Bhavna Arora

Reactive transport codes for subsurface environmental simulation

A general description of the mathematical and numerical formulations used in modern numerical reactive transport codes relevant for subsurface environmental simulations is presented. The formulations are followed by short descriptions of commonly used and available subsurface simulators that consider continuum representations of flow, transport, and reactions in porous media. These formulations are applicable to most of the subsurface environmental benchmark problems included in this special issue. The list of codes described briefly here includes PHREEQC, HPx, PHT3D, OpenGeoSys (OGS), HYTEC, ORCHESTRA, TOUGHREACT, eSTOMP, HYDROGEOCHEM, CrunchFlow, MIN3P, and PFLOTRAN. The descriptions include a high-level list of capabilities for each of the codes, along with a selective list of applications that highlight their capabilities and historical development.

A reactive transport benchmark on heavy metal cycling in lake sediments

Sediments are active recipients of anthropogenic inputs, including heavy metals, but may be difficult to interpret without the use of numerical models that capture sediment-metal interactions and provide an accurate representation of the intricately coupled sedimentological, geochemical, and biological processes. The focus of this study is to present a benchmark problem on heavy metal cycling in lake sediments and to compare reactive transport models (RTMs) in their treatment of the local-scale physical and biogeochemical processes. This benchmark problem has been developed based on a previously published reactive-diffusive model of metal transport in the sediments of Lake Coeur d’Alene, Idaho. Key processes included in this model are microbial reductive dissolution of iron hydroxides (i.e., ferrihydrite), the release of sorbed metals into pore water, reaction of these metals with biogenic sulfide to form sulfide minerals, and sedimentation driving the burial of ferrihydrite and other minerals. This benchmark thus considers a multicomponent biotic reaction network with multiple terminal electron acceptors (TEAs), Fickian diffusive transport, kinetic and equilibrium mineral precipitation and dissolution, aqueous and surface complexation, as well as (optionally) sedimentation. To test the accuracy of the reactive transport problem solution, four RTMs—TOUGHREACT (TR), CrunchFlow (CF), PHREEQC, and PHT3D—have been used. Without sedimentation, all four models are able to predict similar trends of TEAs and dissolved metal concentrations, as well as mineral abundances. TR and CF are further used to compare sedimentation and compaction test cases. Results with different sedimentation rates are captured by both models, but since the codes do not use the same formulation for compaction, the results differ for this test case. Although, both TR and CF adequately capture the trends of aqueous concentrations and mineral abundances, the difference in results highlights the need to consider further the conceptual and numerical models that link transport, biogeochemical reactions, and sedimentation.

Water Table Dynamics and Biogeochemical Cycling in a Shallow, Variably-Saturated Floodplain

Three-dimensional variably saturated flow and multicomponent biogeochemical reactive transport modeling, based on published and newly generated data, is used to better understand the interplay of hydrology, geochemistry, and biology controlling the cycling of carbon, nitrogen, oxygen, iron, sulfur, and uranium in a shallow floodplain. In this system, aerobic respiration generally maintains anoxic groundwater below an oxic vadose zone until seasonal snowmelt-driven water table peaking transports dissolved oxygen (DO) and nitrate from the vadose zone into the alluvial aquifer. The response to this perturbation is localized due to distinct physico-biogeochemical environments and relatively long time scales for transport through the floodplain aquifer and vadose zone. Naturally reduced zones (NRZs) containing sediments higher in organic matter, iron sulfides, and non-crystalline U(IV) rapidly consume DO and nitrate to maintain anoxic conditions, yielding Fe(II) from FeS oxidative dissolution, nitrite from denitrification, and U(VI) from nitrite-promoted U(IV) oxidation. Redox cycling is a key factor for sustaining the observed aquifer behaviors despite continuous oxygen influx and the annual hydrologically induced oxidation event. Depth-dependent activity of fermenters, aerobes, nitrate reducers, sulfate reducers, and chemolithoautotrophs (e.g., oxidizing Fe(II), S compounds, and ammonium) is linked to the presence of DO, which has higher concentrations near the water table.

Identifying geochemical hot moments and their controls on a contaminated river floodplain system using wavelet and entropy approaches

Geochemical hot moments are defined here as short periods of time that are associated with disproportionally high levels of concentrations (biogeochemically-driven or transport-related) relative to longer intervening time periods. We used entropy and wavelet techniques to identify temporal variability in geochemical constituents and their controls along three transects within a contaminated floodplain system near Rifle CO. Results indicated that transport-dominated hot moments drove overall geochemical processing in the contaminated groundwater and seep zones. These hot moments were associated with seasonal hydrologic variability (~4 months) in the contaminated aquifer and with annual hydrologic cycle and residence times in the seep zone. Hot moments associated with a naturally reduced zone within the aquifer were found to be biogeochemically-driven, with a different dominant frequency (~3 months) and no correlation to hydrologic or weather variations, in contrast to what is observed in other regions of the floodplain. We interrogated complex, multivariate geochemical datasets to identify hot moments in a floodplain environment.We introduced a novel wavelet-entropy approach to classify hot moments and their distribution.Geochemical hot moments were found to be primarily transport-related/hydrologically-driven at the site.Within a naturally reduced zone, hot moments were dominated by lithologic characteristics (biogeochemically-driven).Water quality managers can use this wavelet-entropy tool for identifying contaminant hot moments in other floodplain settings.

Hot Spots and Hot Moments of Nitrogen in a Riparian Corridor

Author(s): Dwivedi, D; Arora, B; Steefel, CI; Dafflon, B; Versteeg, R | Abstract:

Benchmark problems for reactive transport modeling of the generation and attenuation of acid rock drainage

Acid rock drainage (ARD) is a problem of international relevance with substantial environmental and economic implications. Reactive transport modeling has proven a powerful tool for the process-based assessment of metal release and attenuation at ARD sites. Although a variety of models has been used to investigate ARD, a systematic model intercomparison has not been conducted to date. This contribution presents such a model intercomparison involving three synthetic benchmark problems designed to evaluate model results for the most relevant processes at ARD sites. The first benchmark (ARD-B1) focuses on the oxidation of sulfide minerals in an unsaturated tailing impoundment, affected by the ingress of atmospheric oxygen. ARD-B2 extends the first problem to include pH buffering by primary mineral dissolution and secondary mineral precipitation. The third problem (ARD-B3) in addition considers the kinetic and pH-dependent dissolution of silicate minerals under low pH conditions. The set of benchmarks was solved by four reactive transport codes, namely CrunchFlow, Flotran, HP1, and MIN3P. The results comparison focused on spatial profiles of dissolved concentrations, pH and pE, pore gas composition, and mineral assemblages. In addition, results of transient profiles for selected elements and cumulative mass loadings were considered in the intercomparison. Despite substantial differences in model formulations, very good agreement was obtained between the various codes. Residual deviations between the results are analyzed and discussed in terms of their implications for capturing system evolution and long-term mass loading predictions.

Attenuating Sulfidogenesis in a Soured Continuous Flow Column System with Perchlorate Treatment

Hydrogen sulfide production by sulfate reducing bacteria (SRB) is the primary cause of oil reservoir souring. Amending environments with chlorate or perchlorate [collectively denoted (per)chlorate] represents an emerging technology to prevent the onset of souring. Recent studies with perchlorate reducing bacteria (PRB) monocultures demonstrated that they have the innate capability to enzymatically oxidize sulfide, thus PRB may offer an effective means of reversing souring. (Per)chlorate may be effective by (i) direct toxicity to SRB; (ii) competitive exclusion of SRB by PRB; or (iii) reversal of souring through re-oxidation of sulfide by PRB. To determine if (per)chlorate could sweeten a soured column system and assign a quantitative value to each of the mechanisms we treated columns flooded with San Francisco bay water with temporally decreasing amounts (50, 25, and 12.5 mM) of (per)chlorate. Geochemistry and the microbial community structure were monitored and a reactive transport model was developed, Results were compared to columns treated with nitrate or untreated. Souring was reversed by all treatments at 50 mM but nitrate-treated columns began to re-sour when treatment concentrations decreased (25 mM). Re-souring was only observed in (per)chlorate-treated columns when concentrations were decreased to 12.5 mM and the extent of re-souring was less than the control columns. Microbial community analyses indicated treatment-specific community shifts. Nitrate treatment resulted in a distinct community enriched in genera known to perform sulfur cycling metabolisms and genera capable of nitrate reduction. (Per)chlorate treatment enriched for (per)chlorate reducing bacteria. (Per)chlorate treatments only enriched for sulfate reducing organisms when treatment levels were decreased. A reactive transport model of perchlorate treatment was developed and a baseline case simulation demonstrated that the model provided a good fit to the effluent geochemical data. Subsequent simulations teased out the relative role that each of the three perchlorate inhibition mechanisms played during different phases of the experiment. These results indicate that perchlorate addition is an effective strategy for both souring prevention and souring reversal. It provides insight into which organisms are involved, and illuminates the interactive effects of the inhibition mechanisms, further highlighting the versatility of perchlorate as a sweetening agent.

Evaluating temporal controls on greenhouse gas (GHG) fluxes in an Arctic tundra environment: An entropy-based approach

There is significant spatial and temporal variability associated with greenhouse gas (GHG) fluxes in high-latitude Arctic tundra environments. The objectives of this study are to investigate temporal variability in CO2 and CH4 fluxes at Barrow, AK and to determine the factors causing this variability using a novel entropy-based classification scheme. In particular, we analyzed which geomorphic, soil, vegetation and climatic properties most explained the variability in GHG fluxes (opaque chamber measurements) during the growing season over three successive years. Results indicate that multi-year variability in CO2 fluxes was primarily associated with soil temperature variability as well as vegetation dynamics during the early and late growing season. Temporal variability in CH4 fluxes was primarily associated with changes in vegetation during the growing season and its interactions with primary controls like seasonal thaw. Polygonal ground features, which are common to Arctic regions, also demonstrated significant multi-year variability in GHG fluxes. Our results can be used to prioritize field sampling strategies, with an emphasis on measurements collected at locations and times that explain the most variability in GHG fluxes. For example, we found that sampling primary environmental controls at the centers of high centered polygons in the month of September (when freeze-back period begins) can provide significant constraints on GHG flux variability - a requirement for accurately predicting future changes to GHG fluxes. Overall, entropy results document the impact of changing environmental conditions (e.g., warming, growing season length) on GHG fluxes, thus providing clues concerning the manner in which ecosystem properties may be shifted regionally in a future climate.

Comparison of Electrostatic and Non‐Electrostatic Models for U(VI) Sorption on Aquifer Sediments

A non-electrostatic generalized composite surface complexation model (SCM) was developed for U(VI) sorption on contaminated F-Area sediments from the U.S. Department of Energy Savannah River Site, South Carolina. The objective of this study was to test if a simpler, semi-empirical, non-electrostatic U(VI) sorption model (NEM) could achieve the same predictive performance as a SCM with electrostatic correction terms in describing U(VI) plume evolution and long-term mobility. One-dimensional reactive transport simulations considering key hydrodynamic processes, Al and Fe minerals, as well as H+ and U surface complexation, with and without electrostatic correction terms, were conducted. The NEM was first calibrated with laboratory batch H+ and U(VI) sorption data on F-Area sediments, and then the surface area of the NEM was adjusted to match field observations of dissolved U(VI). Modeling results indicate that the calibrated NEM was able to perform as well as the previously developed electrostatic model in predicting the long-term evolution of H+ and U(VI) at the site, given the variability of field-site data. The electrostatic and NEM models yield somewhat different results for the time period when basin discharge was active; however, it is not clear which modeling approach may be better to model this early time period because groundwater quality data during this period were not available. A key finding of this study is that the applicability of NEM (and thus robustness of its predictions) to the field system evolves with time and is strongly dependent on the pH range that was used to develop the model.