James W. Jawitz

Nutrient loads exported from managed catchments reveal emergent biogeochemical stationarity

Complexity of heterogeneous catchments poses challenges in predicting biogeochemical responses to human alterations and stochastic hydro?climatic drivers. Human interferences and climate change may have contributed to the demise of hydrologic stationarity, but our synthesis of a large body of observational data suggests that anthropogenic impacts have also resulted in the emergence of effective biogeochemical stationarity in managed catchments. Long?term monitoring data from the Mississippi?Atchafalaya River Basin (MARB) and the Baltic Sea Drainage Basin (BSDB) reveal that inter?annual variations in loads (LT) for total?N (TN) and total?P (TP), exported from a catchment are dominantly controlled by discharge (QT) leading inevitably to temporal invariance of the annual, flow?weighted concentration, Cf = (LT/QT). Emergence of this consistent pattern across diverse managed catchments is attributed to the anthropogenic legacy of accumulated nutrient sources generating memory, similar to ubiquitously present sources for geogenic constituents that also exhibit a linear LT?QT relationship. These responses are characteristic of transport?limited systems. In contrast, in the absence of legacy sources in less?managed catchments, Cf values were highly variable and supply limited. We offer a theoretical explanation for the observed patterns at the event scale, and extend it to consider the stochastic nature of rainfall/flow patterns at annual scales. Our analysis suggests that: (1) expected inter?annual variations in LT can be robustly predicted given discharge variations arising from hydro?climatic or anthropogenic forcing, and (2) water?quality problems in receiving inland and coastal waters would persist until the accumulated storages of nutrients have been substantially depleted. The finding has notable implications on catchment management to mitigate adverse water?quality impacts, and on acceleration of global biogeochemical cycles.

Do geographically isolated wetlands influence landscape functions

Geographically isolated wetlands (GIWs), those surrounded by uplands, exchange materials, energy, and organisms with other elements in hydrological and habitat networks, contributing to landscape functions, such as flow generation, nutrient and sediment retention, and biodiversity support. GIWs constitute most of the wetlands in many North American landscapes, provide a disproportionately large fraction of wetland edges where many functions are enhanced, and form complexes with other water bodies to create spatial and temporal heterogeneity in the timing, flow paths, and magnitude of network connectivity. These attributes signal a critical role for GIWs in sustaining a portfolio of landscape functions, but legal protections remain weak despite preferential loss from many landscapes. GIWs lack persistent surface water connections, but this condition does not imply the absence of hydrological, biogeochemical, and biological exchanges with nearby and downstream waters. Although hydrological and biogeochemical connectivity is often episodic or slow (e.g., via groundwater), hydrologic continuity and limited evaporative solute enrichment suggest both flow generation and solute and sediment retention. Similarly, whereas biological connectivity usually requires overland dispersal, numerous organisms, including many rare or threatened species, use both GIWs and downstream waters at different times or life stages, suggesting that GIWs are critical elements of landscape habitat mosaics. Indeed, weaker hydrologic connectivity with downstream waters and constrained biological connectivity with other landscape elements are precisely what enhances some GIW functions and enables others. Based on analysis of wetland geography and synthesis of wetland functions, we argue that sustaining landscape functions requires conserving the entire continuum of wetland connectivity, including GIWs.

Controlled release, blind test of DNAPL remediation by ethanol flushing

A dense nonaqueous phase liquid (DNAPL) source zone was established within a sheet-pile isolated cell through a controlled release of perchloroethylene (PCE) to evaluate DNAPL remediation by in-situ cosolvent flushing. Ethanol was used as the cosolvent, and the main remedial mechanism was enhanced dissolution based on the phase behavior of the water-ethanol-PCE system. Based on the knowledge of the actual PCE volume introduced into the cell, it was estimated that 83 L of PCE were present at the start of the test. Over a 40-day period, 64% of the PCE was removed by flushing the cell with an alcohol solution of approximately 70% ethanol and 30% water. High removal efficiencies at the end of the test indicated that more PCE could have been removed had it been possible to continue the demonstration. The ethanol solution extracted from the cell was recycled during the test using activated carbon and air stripping treatment. Both of these treatment processes were successful in removing PCE for recycling purposes, with minimal impact on the ethanol content in the treated fluids. Results from pre- and post-flushing partitioning tracer tests overestimated the treatment performance. However, both of these tracer tests missed significant amounts of the PCE present, likely due to inaccessibility of the PCE. The tracer results suggest that some PCE was inaccessible to the ethanol solution which led to the inefficient PCE removal rates observed. The flux-averaged aqueous PCE concentrations measured in the post-flushing tracer test were reduced by a factor of 3 to 4 in the extraction wells that showed the highest PCE removal compared to those concentrations in the pre-flushing tracer test.

Miscible fluid displacement stability in unconfined porous media:: Two-dimensional flow experiments and simulations

In situ flushing groundwater remediation technologies, such as cosolvent flushing, rely on the stability of the interface between the resident and displacing fluids for efficient removal of contaminants. Contrasts in density and viscosity between the resident and displacing fluids can adversely affect the stability of the displacement front. Petroleum engineers have developed techniques to describe these types of processes; however, their findings do not necessarily translate directly to aquifer remediation. The purpose of this laboratory study was to investigate how density and viscosity contrasts affected cosolvent displacements in unconfined porous media characterized by the presence of a capillary fringe. Two-dimensional flow laboratory experiments, which were partially scaled to a cosolvent flushing field experiment, were conducted to determine potential implications of flow instabilities in homogeneous sand packs. Numerical simulations were also conducted to investigate the differential impact of fluid property contrasts in unconfined and confined systems. The results from these experiments and simulations indicated that the presence of a capillary fringe was an important factor in the displacement efficiency. Buoyant forces can act to carry a lighter-than-water cosolvent preferentially into the capillary fringe during displacement of the resident groundwater. During subsequent water flooding, buoyancy forces can act to effectively trap the cosolvent in the capillary fringe, contributing to the inefficient removal of cosolvent from the aquifer.

Laboratory investigation of flux reduction from dense non-aqueous phase liquid (DNAPL) partial source zone remediation by enhanced dissolution.

This study investigated the benefits of partial removal of dense nonaqueous phase liquid (DNAPL) source zones using enhanced dissolution in eight laboratory scale experiments. The benefits were assessed by characterizing the relationship between reductions in DNAPL mass and the corresponding reduction in contaminant mass flux. Four flushing agents were evaluated in eight controlled laboratory experiments to examine the effects of displacement fluid property contrasts and associated override and underride on contaminant flux reduction (R(j)) vs. mass reduction (R(m)) relationships (R(j)(R(m))): 1) 50% ethanol/50% water (less dense than water), 2) 40% ethyl-lactate/60% water (more dense than water), 3) 18% ethanol/26% ethyl-lactate/56% water (neutrally buoyant), and 4) 2% Tween-80 surfactant (also neutrally buoyant). For each DNAPL architecture evaluated, replicate experiments were conducted where source zone dissolution was conducted with a single flushing event to remove most of the DNAPL from the system, and with multiple shorter-duration floods to determine the path of the R(j)(R(m)) relationship. All of the single-flushing experiments exhibited similar R(j)(R(m)) relationships indicating that override and underride effects associated with cosolvents did not significantly affect the remediation performance of the agents. The R(j)(R(m)) relationship of the multiple injection experiments for the cosolvents with a density contrast with water tended to be less desirable in the sense that there was less R(j) for a given R(m). UTCHEM simulations supported the observations from the laboratory experiments and demonstrated the capability of this model to predict R(j)(R(m)) relationships for non-uniformly distributed NAPL sources.

Simplified contaminant source depletion models as analogs of multiphase simulators

Four simplified dense non-aqueous phase liquid (DNAPL) source depletion models recently introduced in the literature are evaluated for the prediction of long-term effects of source depletion under natural gradient flow. These models are simple in form (a power function equation is an example) but are shown here to serve as mathematical analogs to complex multiphase flow and transport simulators. The spill and subsequent dissolution of DNAPLs was simulated in domains having different hydrologic characteristics (variance of the log conductivity field=0.2, 1 and 3) using the multiphase flow and transport simulator UTCHEM. The dissolution profiles were fitted using four analytical models: the equilibrium streamtube model (ESM), the advection dispersion model (ADM), the power law model (PLM) and the Damkohler number model (DaM). All four models, though very different in their conceptualization, include two basic parameters that describe the mean DNAPL mass and the joint variability in the velocity and DNAPL distributions. The variability parameter was observed to be strongly correlated with the variance of the log conductivity field in the ESM and ADM but weakly correlated in the PLM and DaM. The DaM also includes a third parameter that describes the effect of rate-limited dissolution, but here this parameter was held constant as the numerical simulations were found to be insensitive to local-scale mass transfer. All four models were able to emulate the characteristics of the dissolution profiles generated from the complex numerical simulator, but the one-parameter PLM fits were the poorest, especially for the low heterogeneity case.

Remediation of NAPL Source Zones: Lessons Learned from Field Studies at Hill and Dover AFB

Innovative remediation studies were conducted between 1994 and 2004 at sites contaminated by nonaqueous phase liquids (NAPLs) at Hill and Dover AFB, and included technologies that mobilize, solubilize, and volatilize NAPL: air sparging (AS), surfactant flushing, cosolvent flooding, and flushing with a complexing-sugar solution. The experiments proved that aggressive remedial efforts tailored to the contaminant can remove more than 90% of the NAPL-phase contaminant mass. Site-characterization methods were tested as part of these field efforts, including partitioning tracer tests, biotracer tests, and mass-flux measurements. A significant reduction in the groundwater contaminant mass flux was achieved despite incomplete removal of the source. The effectiveness of soil, groundwater, and tracer based characterization methods may be site and technology specific. Employing multiple methods can improve characterization. The studies elucidated the importance of small-scale heterogeneities on remediation effectiveness, and fomented research on enhanced-delivery methods. Most contaminant removal occurs in hydraulically accessible zones, and complete removal is limited by contaminant mass stored in inaccessible zones. These studies illustrated the importance of understanding the fluid dynamics and interfacial behavior of injected fluids on remediation design and implementation. The importance of understanding the dynamics of NAPL-mixture dissolution and removal was highlighted. The results from these studies helped researchers better understand what processes and scales are most important to include in mathematical models used for design and data analysis. Finally, the work at these sites emphasized the importance and feasibility of recycling and reusing chemical agents, and enabled the implementation and success of follow-on full-scale efforts.

Convergence of DNAPL Source Strength Functions with Site Age

Dissolution of dense nonaqueous phase liquid (DNAPL) source zones can be accurately predicted based on appropriate characterization of the source zone architecture, which controls the rate of mass discharge or source strength function. However, the architecture changes temporally as the source zone mass is depleted by dissolution. To generalize comparisons between contaminated sites with different porewater velocities or contaminant solubilities, site age is defined in terms of the fraction of contaminant mass that has been eluted from the source zone by aqueous dissolution. Here changes in DNAPL architecture during dissolution of a source zone were measured by light transmission visualization in laboratory flow chambers. Architectures measured at ages corresponding to initial conditions, 20, 50, and 90% mass removal were used in an equilibrium streamtube (EST) model to accurately predict subsequent dissolution. It is shown both experimentally and theoretically that as DNAPL contaminated sites age, fractional reductions in contaminant discharge and mass converge to become equal, regardless of the initial architecture. This behavior is a consequence of convergence from log-normal to exponential behavior. Analysis of errors in dissolution predictions suggests that the age of many contaminated sites is likely sufficient that architecture and source strength function characterization may not be necessary as it can be assumed with reasonable accuracy that future dissolution will follow an exponential decay model.

Back diffusion from thin low permeability zones.

Aquitards can serve as long-term contaminant sources to aquifers when contaminant mass diffuses from the aquitard following aquifer source mass depletion. This study describes analytical and experimental approaches to understand reactive and nonreactive solute transport in a thin aquitard bounded by an adjacent aquifer. A series of well-controlled laboratory experiments were conducted in a two-dimensional flow chamber to quantify solute diffusion from a high-permeability sand into and subsequently out of kaolinite clay layers of vertical thickness 15 mm, 20 mm, and 60 mm. One-dimensional analytical solutions were developed for diffusion in a finite aquitard with mass exchange with an adjacent aquifer using the method of images. The analytical solutions showed very good agreement with measured breakthrough curves and aquitard concentration distributions measured in situ by light reflection visualization. Solutes with low retardation accumulated more stored mass with greater penetration distance in the aquitard compared to high-retardation solutes. However, because the duration of aquitard mass release was much longer, high-retardation solutes have a greater long-term back diffusion risk. The error associated with applying a semi-infinite domain analytical solution to a finite diffusion domain increases as a function of the system relative diffusion length scale, suggesting that the solutions using image sources should be applied in cases with rapid solute diffusion and/or thin clay layers. The solutions presented here can be extended to multilayer aquifer/low-permeability systems to assess the significance of back diffusion from thin layers.

Mechanistic Biogeochemical Model Applications for Everglades Restoration: A Review of Case Studies and Suggestions for Future Modeling Needs

Mechanistic biogeochemical model applications for freshwater wetland ecosystems are reviewed with an emphasis on applications in the Florida Everglades. Two significant human impacts on the Everglades have been hydrologic alteration and phosphorus (P) enrichment. Thus, it is important for research conducted in support of Everglades restoration to integrate understanding of the coupled effects of hydrologic and biogeochemical processes. Models are tools that can facilitate such integration, but an important challenge in model development is determining the appropriate level of model complexity. Previous wetland biogeochemical and flow modeling efforts are categorized across the spectrum of complexity from empirical and spatially aggregated to mechanistic and spatially distributed. The focus of this review is on mercury and P, as these two elements represent major environmental concerns in this ecosystem. Two case studies of coupled hydrologic and biogeochemical modeling for P transport are described in further detail to illustrate the implications of different levels of model complexity. The case study simulation results on time series TP data revealed that the mechanistic biogeochemical model with more complexity did not guarantee significantly better simulation accuracy compared to the simpler one. It is concluded that the level of model complexity should be represented appropriately based on the modeling objectives, hypotheses to be tested, and data availability. Finally, better integration between data collection and model development is encouraged as cross-fertilization between these processes may stimulate improved system understanding.