SecurEarth: A Crosscutting Initiative for the Geo- and Environmental Sciences

"..addressing critical energy and environmental problems will probably have a larger societal impact than curing cancer. Now we just have to convince Congress of that." - Steven Chu, Nobel Laureate and Director of the Lawrence Berkeley National Laboratory, in a 2005 presentation at the LBNL "..a new national energy program is essential and must be initiated with the intensity and commitment of the Manhattan Project, and sustained until this problem is solved" "Considering the urgency of the energy problem, the magnitude of the needed scientific breakthroughs, and the historic rate of scientific discovery, current efforts will likely be too little, too late." - 2003, Basic Energy Science Advisory Committee recommendation Over the next several decades, the U.S. will be facing critical decisions regarding extraction and utilization of the Earth’s resources and stewardship of the Earth. Demands for energy (e.g., fossil, geothermal) and useable water supplies, as well as for places and methods to deal with waste products (e.g., carbon dioxide, radioactive waste), are increasing rapidly. Moreover, the demands are usually interdependent and conflicting. Postponing decisions will become increasingly difficult and unpopular. Complex policy decisions (examples?) with long-range consequences that must be made in the near future will depend on several types of information: social, economic, political and scientific. To balance the urgency with which social, economic, and political information will be used, pertinent scientific information must also be readily available, practical, and possessed with high degree of certainty. Therefore, there is a vital need for timely and relevant scientific information related to energy, resource and environmental issues that will enable decision makers to make better decisions related to public policy. SECUREarth was launched several years ago as a proposition by scientists from DOE national laboratories, universities and industry who recognized two fundamental issues related to the role of the earth sciences, particularly subsurface science, in addressing resource and environmental issues. The first is that we are still struggling to make connections between pore-, molecular- and cellular-scale information and the complex, large-scale systems where we most need predictive capabilities. To take advantage of the growing wealth of scientific information about physical, chemical and biological processes we need to facilitate research leading to an understanding of how individual processes are coupled, how whole-systems behave and can be modeled, and how the response of large-scale systems to natural or engineered changes can be reasonably predicted. It will also be important to assess both the level of uncertainty associated with predictions and the potential consequences of that uncertainty, as well as to develop strategies for minimizing that uncertainty. The second issue for SECUREarth is that the rate at which the science related to the earth’s environment is progressing will not produce some of the most critically needed information by the time policy decisions must be made. Therefore, SECUREarth is concerned both with opening new frontiers for the earth sciences, and also with increasing the rate at which the science becomes useful and available to inform decision makers. The vision for SECUREarth is to facilitate the direction of funding from government and industry sources in order t

Hybrid Numerical Methods for Multiscale Simulations of Subsurface Biogeochemical Processes

Many subsurface flow and transport problems of importance today involve coupled non-linear flow, transport, and reaction in media exhibiting complex heterogeneity. In particular, problems involving biological mediation of reactions fall into this class of problems. Recent experimental research has revealed important details about the physical, chemical, and biological mechanisms involved in these processes at a variety of scales ranging from molecular to laboratory scales. However, it has not been practical or possible to translate detailed knowledge at small scales into reliable predictions of field-scale phenomena important for environmental management applications. A large assortment of numerical simulation tools have been developed, each with its own characteristic scale including molecular (e.g., molecular dynamics), microbial (e.g., cellular automata or particle individual-based models), pore (e.g., lattice-Boltzmann, pore network models, and discrete particle methods such as smoothed particle hydrodynamics) and continuum scales (e.g., traditional partial differential equations solved by finite difference or finite element methods). While many problems can be effectively addressed by one of these models at a single scale, some problems may require explicit integration of models across multiple scales. We are developing a hybrid multi-scale subsurface reactive transport modeling framework that integrates models with diverse representations of physics, chemistry and biology at different scales (sub-pore, pore and continuum). The modeling framework is being designed to take advantage of advanced computational technologies including parallel code components using the Common Component Architecture, parallel solvers, gridding, data and workflow management, and visualization. This paper describes the specific methods/codes being used at each scale, techniques used to directly and adaptively couple across model scales, and preliminary results of application to a multi-scale model of mineral precipitation at a solute mixing interface

Advancing Reactive Tracer Methods for Measurement of Thermal Evolution in Geothermal Reservoirs: Final Report

The injection of cold fluids into engineered geothermal system (EGS) and conventional geothermal reservoirs may be done to help extract heat from the subsurface or to maintain pressures within the reservoir (e.g., Rose et al., 2001). As these injected fluids move along fractures, they acquire heat from the rock matrix and remove it from the reservoir as they are extracted to the surface. A consequence of such injection is the migration of a cold-fluid front through the reservoir (Figure 1) that could eventually reach the production well and result in the lowering of the temperature of the produced fluids (thermal breakthrough). Efficient operation of an EGS as well as conventional geothermal systems involving cold-fluid injection requires accurate and timely information about thermal depletion of the reservoir in response to operation. In particular, accurate predictions of the time to thermal breakthrough and subsequent rate of thermal drawdown are necessary for reservoir management, design of fracture stimulation and well drilling programs, and forecasting of economic return. A potential method for estimating migration of a cold front between an injection well and a production well is through application of reactive tracer tests, using chemical whose rate of degradation is dependent on the reservoir temperature between the two wells (e.g., Robinson 1985). With repeated tests, the rate of migration of the thermal front can be determined, and the time to thermal breakthrough calculated. While the basic theory behind the concept of thermal tracers has been understood for some time, effective application of the method has yet to be demonstrated. This report describes results of a study that used several methods to investigate application of reactive tracers to monitoring the thermal evolution of a geothermal reservoir. These methods included (1) mathematical investigation of the sensitivity of known and hypothetical reactive tracers, (2) laboratory testing of novel tracers that would improve method sensitivity, (3) development of a software tool for design and interpretation of reactive tracer tests and (4) field testing of the reactive tracer temperature monitoring concept

FLUID FLOW, SOLUTE MIXING AND PRECIPITATION IN POROUS MEDIA

Reactions that lead to the formation of mineral precipitates, colloids or growth of biofilms in porous media often depend on the molecular-level diffusive mixing. For example, for the formation of mineral phases, exceeding the saturation index for a mineral is a minimum requirement for precipitation to proceed. Solute mixing frequently occurs at the interface between two solutions each containing one or more soluble reactants, particularly in engineered systems where contaminant degradation or modification or fluid flow are objectives. Although many of the fundamental component processes involved in the deposition or solubilization of solid phases are reasonably well understood, including precipitation equilibrium and kinetics, fluid flow and solute transport, the deposition of chemical precipitates, biofilms and colloidal particles are all coupled to flow, and the science of such coupled processes is not well developed. How such precipitates (and conversely, dissolution of solids) are distributed in the subsurface along flow paths with chemical gradients is a complex and challenging problem. This is especially true in systems that undergo rapid change where equilibrium conditions cannot be assumed, particularly in subsurface systems where reactants are introduced rapidly, compared to most natural flow conditions, and where mixing fronts are generated. Although the concept of dispersion in porous media is frequently used to approximate mixing at macroscopic scales, dispersion does not necessarily describe pore-level or molecular level mixing that must occur for chemical and biological reactions to be possible. An example of coupling between flow, mixing and mineral precipitation, with practical applications to controlling fluid flow or contaminant remediation in subsurface environments is shown in the mixing zone between parallel flowing solutions. Two- and three-dimensional experiments in packed-sand media were conducted where solutions containing calcium and carbonate ions came into contact along a parallel flow boundary and mixed by dispersion and diffusion. The result is the propagation of calcium carbonate precipitates along the solution-solution boundary in the direction of flow. As carbonate precipitates fill the pore space mixing of the two solutions is restricted and therefore precipitation, flow, and transport are coupled. The distribution of carbonate phases is a complex interaction involving precipitation and dissolution kinetics, which are functions of pore-scale saturation indices and solute ratios, heterogeneous vs. homogeneous nucleation and growth mechanisms and changes in porosity and flow. Experimental and modeling results illustrate challenges in understanding the macroscopic and microscopic phenomena that depend on solute mixing, the relevance of molecular and pore-scale processes to the macroscopic behavior, and potential impact on metal mobility in porous media. Mineral precipitation and changes in porosity are simulated at the pore-scale using the Smooth Particle Hydrodynamics method. Macroscopic simulations were performed using discretized, continuum-scale modeling with parameterization representing macroscopic media properties. One of the modeling goals is to use pore-scale simulations to provide the basis for parameterization of macroscopic (more practical) model predictions

The Effect of the CO32- to Ca2+ Ion activity ratio on calcite precipitation kinetics and Sr2+ partitioning

<p>Abstract</p> <p>Background</p> <p>A proposed strategy for immobilizing trace metals in the subsurface is to stimulate calcium carbonate precipitation and incorporate contaminants by co-precipitation. Such an approach will require injecting chemical amendments into the subsurface to generate supersaturated conditions that promote mineral precipitation. However, the formation of reactant mixing zones will create gradients in both the saturation state and ion activity ratios (i.e., <inline-formula><m:math name="1467-4866-13-1-i1" xmlns:m="http://www.w3.org/1998/Math/MathML"><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:msub><m:mrow><m:mi>O</m:mi></m:mrow><m:mrow><m:mn>3</m:mn></m:mrow></m:msub></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">-</m:mo></m:mrow></m:msup></m:mrow></m:msub><m:mo class="MathClass-bin">/</m:mo><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">+</m:mo></m:mrow></m:msup></m:mrow></m:msub></m:math></inline-formula>). To better understand the effect of ion activity ratios on CaCO₃precipitation kinetics and Sr²⁺co-precipitation, experiments were conducted under constant composition conditions where the supersaturation state (Ω) for calcite was held constant at 9.4, but the ion activity ratio <inline-formula><m:math name="1467-4866-13-1-i2" xmlns:m="http://www.w3.org/1998/Math/MathML"><m:mrow><m:mo class="MathClass-open">(</m:mo><m:mrow><m:mi>r</m:mi><m:mo class="MathClass-rel">=</m:mo><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:msub><m:mrow><m:mi>O</m:mi></m:mrow><m:mrow><m:mn>3</m:mn></m:mrow></m:msub></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">-</m:mo></m:mrow></m:msup></m:mrow></m:msub><m:mo class="MathClass-bin">/</m:mo><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">+</m:mo></m:mrow></m:msup></m:mrow></m:msub></m:mrow><m:mo class="MathClass-close">)</m:mo></m:mrow></m:math></inline-formula> was varied between 0.0032 and 4.15.</p> <p>Results</p> <p>Calcite was the only phase observed, by XRD, at the end of the experiments. Precipitation rates increased from 41.3 ± 3.4 μmol m^-2min^-1at <it>r = </it>0.0315 to a maximum rate of 74.5 ± 4.8 μmol m^-2min^-1at <it>r = </it>0.306 followed by a decrease to 46.3 ± 9.6 μmol m^-2min^-1at <it>r </it>= 1.822. The trend was simulated using a simple mass transfer model for solute uptake at the calcite surface. However, precipitation rates at fixed saturation states also evolved with time. Precipitation rates accelerated for low <it>r </it>values but slowed for high <it>r </it>values. These trends may be related to changes in effective reactive surface area. The <inline-formula><m:math xmlns:m="http://www.w3.org/1998/Math/MathML" name="1467-4866-13-1-i1"><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:msub><m:mrow><m:mi>O</m:mi></m:mrow><m:mrow><m:mn>3</m:mn></m:mrow></m:msub></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">-</m:mo></m:mrow></m:msup></m:mrow></m:msub><m:mo class="MathClass-bin">/</m:mo><m:msub><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mi>C</m:mi><m:msup><m:mrow><m:mi>a</m:mi></m:mrow><m:mrow><m:mn>2</m:mn><m:mo class="MathClass-bin">+</m:mo></m:mrow></m:msup></m:mrow></m:msub></m:math></inline-formula> ratios did not affect the distribution coefficient for Sr in calcite (D^P_Sr²⁺), apart from the indirect effect associated with the established positive correlation between D^P_Sr²⁺and calcite precipitation rate.</p> <p>Conclusion</p> <p>At a constant supersaturation state (Ω = 9.4), varying the ion activity ratio affects the calcite precipitation rate. This behavior is not predicted by affinity-based rate models. Furthermore, at the highest ion ratio tested, no precipitation was observed, while at the lowest ion ratio precipitation occurred immediately and valid rate measurements could not be made. The maximum measured precipitation rate was 2-fold greater than the minima, and occurred at a carbonate to calcium ion activity ratio of 0.306. These findings have implications for predicting the progress and cost of remediation operations involving enhanced calcite precipitation where mineral precipitation rates, and the spatial/temporal distribution of those rates, can have significant impacts on the mobility of contaminants.</p

EMSL Pore Scale Modeling Challenge/Workshop

Report covers the background for the workshop, objectives, important research directions, necessary capabilities and overall recommendations

Oral abstracts 3: RA Treatment and outcomesO13. Validation of jadas in all subtypes of juvenile idiopathic arthritis in a clinical setting

Background: Juvenile Arthritis Disease Activity Score (JADAS) is a 4 variable composite disease activity (DA) score for JIA (including active 10, 27 or 71 joint count (AJC), physician global (PGA), parent/child global (PGE) and ESR). The validity of JADAS for all ILAR subtypes in the routine clinical setting is unknown. We investigated the construct validity of JADAS in the clinical setting in all subtypes of JIA through application to a prospective inception cohort of UK children presenting with new onset inflammatory arthritis. Methods: JADAS 10, 27 and 71 were determined for all children in the Childhood Arthritis Prospective Study (CAPS) with complete data available at baseline. Correlation of JADAS 10, 27 and 71 with single DA markers was determined for all subtypes. All correlations were calculated using Spearman's rank statistic. Results: 262/1238 visits had sufficient data for calculation of JADAS (1028 (83%) AJC, 744 (60%) PGA, 843 (68%) PGE and 459 (37%) ESR). Median age at disease onset was 6.0 years (IQR 2.6-10.4) and 64% were female. Correlation between JADAS 10, 27 and 71 approached 1 for all subtypes. Median JADAS 71 was 5.3 (IQR 2.2-10.1) with a significant difference between median JADAS scores between subtypes (p < 0.01). Correlation of JADAS 71 with each single marker of DA was moderate to high in the total cohort (see Table 1). Overall, correlation with AJC, PGA and PGE was moderate to high and correlation with ESR, limited JC, parental pain and CHAQ was low to moderate in the individual subtypes. Correlation coefficients in the extended oligoarticular, rheumatoid factor negative and enthesitis related subtypes were interpreted with caution in view of low numbers. Conclusions: This study adds to the body of evidence supporting the construct validity of JADAS. JADAS correlates with other measures of DA in all ILAR subtypes in the routine clinical setting. Given the high frequency of missing ESR data, it would be useful to assess the validity of JADAS without inclusion of the ESR. Disclosure statement: All authors have declared no conflicts of interest. Table 1Spearman's correlation between JADAS 71 and single markers DA by ILAR subtype ILAR Subtype Systemic onset JIA Persistent oligo JIA Extended oligo JIA Rheumatoid factor neg JIA Rheumatoid factor pos JIA Enthesitis related JIA Psoriatic JIA Undifferentiated JIA Unknown subtype Total cohort Number of children 23 111 12 57 7 9 19 7 17 262 AJC 0.54 0.67 0.53 0.75 0.53 0.34 0.59 0.81 0.37 0.59 PGA 0.63 0.69 0.25 0.73 0.14 0.05 0.50 0.83 0.56 0.64 PGE 0.51 0.68 0.83 0.61 0.41 0.69 0.71 0.9 0.48 0.61 ESR 0.28 0.31 0.35 0.4 0.6 0.85 0.43 0.7 0.5 0.53 Limited 71 JC 0.29 0.51 0.23 0.37 0.14 -0.12 0.4 0.81 0.45 0.41 Parental pain 0.23 0.62 0.03 0.57 0.41 0.69 0.7 0.79 0.42 0.53 Childhood health assessment questionnaire 0.25 0.57 -0.07 0.36 -0.47 0.84 0.37 0.8 0.66 0.4

Transport, Targeting, and Applications of Metallic Functional Nanoparticles for Degradation of DNAPL Chlorinated Organic solvents

The goals of this project have been to synthesize reactive metal colloids capable of: (1) reductively degrading chlorinated solvents, (2) being transported in porous media, and (3) partitioning from aqueous to non-aqueous solvents or accumulating at water/organic solvent interfaces. This project addresses the need for methods to efficiently remove or degrade dense non-aqueous phase liquid (DNAPL) contaminants, and that act as long-term sources of groundwater contamination through slow solubilization. This project builds on a general particle-based approach to subsurface contaminant remediation that has been demonstrated by others in the successful degradation of chlorinated compounds dissolved in groundwater using Fe(0) colloids. Delivering reactive particles directly to the surface of the DNAPL will decompose the pollutant into benign materials, reduce the migration of pollutant during treatment, possibly lead to encapsulation of the DNAPL, and reduce the time needed to remove residual pollution by other means, such as natural attenuation. Specific research challenges include: Synthesis of reactive particles that can be deployed in aqueous environments, modification of the particle surfaces, and modeling the transport behavior in porous media containing pendant chlorinated solvent

Advancing Reactive Tracer Methods for Measurement of Thermal Evolution in Geothermal Reservoirs: Final Report

The injection of cold fluids into engineered geothermal system (EGS) and conventional geothermal reservoirs may be done to help extract heat from the subsurface or to maintain pressures within the reservoir (e.g., Rose et al., 2001). As these injected fluids move along fractures, they acquire heat from the rock matrix and remove it from the reservoir as they are extracted to the surface. A consequence of such injection is the migration of a cold-fluid front through the reservoir (Figure 1) that could eventually reach the production well and result in the lowering of the temperature of the produced fluids (thermal breakthrough). Efficient operation of an EGS as well as conventional geothermal systems involving cold-fluid injection requires accurate and timely information about thermal depletion of the reservoir in response to operation. In particular, accurate predictions of the time to thermal breakthrough and subsequent rate of thermal drawdown are necessary for reservoir management, design of fracture stimulation and well drilling programs, and forecasting of economic return. A potential method for estimating migration of a cold front between an injection well and a production well is through application of reactive tracer tests, using chemical whose rate of degradation is dependent on the reservoir temperature between the two wells (e.g., Robinson 1985). With repeated tests, the rate of migration of the thermal front can be determined, and the time to thermal breakthrough calculated. While the basic theory behind the concept of thermal tracers has been understood for some time, effective application of the method has yet to be demonstrated. This report describes results of a study that used several methods to investigate application of reactive tracers to monitoring the thermal evolution of a geothermal reservoir. These methods included (1) mathematical investigation of the sensitivity of known and hypothetical reactive tracers, (2) laboratory testing of novel tracers that would improve method sensitivity, (3) development of a software tool for design and interpretation of reactive tracer tests and (4) field testing of the reactive tracer temperature monitoring concept