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Yabusaki, Steven B.

Publications and source records attributed to Yabusaki, Steven B..

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Quantifying Drivers of Methane Hydrobiogeochemistry in a Tidal River Floodplain System

The influence of coastal ecosystems on global greenhouse gas (GHG) budgets and their response to increasing inundation and salinization remains poorly constrained. In this study, we have integrated an uncertainty quantification (UQ) and ensemble machine learning (ML) framework to identify and rank the most influential processes, properties, and conditions controlling methane behavior in a freshwater floodplain responding to recently restored seawater inundation. Our unique multivariate, multiyear, and multi-site dataset comprises tidal creek and floodplain porewater observations encompassing water level, salinity, pH, temperature, dissolved oxygen (DO), dissolved organic carbon (DOC), total dissolved nitrogen (TDN), partial pressure of carbon dioxide (pCO 2 ), nitrous oxide (pN 2 O), methane (pCH 4 ), and the stable isotopic composition of methane (δ 13 CH 4 ). Additionally, we incorporated topographical data, soil porosity, hydraulic conductivity, and water retention parameters for UQ analysis using a previously developed 3D variably saturated flow and transport floodplain model for a physical mechanistic understanding of factors influencing groundwater levels and salinity and, therefore, CH 4 . Principal component analysis revealed that groundwater level and salinity are the most significant predictors of overall biogeochemical variability. The ensemble ML models and UQ analyses identified DO, water level, salinity, and temperature as the most influential factors for porewater methane levels and indicated that approximately 80% of the total variability in hourly water levels and around 60% of the total variability in hourly salinity can be explained by permeability, creek water level, and two van Genuchten water retention function parameters: the air-entry suction parameter α and the pore size distribution parameter m. These findings provide insights on the physicochemical factors in methane behavior in coastal ecosystems and their representation in local- to global-scale Earth system models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Resolving dynamic mineral-organic interactions in the rhizosphere by combining in-situ microsensors with plant-soil reactive transport modeling

Associations between minerals and organic matter represent one of the most important carbon storage mechanisms in soils. Plant roots are major sources of soil carbon, and resolving the dynamics and dominance of microbial consumption versus mineral sorption of root-derived carbon is critical to understanding soil carbon storage. Here we integrate in-situ rhizosphere microsensor and plant physiological measurements with a 3-D plant-soil reactive transport model to explore the fate of dissolved organic carbon (DOC) in the rhizosphere, particularly its microbial consumption and interaction with Fe oxide minerals. Over several days, a microdialysis probe sampling pore water at the root-soil interface of growing Vicia faba roots in live soil, revealed clear diel patterns of DOC concentration. Daytime DOC spikes coincided with peaks in leaf-level photosynthesis rates and were accompanied by declining redox potential and dissolved oxygen as well as increasing pH in the rhizosphere. Incorporating microsensor data into our modeling framework showed that the measured rapid loss of DOC after each mid-day spike could not be explained by consumption via aerobic respiration, nor via anaerobic respiration dominated by Fe oxide reduction. Rather, in the model, a large fraction of rhizosphere DOC was rapidly immobilized each day by adsorption to Fe oxides. Further, modeled microbial Fe reduction (fueled by DOC) did not mobilize significant organic carbon from Fe oxides during the day. Instead, the model predicted equilibrium desorption of organic carbon from Fe oxides at night. This new mechanistic modeling framework, which couples aboveground plant physiological measurements with non-destructive high-resolution monitoring of rhizosphere processes, has great potential for exploring the dynamics and balance of the various microbial reactions and mineral interactions controlling carbon transformations and storage in soils.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Severe declines in hydraulic capacity and associated carbon starvation drive mortality in seawater exposed Sitka-spruce (Picea sitchensis) trees

Abstract Sea-level rise is causing widespread tree mortality of coastal forests, with large consequences on the Earth system as a result of these forests’ importance in carbon and nutrient export. The mechanisms of mortality under these conditions are, however, poorly tested. We used wood anatomy traits, wood δ 13 C, and tree radial growth to retrospectively assess the physiological process of seawater effects on whole tree xylem hydraulic capacity, gas exchange, and radial growth. During the latter stages of mortality (2018–2019), we directly measured metrics of water use and carbon metabolism across trees having crowns ranging from fully foliated to completely defoliated to investigate mortality processes at the sub-annual scale. Upon seawater exposure, soil salinity increased and allocation to hydraulic function declined, resulting in a dramatic reduction in water supply to the crown, increased crown-level water stress, and subsequent crown foliage loss. Simultaneously, leaf-level photosynthetic capacity declined steeply with increasing salinity. The combined loss of crown foliage area and photosynthetic rates per unit leaf area promoted carbon starvation, while no evidence of hydraulic failure was observed. These results elucidate mechanisms of coastal forest death under seawater exposure, enabling more accurate modeling in the future.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Seawater exposure causes hydraulic damage in dying Sitka-spruce trees

Sea-level rise is one of the most critical challenges facing coastal ecosystems under climate change. Observations of elevated tree mortality in global coastal forests are increasing, but the mechanism of salinity-stress induced tree mortality is currently unknown. We monitored progressive mortality and associated gas exchange and hydraulic shifts in Sitka-spruce (Picea sitchensis) trees located within a salinity gradient under an ecosystem-scale change of seawater exposure in Washington State, USA. Percentage of live foliated crown (PLFC) decreased and tree mortality increased with increasing soil salinity during the study period. A strong reduction in gas exchange and xylem hydraulic conductivity (Ks) occurred during tree death, with an increase of the percentage loss of xylem conductivity (PLC) and turgor loss point (ptlp). Hydraulic and osmotic shifts reflected that hydraulic function declined from seawater exposure and dying trees were unable to support osmotic adjustment. Constrained gas exchange was strongly related to hydraulic damage at both stem and leaf levels. Significant correlations between foliar sodium (Na+) concentration and gas exchange and key hydraulic parameters (Ks, PLC and ptlp ) suggest that cellular injury related to the toxic effects of ion accumulation impacted the physiology of these dying trees. This study provides evidence of toxic effects on cellular function that become manifest in all aspects of plant functioning, leading to unfavourable osmotic and hydraulic conditions.

Zhang, Hongxia↗
DOE OSTI2021

Declining carbohydrate content of Sitka-spruce treesdying from seawater exposure

Abstract Increasing sea levels associated with climate change threaten the survival of coastal forests, yet the mechanisms by which seawater exposure causes tree death remain poorly understood. Despite the potentially crucial role of nonstructural carbohydrate (NSC) reserves in tree survival, their dynamics in the process of death under seawater exposure are unknown. Here we monitored progressive tree mortality and associated NSC storage in Sitka-spruce (Picea sitchensis) trees dying under ecosystem-scale increases in seawater exposure in western Washington, USA. All trees exposed to seawater, because of monthly tidal intrusion, experienced declining crown foliage during the sampling period, and individuals with a lower percentage of live foliated crown (PLFC) died faster. Tree PLFC was strongly correlated with subsurface salinity and needle ion contents. Total NSC concentrations in trees declined remarkably with crown decline, and reached extremely low levels at tree death (2.4% and 1.6% in leaves and branches, respectively, and 0.4% in stems and roots). Starch in all tissues was almost completely consumed, while sugars remained at a homeostatic level in foliage. The decreasing NSC with closer proximity to death and near zero starch at death are evidences that carbon starvation occurred during Sitka-spruce mortality during seawater exposure. Our results highlight the importance of carbon storage as an indicator of tree mortality risks under seawater exposure.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Antecedent conditions determine the biogeochemical response of coastal soils to seawater exposure

Coastal landscapes are increasingly exposed to seawater due to sea level rise and extreme weather events. The biogeochemical responses of these vulnerable ecosystems are poorly understood, limiting our ability to predict how their role in local and global biogeochemical cycles will shift under future conditions. Here we evaluate how antecedent conditions influence the biogeochemical response of soil to seawater inundation events based on a 42-day laboratory incubation experiment with soils collected from a natural salinity gradient across a coastal floodplain. We quantified influences of seawater inundation on intact soil cores through high-frequency carbon dioxide (CO 2 ) and methane (CH 4 ) gas fluxes measurements as well as ultrahigh resolution characterization of organic matter chemistry and metabolites. Mean CO 2 and CH 4 fluxes were higher after inundation compared to control cores for soils that had low in situ salinity. Soils with low in situ salinity also exhibited significant shifts in organic matter profiles after inundation, with surficial soils (0-7.5 cm) becoming more enriched in phenolic compounds, compared to deeper soils (7.5-15 cm). The number of biochemical transformations inferred from mass spectrometry increased significantly after inundation for soils with low in situ salinity, and a trend of decreasing thermodynamic favorability with increasing salinity was observed, suggesting an increase in microbial activity following inundation. Our results suggest that seawater inundation of low-salinity terrestrial environments can lead to increased microbial activity, preferential depletion of more thermodynamically favorable compounds, and increased soil carbon release. Finally, we conclude that the biogeochemical impacts of future seawater exposure will be modulated by antecedent conditions associated with landscape position within coastal watersheds.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

An efficient three-dimensional rhizosphere modeling capability to study the effect of root system architecture on soil water and reactive transport

This research was to develop a rhizosphere modeling capability for plant-soil interactions by integrating water and ion uptake and release from three dimensional (3D) root systems and 3D variably saturated flow and multicomponent reactive transport in soil. We combined open source software for simulating plant and soil interactions with parallel processing computational technologies to address highly-resolved root system architecture and soil hydrobiogeochemical processes. Simulation capability was demonstrated on Brachypodium distachyon . Our demonstration problem showed that availability of water and plant nutrients is controlled by the interplay between 1) transpiration-driven cycles of water uptake, root zone saturation and desaturation; 2) sorption and desorption via competitive ion exchange; 3) buildup of ions not taken up during kinetic uptake of nutrients/ions from pore water; and 4) advection, dispersion, and diffusion of ions in the soil. The uptake of water and ions by individual roots leads to dynamic, local gradients in ion concentrations. The resulting higher solution ionic strength can lead to increasing sorption of K+ and NH4+ on the soil exchange sites, despite their preferential absorption by roots. The modeling framework makes it possible to explore alternative conceptual models and improve the understanding of the biogeochemical and physical environment within the rhizosphere.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

Snowmelt Induced Hydrologic Perturbations Drive Dynamic Microbiological and Geochemical Behaviors across a Shallow Riparian Aquifer

Shallow riparian aquifers represent hotspots of biogeochemical activity in the arid western US. While these environments provide extensive ecosystem services, little is known of how natural environmental perturbations influence subsurface microbial communities and associated biogeochemical processes. Over a 6-month period we tracked the annual snowmelt-driven incursion of groundwater into the vadose zone of an aquifer adjacent to the Colorado River, leading to increased dissolved oxygen (DO) concentrations in the normally suboxic saturated zone. Strong biogeochemical heterogeneity was measured across the site, with abiotic reactions between DO and sulfide minerals driving rapid DO consumption and mobilization of redox active species in reduced aquifer regions. Conversely, extensive DO increases were detected in less reduced sediments. 16S rRNA gene surveys tracked microbial community composition within the aquifer, revealing strong correlations between increases in putative oxygen-utilizing chemolithoautotrophs and heterotrophs and rising DO concentrations. The gradual return to suboxic aquifer conditions favored increasing abundances of 16S rRNA sequences matching members of the Microgenomates (OP11) and Parcubacteria (OD1) that have been strongly implicated in fermentative processes. Microbial community stability measurements indicated that deeper aquifer locations were relatively less affected by geochemical perturbations, while communities in shallower locations exhibited the greatest change. Thus, reactive transport modeling of the geochemical and microbiological results supported field observations, suggesting that a predictive framework can be applied to develop a greater understanding of such environments.

58 GEOSCIENCES↗
DOE OSTI2016

Benchmarking Initiatives

Benchmarking has been recognized as an efficient tool for model validation as well as scientific collaboration. Several workshop series have been established to foster the benchmarking idea: setting up test cases with increasing complexity for method development and code comparison. In addition to representing model complexity, one of the key efforts is to develop codes that are suitable for modern HPC platforms such as PetaFlop supercomputers. It has been realized that those challenges are beyond single team capabilities. The Subsurface Environmental Simulation Benchmarking (SSBench) working group was initiated to develop, publish, and make publicly available well-described benchmark problems that could be used to demonstrate simulator conformance with norms established by the subsurface science and engineering community. SSBench supports the development of environmentally-relevant benchmark problem sets that provide rigorous tests for process model conceptualization, numerical implementation, process coupling, and accuracy. The initial SSBench focus on multicomponent reactive transport modeling reflects the expanding range of mechanisms and increasing complexity needed to address issues relevant to climate change, nuclear waste management, contaminant remediation, and pollution prevention.

benchmarking↗
DOE OSTI2016

Influence of hydrological, biogeochemical and temperature transients on subsurface carbon fluxes in a flood plain environment

Flood plains play a potentially important role in the global carbon cycle. The accumulation of organic matter in flood plains often induces the formation of chemically reduced groundwater and sediments along riverbanks. In this study, our objective is to evaluate the cumulative impact of such reduced zones, water table fluctuations, and temperature gradients on subsurface carbon fluxes in a flood plain at Rifle, Colorado located along the Colorado River. 2-D coupled variably-saturated, non-isothermal flow and biogeochemical reactive transport modeling was applied to improve our understanding of the abiotic and microbially mediated reactions controlling carbon dynamics at the Rifle site. Model simulations considering only abiotic reactions (thus ignoring microbial reactions) underestimated CO 2 partial pressures observed in the unsaturated zone and severely underestimated inorganic (and overestimated organic) carbon fluxes to the river compared to simulations with biotic pathways. Both model simulations and field observations highlighted the need to include microbial contributions from chemolithoautotrophic processes (e.g., Fe +2 and S -2 oxidation) to match locally-observed high CO 2 concentrations above reduced zones. Observed seasonal variations in CO 2 concentrations in the unsaturated zone could not be reproduced without incorporating temperature gradients in the simulations. Incorporating temperature fluctuations resulted in an increase in the annual groundwater carbon fluxes to the river by 170 % to 3.3 g m -2 d -1 , while including water table variations resulted in an overall decrease in the simulated fluxes. We thus conclude that spatial microbial and redox zonation as well as temporal fluctuations of temperature and water table depth contribute significantly to subsurface carbon fluxes in flood plains and need to be represented appropriately in model simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

A Uranium Bioremediation Reactive Transport Benchmark

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.

bioremediation↗
DOE OSTI2015

Reactive transport benchmarks for subsurface environmental simulation

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-resolution X-ray spectroscopy, have created new lines of research that can be used to inform the conceptualization of reactions and rate laws and validate mechanistic models. For example, spectroscopy has identified the oxidation states of key components and elemental distributions at increasingly smaller scales and lower concentrations; molecular biology has progressed from identifying the presence of microbes to characterization of which microbial communities are active and what they are doing (i.e., microbial function), which has led in turn to the identification of active processes under conditions beyond what analytical chemistry can discern; isotope ratios in pore water and solid phases that can be used to distinguish between biotic from abiotic processes, sorption from precipitation, and origin and age of groundwater. The other noteworthy development that is expanding the role of RTM in subsurface environmental modeling is he advance in computational technology that is enabling the simulation of more coupled processes with increasing mechanistic detail. In some cases, this involves the inclusion of more reactive species and/or microbial populations in the simulations; in other cases, the impact is through the ability to achieve high resolution of property distributions over longer simulated times. To achieve these ambitious objectives for subsurface reactive transport simulation, the subsurface science and engineering community is being driven 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. This expansion was enabled, in part, by advances in measurement technology, computing technology, and numerical techniques.

benchmarking↗
DOE OSTI2015

Technical Approach for Determining Key Parameters Needed for Modeling the Performance of Cast Stone for the Integrated Disposal Facility Performance Assessment

Washington River Protection Solutions (WRPS) and its contractors at Pacific Northwest National Laboratory (PNNL) and Savannah River National Laboratory (SRNL) are conducting a development program to develop / refine the cementitious waste form for the wastes treated at the ETF and to provide the data needed to support the IDF PA. This technical approach document is intended to provide guidance to the cementitious waste form development program with respect to the waste form characterization and testing information needed to support the IDF PA. At the time of the preparation of this technical approach document, the IDF PA effort is just getting started and the approach to analyze the performance of the cementitious waste form has not been determined. Therefore, this document looks at a number of different approaches for evaluating the waste form performance and describes the testing needed to provide data for each approach. Though the approach addresses a cementitious secondary aqueous waste form, it is applicable to other waste forms such as Cast Stone for supplemental immobilization of Hanford LAW. The performance of Cast Stone as a physical and chemical barrier to the release of contaminants of concern (COCs) from solidification of Hanford liquid low activity waste (LAW) and secondary wastes processed through the Effluent Treatment Facility (ETF) is of critical importance to the Hanford Integrated Disposal Facility (IDF) total system performance assessment (TSPA). The effectiveness of cementitious waste forms as a barrier to COC release is expected to evolve with time. PA modeling must therefore anticipate and address processes, properties, and conditions that alter the physical and chemical controls on COC transport in the cementitious waste forms over time. Most organizations responsible for disposal facility operation and their regulators support an iterative hierarchical safety/performance assessment approach with a general philosophy that modeling provides the critical link between the short-term understanding from laboratory and field tests, and the prediction of repository performance over repository time frames and scales. One common recommendation is that experiments be designed to permit the appropriate scaling in the models. There is a large contrast in the physical and chemical properties between the Cast Stone waste package and the IDF backfill and surrounding sediments. Cast Stone exhibits low permeability, high tortuosity, low carbonate, high pH, and low Eh whereas the backfill and native sediments have high permeability, low tortuosity, high carbonate, circumneutral pH, and high Eh. These contrasts have important implications for flow, transport, and reactions across the Cast Stone – backfill interface. Over time with transport across the interface and subsequent reactions, the sharp geochemical contrast will blur and there will be a range of spatially-distributed conditions. In general, COC mobility and transport will be sensitive to these geochemical variations, which also include physical changes in porosity and permeability from mineral reactions. Therefore, PA modeling must address processes, properties, and conditions that alter the physical and chemical controls on COC transport in the cementitious waste forms over time. Section 2 of this document reviews past Hanford PAs and SRS Saltstone PAs, which to date have mostly relied on the lumped parameter COC release conceptual models for TSPA predictions, and provides some details on the chosen values for the lumped parameters. Section 3 provides more details on the hierarchical modeling strategy and processes and mechanisms that control COC release. Section 4 summarizes and lists the key parameters for which numerical values are needed to perform PAs. Section 5 provides brief summaries of the methods used to measure the needed parameters and references to get more details.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Bicarbonate impact on U(VI) bioreduction in a shallow alluvial aquifer

Field-scale biostimulation and desorption tracer experiments conducted in a uranium (U) contaminated, shallow alluvial aquifer have provided insight into the coupling of microbiology, biogeochemistry, and hydrogeology that control U mobility in the subsurface. Initial experiments successfully tested the concept that Fe-reducing bacteria such as Geobacter sp. could enzymatically reduce soluble U(VI) to insoluble U(IV) during in situ electron donor amendment (Anderson et al., 2003; Williams et al., 2011). In parallel, in situ desorption tracer tests using bicarbonate amendment demonstrated rate-limited U(VI) desorption (Fox et al., 2012). These results and prior laboratory studies underscored the importance of enzymatic U(VI)-reduction and suggested the ability to combine desorption and bioreduction of U(VI). Here in this paper we report the results of a new field experiment in which bicarbonate-promoted uranium desorption and acetate amendment were combined and compared to an acetate amendment-only experiment in the same experimental plot. Results confirm that bicarbonate amendment to alluvial aquifer sediments desorbs U(VI) and increases the abundance of Ca-uranyl-carbonato complexes. At the same time, the rate of acetate-promoted enzymatic U(VI) reduction was greater in the presence of added bicarbonate in spite of the increased dominance of Ca-uranyl-carbonato aqueous complexes. A model-simulated peak rate of U(VI) reduction was ~3.8 times higher during acetate-bicarbonate treatment than under acetate-only conditions. Lack of consistent differences in microbial community structure between acetate-bicarbonate and acetate-only treatments suggest that a significantly higher rate of U(VI) reduction in the bicarbonate-impacted sediment may be due to a higher intrinsic rate of microbial reduction induced by elevated concentrations of the bicarbonate oxyanion. The findings indicate that bicarbonate amendment may be useful in improving the engineered bioremediation of uranium in aquifers.

58 GEOSCIENCES↗
DOE OSTI2014

Geochemical and Mineralogical Investigation of Uranium in Multi–element Contaminated, Organic–rich Subsurface Sediment

Alluvial sediments characterized by an abundance of refractory or lignitic organic carbon compounds and reduced Fe and S bearing mineral phases have been identified through drilling activities at the U.S. Department of Energy’s (DOE) Integrated Field Research Challenge (IFRC) site at Rifle, CO. Regions of the subsurface from which such sediments are derived are referred to as Naturally Reduced Zones (NRZ). We conducted a study with NRZ sediments with the objective to: i.) Characterize solid phase contamination of U and other co-contaminants; ii.) Document the occurrence of potential U host minerals; iii.) Determine U valence state and micron scale spatial association with co-contaminants. Macroscopic (wet chemical batch extractions and a column experiment), microscopic (SEM-EDS), and spectroscopic (Mössbauer, µ-XRF and XANES) techniques were employed. Results showed that sediments’ solid phase had significant concentrations of U, S, As, Zn, V, Cr, Cu and Se, and a remarkable assortment of potential U hosts (sorbents and/or electron donors), such as Fe oxides (hematite, magnetite, Al-substituted goethite), siderite, reduced Fe(II) bearing clays, sulfides of different types, Zn sulfide framboids and multi – element sulfides. Multi-contaminants, micron size (ca. 5 to 30 µm) areas of mainly U(IV) and some U(VI), and/or other electron scavengers or donors such as Se, As, Cr, and V were discovered in the sediments, suggesting complex micron-scale system responses to transient redox conditions, and different extent and rates of competing U redox reactions than those of single contaminant systems. Collectively, the results improve our understanding and ability to predict U and NRZ’s complex behavior and will delineate future research directions to further study both the natural attenuation and persistence of contaminant plumes and their contribution to groundwater contamination.

bioavailability↗
DOE OSTI2013

Effects of error covariance structure on estimation of model averaging weights and predictive performance

When conducting model averaging for assessing groundwater conceptual model uncertainty, the averaging weights are often evaluated using model selection criteria such as AIC, AICc, BIC, and KIC (Akaike Information Criterion, Corrected Akaike Information Criterion, Bayesian Information Criterion, and Kashyap Information Criterion, respectively). However, this method often leads to an unrealistic situation in which the best model receives overwhelmingly large averaging weight (close to 100%), which cannot be justified by available data and knowledge. It was found in this study that this problem was caused by using the covariance matrix, CE, of measurement errors for estimating the negative log likelihood function common to all the model selection criteria. This problem can be resolved by using the covariance matrix, Cek, of total errors (including model errors and measurement errors) to account for the correlation between the total errors. An iterative two-stage method was developed in the context of maximum likelihood inverse modeling to iteratively infer the unknown Cek from the residuals during model calibration. The inferred Cek was then used in the evaluation of model selection criteria and model averaging weights. While this method was limited to serial data using time series techniques in this study, it can be extended to spatial data using geostatistical techniques. The method was first evaluated in a synthetic study and then applied to an experimental study, in which alternative surface complexation models were developed to simulate column experiments of uranium reactive transport. It was found that the total errors of the alternative models were temporally correlated due to the model errors. The iterative two-stage method using Cek resolved the problem that the best model receives 100% model averaging weight, and the resulting model averaging weights were supported by the calibration results and physical understanding of the alternative models. Using Cek obtained from the iterative two-stage method also improved predictive performance of the individual models and model averaging in both synthetic and experimental studies.

error correlation↗