speciation resulting from CO2 chemisorption enabled us to capture the qualitative changes in extent of absorption and fluidity with time that are observed in thermogravimetric experiments. Simulations reveal that high enough concentration of reacted CO2 leads to strong intermolecular ionic interactions and the arrest of molecular translations. The transport properties obtained from the simulations of the ionic speciated mixtures are also used to construct an approximate continuum-level model for the CO2 absorption process that mimics thermogravimetric experiments.

  6. Final Report Coupling in silico microbial models with reactive transport models to predict the fate of contaminants in the subsurface.

    SciTech Connect

    Lovley, Derek R.

    2012-10-31

    This project successfully accomplished its goal of coupling genome-scale metabolic models with hydrological and geochemical models to predict the activity of subsurface microorganisms during uranium bioremediation. Furthermore, it was demonstrated how this modeling approach can be used to develop new strategies to optimize bioremediation. The approach of coupling genome-scale metabolic models with reactive transport modeling is now well enough established that it has been adopted by other DOE investigators studying uranium bioremediation. Furthermore, the basic principles developed during our studies will be applicable to much broader investigations of microbial activities, not only for other types of bioremediation, but microbial metabolism in diversity of environments. This approach has the potential to make an important contribution to predicting the impact of environmental perturbations on the cycling of carbon and other biogeochemical cycles.

  7. Evolution of REDOX Tank Waste Plumes in Hanford Vadose Zone: A Conceptual Model Developed Through Reactive Transport Studies

    SciTech Connect

    Wan, Jiamin; Tokunaga, Tetsu K.; Larsen, Joern T.; Zheng, Zuoping

    2003-03-27

    Decisions on remedial actions for leakage of highly radioactive tank waste solutions at the Hanford Site will depend highly on understanding of the current distribution and future migration of contaminants in the subsurface. The geochemical data obtained from borehole drilling at SX tank farm in the 200 Area, by Tank Farm Vadose Zone Characterization Project of the U.S. Department of Energy, revealed valuable insights as well as some results that challenge our basic understanding of waste plume evolution. In response to these needs and challenges, we have been investigating reactive transport of tank waste solutions in Hanford sediments through laboratory column experiments combined with geochemical modeling. Analyses of solid and aqueous phases within different zones of contaminant plumes, along with thermodynamic predictions provide the basis for our conceptual model. This model reveals the primary processes controlling evolution of REDOX waste plumes in the Hanford vadose zone.

  8. A fully coupled model for water-gas-heat reactive transport with methane oxidation in landfill covers.

    PubMed

    Ng, C W W; Feng, S; Liu, H W

    2015-03-01

    Methane oxidation in landfill covers is a complex process involving water, gas and heat transfer as well as microbial oxidation. The coupled phenomena of microbial oxidation, water, gas, and heat transfer are not fully understood. In this study, a new model is developed that incorporates water-gas-heat coupled reactive transport in unsaturated soil with methane oxidation. Effects of microbial oxidation-generated water and heat are included. The model is calibrated using published data from a laboratory soil column test. Moreover, a series of parametric studies are carried out to investigate the influence of microbial oxidation-generated water and heat, initial water content on methane oxidation efficiency. Computed and measured results of gas concentration and methane oxidation rate are consistent. It is found that the coupling effects between water-gas-heat transfer and methane oxidation are significant. Ignoring microbial oxidation-generated water and heat can result in a significant difference in methane oxidation efficiency by 100%.

  9. Modelling the dispersion and transport of reactive pollutants in a deep urban street canyon: using large-eddy simulation.

    PubMed

    Zhong, Jian; Cai, Xiao-Ming; Bloss, William James

    2015-05-01

    This study investigates the dispersion and transport of reactive pollutants in a deep urban street canyon with an aspect ratio of 2 under neutral meteorological conditions using large-eddy simulation. The spatial variation of pollutants is significant due to the existence of two unsteady vortices. The deviation of species abundance from chemical equilibrium for the upper vortex is greater than that for the lower vortex. The interplay of dynamics and chemistry is investigated using two metrics: the photostationary state defect, and the inferred ozone production rate. The latter is found to be negative at all locations within the canyon, pointing to a systematic negative offset to ozone production rates inferred by analogous approaches in environments with incomplete mixing of emissions. This study demonstrates an approach to quantify parameters for a simplified two-box model, which could support traffic management and urban planning strategies and personal exposure assessment.

  10. A simple reactive-transport model of calcite precipitation in soils and other porous media

    NASA Astrophysics Data System (ADS)

    Kirk, G. J. D.; Versteegen, A.; Ritz, K.; Milodowski, A. E.

    2015-09-01

    Calcite formation in soils and other porous media generally occurs around a localised source of reactants, such as a plant root or soil macro-pore, and the rate depends on the transport of reactants to and from the precipitation zone as well as the kinetics of the precipitation reaction itself. However most studies are made in well mixed systems, in which such transport limitations are largely removed. We developed a mathematical model of calcite precipitation near a source of base in soil, allowing for transport limitations and precipitation kinetics. We tested the model against experimentally-determined rates of calcite precipitation and reactant concentration-distance profiles in columns of soil in contact with a layer of HCO3--saturated exchange resin. The model parameter values were determined independently. The agreement between observed and predicted results was satisfactory given experimental limitations, indicating that the model correctly describes the important processes. A sensitivity analysis showed that all model parameters are important, indicating a simpler treatment would be inadequate. The sensitivity analysis showed that the amount of calcite precipitated and the spread of the precipitation zone were sensitive to parameters controlling rates of reactant transport (soil moisture content, salt content, pH, pH buffer power and CO2 pressure), as well as to the precipitation rate constant. We illustrate practical applications of the model with two examples: pH changes and CaCO3 precipitation in the soil around a plant root, and around a soil macro-pore containing a source of base such as urea.

  11. Reactive solute transport in streams. 2. Simulation of a pH modification experiment

    USGS Publications Warehouse

    Runkel, R.L.; McKnight, Diane M.; Bencala, K.E.; Chapra, S.C.

    1996-01-01

    We present an application of an equilibrium-based solute transport model to a pH-modification experiment conducted on the Snake River, an acidic, metal-rich stream located in the Rocky Mountains of Colorado. During the experiment, instream pH decreased from 4.2 to 3.2, causing a marked increase in dissolved iron concentrations. Model application requires specification of several parameters that are estimated using tracer techniques, mass balance calculations, and geochemical data. Two basic questions are addressed through model application: (1) What are the processes responsible for the observed increase in dissolved iron concentrations? (2) Can the identified processes be represented within the equilibrium-based transport model? Simulation results indicate that the increase in iron was due to the dissolution of hydrous iron oxides and the photoreduction of ferric iron. Dissolution from the streambed is represented by considering a trace compartment consisting of freshly precipitated hydrous iron oxide and an abundant compartment consisting of aged precipitates that are less soluble. Spatial variability in the solubility of hydrous iron oxide is attributed to heterogeneity in the streambed sediments, temperature effects, and/or variability in the effects of photoreduction. Solubility products estimated via simulation fall within a narrow range (pK(sp) from 40.2 to 40.8) relative to the 6 order of magnitude variation reported for laboratory experiments (pK(sp) from 37.3 to 43.3). Results also support the use of an equilibrium-based transport model as the predominate features of the iron and p H profiles are reproduced. The model provides a valuable tool for quantifying the nature and extent of pH- dependent processes within the context of hydrologic transport.

  12. TOURGHREACT: A Simulation Program for Non-isothermal MultiphaseReactive Geochemical Transport in Variably Saturated GeologicMedia

    SciTech Connect

    Xu, Tianfu; Sonnenthal, Eric; Spycher, Nicolas; Pruess, Karsten

    2004-12-07

    TOUGHREACT is a numerical simulation program for chemically reactive non-isothermal flows of multiphase fluids in porous and fractured media. The program was written in Fortran 77 and developed by introducing reactive geochemistry into the multiphase fluid and heat flow simulator TOUGH2. A variety of subsurface thermo-physical-chemical processes are considered under a wide range of conditions of pressure, temperature, water saturation, ionic strength, and pH and Eh. Interactions between mineral assemblages and fluids can occur under local equilibrium or kinetic rates. The gas phase can be chemically active. Precipitation and dissolution reactions can change formation porosity and permeability. The program can be applied to many geologic systems and environmental problems, including geothermal systems, diagenetic and weathering processes, subsurface waste disposal, acid mine drainage remediation, contaminant transport, and groundwater quality. Here we present two examples to illustrate applicability of the program: (1) injectivity effects of mineral scaling in a fractured geothermal reservoir and (2) CO2 disposal in a deep saline aquifer.

  13. A nonequilibrium model for reactive contaminant transport through fractured porous media: Model development and semianalytical solution

    NASA Astrophysics Data System (ADS)

    Joshi, Nitin; Ojha, C. S. P.; Sharma, P. K.

    2012-10-01

    In this study a conceptual model that accounts for the effects of nonequilibrium contaminant transport in a fractured porous media is developed. Present model accounts for both physical and sorption nonequilibrium. Analytical solution was developed using the Laplace transform technique, which was then numerically inverted to obtain solute concentration in the fracture matrix system. The semianalytical solution developed here can incorporate both semi-infinite and finite fracture matrix extent. In addition, the model can account for flexible boundary conditions and nonzero initial condition in the fracture matrix system. The present semianalytical solution was validated against the existing analytical solutions for the fracture matrix system. In order to differentiate between various sorption/transport mechanism different cases of sorption and mass transfer were analyzed by comparing the breakthrough curves and temporal moments. It was found that significant differences in the signature of sorption and mass transfer exists. Applicability of the developed model was evaluated by simulating the published experimental data of Calcium and Strontium transport in a single fracture. The present model simulated the experimental data reasonably well in comparison to the model based on equilibrium sorption assumption in fracture matrix system, and multi rate mass transfer model.

  14. Use of Reactive Transport Modeling to Evaluate Remedial Options for an Acid Mine Drainage Stream, With Emphasis on Prediction Uncertainty

    NASA Astrophysics Data System (ADS)

    Runkel, R. L.; Kimball, B. A.; Walton-Day, K.; Verplanck, P. L.

    2006-12-01

    Mineral Creek, a headwater stream in Southwestern Colorado, drains a sub-alpine watershed with numerous abandoned mines. A synoptic study conducted in 1999 indicates that the Mineral Creek watershed contributes 60% of the observed copper load for the Upper Animas River. In addition, zinc concentrations observed during the 1999 study exceed toxicity standards along the entire length of Mineral Creek. Given these findings, Mineral Creek is the potential site of future remedial actions to improve stream-water quality. Using the 1999 data, a reactive transport model was used to predict the effects of a small treatment system that neutralizes acidic inflow waters. Model application indicates that the treatment system would significantly improve water quality, producing higher pH values and lower dissolved metal concentrations downstream. Despite this progress, the results of model application may be of limited use for planning remediation, due to the potential uncertainty of model predictions (e.g. errors in the characterization of hydrologic and geochemical processes). An additional study was therefore conducted in 2005 to develop estimates of prediction uncertainty. The 2005 study implemented a paired-synoptic approach in which two synoptics were conducted under similar hydrologic conditions. The first synoptic was similar to the 1999 study in that the overall goal was to characterize stream-water quality under existing (acidic) conditions. The second synoptic study was conducted during a continuous sodium hydroxide injection that was designed to mimic a small treatment system. As in the initial model application, data collected under existing conditions (synoptic 1) will be used to calibrate the reactive transport model. Model inputs will then be modified to reflect the effects of treatment, and predictions of post-remediation water quality will be obtained by model application. The results of this application will then be compared to data from the post

  15. Metabolism-Induced CaCO 3 Biomineralization During Reactive Transport in a Micromodel: Implications for Porosity Alteration

    DOE PAGES

    Singh, Rajveer; Yoon, Hongkyu; Sanford, Robert A.; ...

    2015-09-08

    We investigated the ability of Pseudomonas stutzeri strain DCP-Ps1 to drive CaCO3 biomineralization in a microfluidic flowcell (i.e., micromodel) that simulates subsurface porous media. Results indicate that CaCO3 precipitation occurs during NO3– reduction with a maximum saturation index (SIcalcite) of ~1.56, but not when NO3– was removed, inactive biomass remained, and pH and alkalinity were adjusted to SIcalcite ~ 1.56. CaCO3 precipitation was promoted by metabolically active cultures of strain DCP-Ps1, which at similar values of SIcalcite, have a more negative surface charge than inactive strain DCP-Ps1. A two-stage NO3– reduction (NO3– → NO2– → N2) pore-scale reactive transport modelmore » was used to evaluate denitrification kinetics, which was observed in the micromodel as upper (NO3– reduction) and lower (NO2– reduction) horizontal zones of biomass growth with CaCO3 precipitation exclusively in the lower zone. Our model results are consistent with two biomass growth regions and indicate that precipitation occurred in the lower zone because the largest increase in pH and alkalinity is associated with NO2– reduction. CaCO3 precipitates typically occupied the entire vertical depth of pores and impacted porosity, permeability, and flow. This study provides a framework for incorporating microbial activity in biogeochemistry models, which often base biomineralization only on SI (caused by biotic or abiotic reactions) and, thereby, underpredict the extent of this complex process. Furthermore, these results have wide-ranging implications for understanding reactive transport in relevance to groundwater remediation, CO2 sequestration, and enhanced oil recovery.« less

  16. Modeling of non-reactive solute transport in fractured clayey till during variable flow rate and time.

    PubMed

    Jørgensen, Peter R; Helstrup, Tina; Urup, Johanne; Seifert, Dorte

    2004-02-01

    Fractures and biopores can act as preferential flow paths in clay aquitards and may rapidly transmit contaminants into underlying aquifers. Reliable numerical models for assessment of groundwater contamination from such aquitards are needed for planning, regulatory and remediation purposes. In this investigation, high resolution preferential water-saturated flow and bromide transport data were used to evaluate the suitability of equivalent porous medium (EPM), dual porosity (DP) and discrete fracture/matrix diffusion (DFMD) numerical modeling approaches for assessment of flow and non-reactive solute transport in clayey till. The experimental data were obtained from four large undisturbed soil columns (taken from 1.5 to 3.5 m depth) in which biopores and channels along fractures controlled 96-99% of water-saturated flow. Simulating the transport data with the EPM effective porosity model (FRACTRAN in EPM mode) was not successful because calibrated effective porosity for the same column had to be varied up to 1 order of magnitude in order to simulate solute breakthrough for the applied flow rates between 11 and 49 mm/day. Attempts to simulate the same data with the DP models CXTFIT and MODFLOW/MT3D were also unsuccessful because fitted values for dispersion, mobile zone porosity, and mass transfer coefficient between mobile and immobile zones varied several orders of magnitude for the different flow rates, and because dispersion values were furthermore not physically realistic. Only the DFMD modeling approach (FRACTRAN in DFMD mode) was capable to simulate the observed changes in solute transport behavior during alternating flow rate without changing values of calibrated fracture spacing and fracture aperture to represent the macropores.

  17. Preliminary reactive geochemical transport simulation study on CO2 geological sequestration at the Changhua Coastal Industrial Park Site, Taiwan

    NASA Astrophysics Data System (ADS)

    Sung, R.; Li, M.

    2013-12-01

    assumed throughout the simulation domain. Comparisons among simulated results with different mesh systems of nested meshes and non-nested meshes and considerations of multiphase reactive transport and physical transport were demonstrated in this study. Preliminary results of injection CO2 for 50 years are: (1) about 7 wt.% of injected CO2 was trapped as carbonate minerals mainly as ankerite; (2) porosities were decreased by 0.014 % and increased by 0.102 % at the injection point and beneath the cap rock, respectively, and were subsequently decreased with time due to minerals precipitation mostly as illite and ankerite; (3) differences of simulated aquifer responses between reactive transport and physical transport were insignificant; and (4) projected CO2 plumes with the nested meshes was smaller than those by the non-nested meshes after cease of CO2 injection. Keywords: CO2-Saline-Mineral Interaction, Reactive Geochemical Transport, TOUGHREACT, Mineral Trapping Assessment, Changhua Costal Industrial Park Site, Taiwan Reference: Marini, L., 2006, Geological Sequestration of Carbon Dioxide, Volume 11: Thermodynamics, Kinetics, and Reaction Path Modeling, Elsevier Science, pp.470. Xu, T., J. A. Apps and K. Pruess, 2004, Numerical simulation of CO2 disposal by mineral trapping in deep aquifers, Applied Geochemistry, Vol. 19:917-936.

  18. Reactive transport modelling of As- and P-species in the rhizosphere

    NASA Astrophysics Data System (ADS)

    Szegedi, K.; Vetterlein, D.; Jahn, R.

    2009-04-01

    The toxic arsenate competes with the nutrient phosphate for binding sites in soil, i.e. at goethite or ferrihydrite surfaces and for binding sites at root membranes. P in soil can be mobilised by plants through exudation of organic anions like citrate or by release of protons. These mechanisms may alter the competition between As(V) and P for binding sites and thus enhance arsenate transfer into the food chain. In a compartment system experiment with corn plants the temporal and spatial dynamics of different parameters (soil solution P, As(V), citrate and proton concentration) were measured with different initial application rates of goethite (Vetterlein et al, 2007). For the integration of the different parameters the experiment was modelled using the RhizoMath code (Szegedi et al, 2008), that is based on coupling the mathematical package MATLAB with the geochemical code PHREEQC. The initialization module of RhizoMath was used to determine the number of surface binding sites of goethite and values of the equilibrium constants of corresponding stoichiometric equations describing the surface complexation of As(V) on goethite as given in Szegedi et al. (2008). The transport module of RhizoMath was used to model transport and speciation in the compartment system. Although the model was able to qualitatively represent experimental observations, a quantitative agreement between modelled and measured data could not be achieved. Thus, in a second step, the transport module was extended with a root compartment factor that expresses the relative coverage of the root compartment by the roots and the active root surface behind the unit area of the compartment cross section. This allowed modelling a growing plant in the compartment system. As temporal changes in water flux and nutrient demand are not necessarily identical, temporal changes in water flux and nutrient demand were scaled independently from each other, using constant, linear or measured water consumption and leaf

  19. Review: Selenium contamination, fate, and reactive transport in groundwater in relation to human health

    NASA Astrophysics Data System (ADS)

    Bailey, Ryan T.

    2016-12-01

    Selenium (Se) is an essential micro-nutrient for humans, but can be toxic at high levels of intake. Se deficiency and Se toxicity are linked with serious diseases, with some regions worldwide experiencing Se deficiency due to Se-poor rocks and soils and other areas dealing with Se toxicity due to the presence of Se-enriched geologic materials. In addition, Se is consumed primarily through plants that take up Se from soil and through animal products that consume these plants. Hence, the soil and groundwater system play important roles in determining the effect of Se on human health. This paper reviews current understanding of Se fate and transport in soil and groundwater systems and its relation to human health, with a focus on alluvial systems, soil systems, and the interface between alluvial systems and Cretaceous shale that release Se via oxidation processes. The review focuses first on the relation between Se and human health, followed by a summary of Se distribution in soil-aquifer systems, with an emphasis on the quantitative relationship between Se content in soil and Se concentration in underlying groundwater. The physical, chemical, and microbial processes that govern Se fate and transport in subsurface systems then are presented, followed by numerical modeling techniques used to simulate these processes in study regions and available remediation strategies for either Se-deficient or Se-toxic regions. This paper can serve as a guide to any field, laboratory or modeling study aimed at assessing Se fate and transport in groundwater systems and its relation to human health.

  20. Optical and electron transport properties of reactively sputtered Cu/sub x/S

    SciTech Connect

    Leong, J.Y.C.

    1980-06-30

    Thin films of Cu/sub x/S were deposited on glass slides by sputtering Cu in a reactive H/sub 2/S/Ar environment. Optical transmittance and reflectance measurements were used to explore the infrared absorption spectra of the material. Analysis of the absorption edge characteristics resulted in the identification of an indirect bandgap at 1.15 (+-.05) eV, a direct bandgap at 1.30 (+-.05) eV, and an electron effective mass of 1.0 (+-0.2) m/sub 0/. Electrical data consisting of resistivity and Hall effect measurements from liquid nitrogen to room temperature were analyzed to determine the dominant scattering mechanisms limiting the hole mobility in the material. Ionized impurity scattering was the dominant mechanism at low temperatures (T < 100/sup 0/K) and polar optical phonon scattering was most effective at high temperatures (T > 150/sup 0/K). All films were p-type. Effects of sputtering gas pressure, heat treatments, and temperature on the properties were studied.

  1. Simulation of reactive transport of injected CO2 on the Colorado Plateau, Utah, USA

    USGS Publications Warehouse

    White, S.P.; Allis, R.G.; Moore, J.; Chidsey, T.; Morgan, C.; Gwynn, W.; Adams, M.

    2005-01-01

    This paper investigates injection of CO2 into non-dome-shaped geological structures that do not provide the traps traditionally deemed necessary for the development of artificial CO2 reservoirs. We have developed a conceptual and two numerical models of the geology and groundwater along a cross-section lying approximately NW-SE and in the vicinity of the Hunter power station on the Colorado Plateau, Central Utah and identified a number of potential sequestration sites on this cross-section. Preliminary modeling identified the White Rim Sandstone as appearing to offer the properties required of a successful sequestration site. Detailed modeling of injection of CO2 into the White Rim Sandstone using the reactive chemical simulator ChemTOUGH found that 1000 years after the 30 year injection period began approximately 21% of the injected CO2 was permanently sequestered as a mineral, 52% was beneath the ground surface as a gas or dissolved in the groundwater and 17% had leaked to the surface and leakage to the surface was continuing. ?? 2005 Elsevier B.V. All rights reserved.

  2. Kinetic Desorption and Sorption of U(VI) During Reactive Transport in a Contaminated Hanford Sediment

    SciTech Connect

    Qafoku, Nik; Zachara, John M.; Liu, Chongxuan; Gassman, Paul L.; Qafoku, Odeta; Smith, Steven C.

    2005-05-12

    Column experiments were conducted to investigate U(VI) desorption and sorption kinetics in a sand-textured, contaminated (22.7 µmol kg-1) capillary fringe sediment that had experienced long-term exposure to U(VI). The clay fraction mineralogy of the sediment was dominated by montmorillonite, muscovite, vermiculite, and chlorite. Saturated column experiments were performed under mildly alkaline/calcareous conditions representative of the Hanford site where uranyl–carbonate and calcium–uranyl–carbonate complexes dominate aqueous speciation. A U(VI) free solution was used to study U(VI) desorption in columns where different flow rates were applied. Uranium(VI) sorption was studied after the desorption of labile contaminant U(VI) using different U(VI) concentrations in the leaching solution. Strong kinetic behavior was observed for both U(VI) desorption and sorption. Although U(VI) is semi–mobile in mildly alkaline, calcareous subsurface environments, our results showed substantial U(VI) sorption, significant retardation during transport, and atypical breakthrough curves with extended tailing. A distributed rate model was applied to describe the effluent data and to allow comparisons between the desorption rate of contaminant U(VI) with the rate of short-term U(VI) sorption. Desorption was the slower process. Our results suggest that U(VI) release and transport in the vadose zone and aquifer system from which the sediment was obtained are kinetically controlled.

  3. Coupling Sorption to Soil Weathering During Reactive Transport: Impacts of Mineral Transformation and Sorbent Aging on Contaminant Speciation and Mobility

    SciTech Connect

    Chorover, J.; Mueller, K. T.; O'Day, P. A.; Serne, R. J.; Steefel, C. I.

    2009-10-30

    This project aimed for a predictive-mechanistic understanding of the coupling between mineral weathering and contaminant (Cs, Sr, I) transport/fate in caustic waste-impacted sediments. Based on our prior studies of model clay mineral systems, we postulated that contaminant uptake to Hanford sediments would reflect concurrent adsorption and co-precipitation effects. Our specific objectives were: (1) to assess the molecular-scale mechanisms responsible for time-dependent sequestration of contaminants (Cs, Sr and I) during penetration of waste-induced weathering fronts; (2) to determine the rate and extent of contaminant release from the sorbed state; (3) to develop a reactive transport model based on molecular mechanisms and macroscopic flow experiments [(1) and (2)] that simulates adsorption, aging, and desorption dynamics. Progress toward achieving each of these objectives is discussed below. We observed unique molecular mechanisms for sequestration of Sr, Cs and I during native silicate weathering in caustic waste. Product solids, which included poorly crystalline aluminosilicates and well-crystallized zeolites and feldspathoids, accumulate contaminant species during crystal growth.

  4. An adaptive hybrid EnKF-OI scheme for efficient state-parameter estimation of reactive contaminant transport models

    NASA Astrophysics Data System (ADS)

    El Gharamti, Mohamad; Valstar, Johan; Hoteit, Ibrahim

    2014-05-01

    Reactive contaminant transport models are used by hydrologists to simulate and study the migration and fate of industrial waste in subsurface aquifers. Accurate transport modeling of such waste requires clear understanding of the system's parameters, such as sorption and biodegradation. In this study, we present an efficient sequential data assimilation scheme that computes accurate estimates of aquifer contamination and spatially variable sorption coefficients. This assimilation scheme is based on a hybrid formulation of the ensemble Kalman filter (EnKF) and optimal interpolation (OI) in which solute concentration measurements are assimilated via a recursive dual estimation of sorption coefficients and contaminant state variables. This hybrid EnKF-OI scheme is used to mitigate background covariance limitations due to ensemble under-sampling and neglected model errors. Numerical experiments are conducted with a two-dimensional synthetic aquifer in which cobalt-60, a radioactive contaminant, is leached in a saturated heterogeneous clayey sandstone zone. Assimilation experiments are investigated under different settings and sources of model and observational errors. Our results suggest that the proposed scheme allows a reduction of around 80% of the ensemble size as compared to the standard EnKF scheme.

  5. An adaptive hybrid EnKF-OI scheme for efficient state-parameter estimation of reactive contaminant transport models

    NASA Astrophysics Data System (ADS)

    Gharamti, M. E.; Valstar, J.; Hoteit, I.

    2014-09-01

    Reactive contaminant transport models are used by hydrologists to simulate and study the migration and fate of industrial waste in subsurface aquifers. Accurate transport modeling of such waste requires clear understanding of the system’s parameters, such as sorption and biodegradation. In this study, we present an efficient sequential data assimilation scheme that computes accurate estimates of aquifer contamination and spatially variable sorption coefficients. This assimilation scheme is based on a hybrid formulation of the ensemble Kalman filter (EnKF) and optimal interpolation (OI) in which solute concentration measurements are assimilated via a recursive dual estimation of sorption coefficients and contaminant state variables. This hybrid EnKF-OI scheme is used to mitigate background covariance limitations due to ensemble under-sampling and neglected model errors. Numerical experiments are conducted with a two-dimensional synthetic aquifer in which cobalt-60, a radioactive contaminant, is leached in a saturated heterogeneous clayey sandstone zone. Assimilation experiments are investigated under different settings and sources of model and observational errors. Simulation results demonstrate that the proposed hybrid EnKF-OI scheme successfully recovers both the contaminant and the sorption rate and reduces their uncertainties. Sensitivity analyses also suggest that the adaptive hybrid scheme remains effective with small ensembles, allowing to reduce the ensemble size by up to 80% with respect to the standard EnKF scheme.

  6. Review of pore network modelling of porous media: Experimental characterisations, network constructions and applications to reactive transport

    NASA Astrophysics Data System (ADS)

    Xiong, Qingrong; Baychev, Todor G.; Jivkov, Andrey P.

    2016-09-01

    Pore network models have been applied widely for simulating a variety of different physical and chemical processes, including phase exchange, non-Newtonian displacement, non-Darcy flow, reactive transport and thermodynamically consistent oil layers. The realism of such modelling, i.e. the credibility of their predictions, depends to a large extent on the quality of the correspondence between the pore space of a given medium and the pore network constructed as its representation. The main experimental techniques for pore space characterisation, including direct imaging, mercury intrusion porosimetry and gas adsorption, are firstly summarised. A review of the main pore network construction techniques is then presented. Particular focus is given on how such constructions are adapted to the data from experimentally characterised pore systems. Current applications of pore network models are considered, with special emphasis on the effects of adsorption, dissolution and precipitation, as well as biomass growth, on transport coefficients. Pore network models are found to be a valuable tool for understanding and predicting meso-scale phenomena, linking single pore processes, where other techniques are more accurate, and the homogenised continuum porous media, used by engineering community.

  7. Reactive-transport model for the prediction of the uniform corrosion behaviour of copper used fuel containers

    NASA Astrophysics Data System (ADS)

    King, F.; Kolar, M.; Maak, P.

    2008-09-01

    Used fuel containers in a deep geological repository will be subject to various forms of corrosion. For containers made from oxygen-free, phosphorus-doped copper, the most likely corrosion processes are uniform corrosion, underdeposit corrosion, stress corrosion cracking, and microbiologically influenced corrosion. The environmental conditions within the repository are expected to evolve with time, changing from warm and oxidizing initially to cool and anoxic in the long-term. In response, the corrosion behaviour of the containers will also change with time as the repository environment evolve. A reactive-transport model has been developed to predict the time-dependent uniform corrosion behaviour of the container. The model is based on an experimentally-based reaction scheme that accounts for the various chemical, microbiological, electrochemical, precipitation/dissolution, adsorption/desorption, redox, and mass-transport processes at the container surface and in the compacted bentonite-based sealing materials within the repository. Coupling of the electrochemical interfacial reactions with processes in the bentonite buffer material allows the effect of the evolution of the repository environment on the corrosion behaviour of the container to be taken into account. The Copper Corrosion Model for Uniform Corrosion predicts the time-dependent corrosion rate and corrosion potential of the container, as well as the evolution of the near-field environment.

  8. Proline Modulates the Trypanosoma cruzi Resistance to Reactive Oxygen Species and Drugs through a Novel D, L-Proline Transporter

    PubMed Central

    Sayé, Melisa; Miranda, Mariana R.; di Girolamo, Fabio; de los Milagros Cámara, María; Pereira, Claudio A.

    2014-01-01

    Trypanosoma cruzi, the etiological agent of Chagas' disease, has a metabolism largely based on the consumption of glucose and proline. This amino acid is essential for host cells infection and intracellular differentiation. In this work we identified a proline transporter (TcAAAP069) by yeasts complementation assays and overexpression in Trypanosoma cruzi epimastigotes. TcAAAP069 is mono-specific for proline but presents an unusual feature; the lack of stereospecificity, because it is competitively inhibited by the D- enantiomer. Parasites overexpressing TcAAAP069 have an increased intracellular proline concentration, 2.6-fold higher than controls, as a consequence of a higher proline transport rate. Furthermore, augmented proline concentration correlates with an improved resistance to trypanocidal drugs and also to reactive oxygen species including hydrogen peroxide and nitric oxide, emulating natural physiological situations. The IC50s for nifurtimox, benznidazole, H2O2 and NO. were 125%, 68%, 44% and 112% higher than controls, respectively. Finally, proline metabolism generates a higher concentration (48%) of ATP in TcAAAP069 parasites. Since proline participates on essential energy pathways, stress and drug resistance responses, these results provide a novel target for the development of new drugs for the treatments for Chagas' disease. PMID:24637744

  9. Inactivation of particle-associated microorganisms in wastewater disinfection: modeling of ozone and chlorine reactive diffusive transport in polydispersed suspensions.

    PubMed

    Dietrich, Joseph P; Loge, Frank J; Ginn, Timothy R; Başağaoğlu, Hakan

    2007-05-01

    Occlusion of microorganisms in wastewater particles often governs the overall performance of a disinfection system, and the associated health risks of post-disinfected effluents. Little is currently known on the penetration of chemical oxidants into particles developed in wastewater treatment. In this work, a reactive transport model that incorporates intra- and extra-particle chemical decay, radial intra-particle diffusion, mass transfer resistance at particle surfaces, and non-linear reaction kinetics within a competitive multi-particle size aqueous environment, was used to analyze the penetration of ozone and chlorine into wastewater particles. Individual characteristics from two secondary wastewater treatment facilities were used in model calibration. Simulations revealed that significant ozone transport within particles greater than 6 microm required large initial concentrations to exhaust the preferential reaction with aqueous soluble matter. Chlorinated samples exhibited apparently slower reactions and thus deeper penetration (22-40 microm). Chlorine penetration was less sensitive to variations in the extra-particle reaction and disinfectant concentration than ozone. Model simulations that considered elevated initial concentrations of chemical disinfectants revealed that complete inactivation of all particle size domains was not possible with current disinfection practices (e.g., contact times). Reduction in the health risks associated with wastewater particles requires treatment that efficiently balances particle removal (filtration) and particle inactivation (disinfection).

  10. A reactive transport model of CO2-water-rock interaction in a push-pull test in basaltic rocks

    NASA Astrophysics Data System (ADS)

    Hidalgo, J. J.; de Dieuleveult, C.; Agrinier, P.; Lagneau, V.

    2010-12-01

    Basaltic rock formations have been proposed as suitable hosts for CO2 storage. Basalts have a high content in silicate minerals, Ca and Mg, which neutralize the acidic CO2 injected solution. Moreover, under such conditions the formation of stable carbonate minerals, which is the safest way to store CO2, is favored. A series of CO2 injection tests were carried out at the Lamont-Doherty Earth Observatory site (Palisades, New York, USA) in 2005 to assess the basalt neutralization capacity [1, 3]. The tests were conducted in the contact zone between the Palisades sill and the underlying Newark Basin sediments. The Palisades sill consists of dolerite rich in plagioclase and pyroxene [2]. The contact zone between the dolerite and the underlying sediments is characterized by chilled dolerite and contact-metamorphosed sedimentary rocks. The essays consisted of single-well push-pull tests in which an CO2-rich solution was injected in the aquifer and pumped after an incubation period. NaCl was added as a inert tracer. In this work, we focus on one of those push-pull tests. HYTEC code [4] was used to make a reactive transport model. Hydraulic and transport parameters were adjusted by fitting the chloride breakthrough curve. The model shows that the chloride arrival is mainly controlled by the product of the porosity times the longitudinal dispersion. Chemistry results show that the composition of the system (total dissolved inorganic carbon, Ca, Na, and Mg) is governed by the dissolution rate of the minerals. In addition, ion exchange is suggested by Na data. As a future work, modeling of isotopic data to better quantify the dissolution rates is considered. References [1] Assayag, N., J. Matter, M. Ader, D. Goldberg, and P. Agrinier (2009),Water-rock interactions during a CO2 injection field-test: Implications on host rock dissolution and alteration effects, Chemical Geology,265(1-2), 227--235. [2] Goldberg, D., and K. Burgdorff (2005), Natural fracturing and petrophysical

  11. Using toughreact to model reactive fluid flow and geochemical transport in hydrothermal systems

    SciTech Connect

    Xu, Tianfu; Sonnenthal, Eric; Spycher, Nicolas; Pruess, Karsten

    2003-07-31

    The interaction between hydrothermal fluids and the rocks through which they migrate alters the earlier formed primary minerals and leads to the formation of secondary minerals, resulting in changes in the physical and chemical properties of the system. We have developed a comprehensive numerical simulator, TOUGHREACT, which considers nonisothermal multi-component chemical transport in both liquid and gas phases. A variety of subsurface thermo-physical-chemical processes is considered under a wide range of conditions of pressure, temperature, water saturation, and ionic strength. The code can be applied to problems in fundamental analysis of the hydrothermal systems and in the exploration of geothermal reservoirs including chemical evolution, mineral alteration, mineral scaling, changes of porosity and permeability, and mineral recovery from geothermal fluids.

  12. Reactive transport controls on sandy acid sulfate soils and impacts on shallow groundwater quality

    NASA Astrophysics Data System (ADS)

    Salmon, S. Ursula; Rate, Andrew W.; Rengel, Zed; Appleyard, Steven; Prommer, Henning; Hinz, Christoph

    2014-06-01

    Disturbance or drainage of potential acid sulfate soils (PASS) can result in the release of acidity and degradation of infrastructure, water resources, and the environment. Soil processes affecting shallow groundwater quality have been investigated using a numerical code that integrates (bio)geochemical processes with water, solute, and gas transport. The patterns of severe and persistent acidification (pH < 4) in the sandy, carbonate-depleted podzols of a coastal plain could be reproduced without calibration, based on oxidation of microcrystalline pyrite after groundwater level decrease and/or residual groundwater acidity, due to slow vertical solute transport rates. The rate of acidification was limited by gas phase diffusion of oxygen and hence was sensitive to soil water retention properties and in some cases also to oxygen consumption by organic matter mineralization. Despite diffusion limitation, the rate of oxidation in sandy soils was rapid once pyrite-bearing horizons were exposed, even to a depth of 7.5 m. Groundwater level movement was thus identified as an important control on acidification, as well as the initial pyrite content. Increase in the rate of Fe(II) oxidation lead to slightly lower pH and greater accumulation of Fe(III) phases, but had little effect on the overall amount of pyrite oxidized. Aluminosilicate (kaolinite) dissolution had a small pH-buffering effect but lead to the release of Al and associated acidity. Simulated dewatering scenarios highlighted the potential of the model for risk assessment of (bio)geochemical impacts on soil and groundwater over a range of temporal and spatial scales.

  13. Characterization of reactive transport by 3-D electrical resistivity tomography (ERT) under unsaturated conditions

    NASA Astrophysics Data System (ADS)

    Wehrer, Markus; Binley, Andrew; Slater, Lee D.

    2016-10-01

    The leaching of nitrate from intensively used arable soil is of major concern in many countries. In this study, we show how time lapse electrical resistivity tomography (ERT) can be used to characterize spatially heterogeneous processes of ion production, consumption, and transport in soils. A controlled release fertilizer was introduced into an undisturbed soil core in a laboratory lysimeter and subjected to infiltration events. The production of ions resulting from processes associated with nitrification and their transport through the soil core was observed by time lapse ERT and analysis of seepage water samples from a multicompartment sampler. ERT images show development and propagation of a high-conductivity plume from the fertilizer source zone. Molar amounts of nitrate produced in and exported from the soil core could be well reproduced by time lapse ERT using a spatial moment analysis. Furthermore, we observed that several shape measures of local breakthrough-curves (BTCs) of seepage water conductivity and nitrate derived by effluent analyses and BTCs of bulk conductivity derived by ERT are highly correlated, indicating the preservation of spatial differences of the plume breakthrough in the ERT data. Also differences between nitrate breakthrough and a conservative tracer breakthrough can be observed by ERT. However, the estimation of target ion concentrations by ERT is error bound and the smoothing algorithm of the inversion masks spatial conductivity differences. This results in difficulties reproducing spatial differences of ion source functions and variances of travel times. Despite the observed limitations, we conclude that time lapse ERT can be qualitatively and quantitatively informative with respect to processes affecting the fate of nitrate in arable soils.

  14. Iron-induced reactive oxygen species mediate transporter DMT1 endocytosis and iron uptake in intestinal epithelial cells.

    PubMed

    Esparza, Andrés; Gerdtzen, Ziomara P; Olivera-Nappa, Alvaro; Salgado, J Cristian; Núñez, Marco T

    2015-10-15

    Recent evidence shows that iron induces the endocytosis of the iron transporter dimetal transporter 1 (DMT1) during intestinal absorption. We, and others, have proposed that iron-induced DMT1 internalization underlies the mucosal block phenomena, a regulatory response that downregulates intestinal iron uptake after a large oral dose of iron. In this work, we investigated the participation of reactive oxygen species (ROS) in the establishment of this response. By means of selective surface protein biotinylation of polarized Caco-2 cells, we determined the kinetics of DMT1 internalization from the apical membrane after an iron challenge. The initial decrease in DMT1 levels in the apical membrane induced by iron was followed at later times by increased levels of DMT1. Addition of Fe(2+), but not of Cd(2+), Zn(2+), Cu(2+), or Cu(1+), induced the production of intracellular ROS, as detected by 2',7'-dichlorofluorescein (DCF) fluorescence. Preincubation with the antioxidant N-acetyl-l-cysteine (NAC) resulted in increased DMT1 at the apical membrane before and after addition of iron. Similarly, preincubation with the hydroxyl radical scavenger dimethyl sulfoxide (DMSO) resulted in the enhanced presence of DMT1 at the apical membrane. The decrease of DMT1 levels at the apical membrane induced by iron was associated with decreased iron uptake