T. Prabhakar Clement

Processes in microbial transport in the natural subsurface

This is a review of physical, chemical, and biological processes governing microbial transport in the saturated subsurface. We begin with the conceptual models of the biophase that underlie mathematical descriptions of these processes and the physical processes that provide the framework for recent focus on less understood processes. Novel conceptual models of the interactions between cell surface structures and other surfaces are introduced, that are more realistic than the oft-relied upon DLVO theory of colloid stability. Biological processes reviewed include active adhesion/detachment (cell partitioning between aqueous and solid phase initiated by cell metabolism) and chemotaxis (motility in response to chemical gradients). We also discuss mathematical issues involved in upscaling results from the cell scale to the Darcy and field scales. Finally, recent studies at the Oyster, Virginia field site are discussed in terms of relating laboratory results to field scale problems of bioremediation and pathogen transport in the natural subsurface.

A modified Langmuir-Freundlich isotherm model for simulating pH-dependent adsorption effects.

Analytical isotherm equations such as Langmuir and Freundlich isotherms are widely used for modeling adsorption data. However, these isotherms are primarily useful for simulating data collected at a fixed pH value and cannot be easily adapted to simulate pH-dependent adsorption effects. Therefore, most adsorption studies currently use numerical surface-complexation models (SCMs), which are more complex and time consuming than traditional analytical isotherm models. In this work, we propose a new analytical isotherm model, identified as the modified Langmuir-Freundlich (MLF) isotherm, which can be used to simulate pH-dependent adsorption. The MLF isotherm uses a linear correlation between pH and affinity coefficient values. We validated the proposed MLF isotherm by predicting arsenic adsorption onto two different types of sorbents: pure goethite and goethite-coated sand. The MLF model gave good predictions for both experimental and surface complexation-model predicted datasets for these two sorbents. The proposed analytical isotherm framework can help reduce modeling complexity, model development time, and computational efforts. One of the limitations of the proposed method is that it is currently valid only for single-component systems. Furthermore, the model requires a system-specific pH. vs. affinity coefficient relation. Despite these limitations, the approach provides a promising analytical framework for simulating pH-dependent adsorption effects.

Natural Attenuation of BTEX Compounds: Model Development and Field-Scale Application

Benzene, toluene, ethyl benzene and xylene (BTEX) dissolved into ground water and migrated from a light nonaqueous phase liquid (LNAPL) source in a sandy aquifer near a petroleum, oil, and lubricants (POL) facility at Hill Air Force Base (AFB), Utah. Field observations indicated that microbially mediated BTEX degradation using multiple terminal electron-accepting processes including aerobic respiration, denitrification, Fe(III) reduction, sulfate reduction, and methanogenesis has occurred in the aquifer. To study the transport and transformation of dissolved BTEX compounds under natural conditions, a reactive flow and transport model incorporating biochemical multispecies interactions and BTEX was developed. The BTEX, oxygen, nitrate, Fe(II), sulfate, and methane plumes calculated by the model agree reasonably well with field observations. The first-order biodegradation rate constants, estimated based on model calibration are 0.051, 0.031, 0.005, 0.004, and 0.002 day(-1) for aerobic respiration, denitrification, Fe(III), sulfate reduction, and methanogenesis, respectively. The results of a sensitivity analysis show that the saturated aquifer thickness, hydraulic conductivity, and reaction rate constants are the most critical parameters controlling the natural attenuation of BTEX at this site. The hydraulic conductivity and aquifer thickness were found to be the key factors affecting the restoration of oxygen, nitrate, and sulfate after their interaction with the BTEX plume. The multispecies reactive transport modeling effort, describing BTEX degradation mediated by multiple electron-accepting processes, represents one of the few attempts to date to quantify a complete sequence of natural attenuation processes with a detailed field data set. Because the case study is representative of many petroleum-product contaminated sites, the results and insights obtained from this study are of general interest and relevance to other fuel-hydrocarbon natural attenuation sites.

Generalized solution to multispecies transport equations coupled with a first‐order reaction network

A generalized solution methodology is presented for deriving analytical solutions to multispecies transport equations coupled with multiparent, serial, parallel, converging, diverging, and/or reversible first-order reactions. The method is flexible for solving one-, two-, or three-dimensional advection-dispersion equations that are coupled with a set of first-order reactions. However, a major limitation is that the method cannot be used for solving multispecies transport equations with different retardation factors. Mathematical steps are provided to illustrate how the general solution method can be derived using linear transformation principles and to show why the method would fail when the retardation factors are different. Derivations are also presented to demonstrate how the Sun et al. (1999b) method for solving sequential reactive transport problems, which was previously presented without any fundamental analysis, can be deduced from the general solution. The results of the presented solution scheme for a test problem compare well with the numerical solution computed using the RT3D code. The proposed methodology is useful for developing simple analytical models that can be used to perform screening simulations and can be used to test complex multispecies transport codes.

Impacts of the 2004 tsunami on groundwater resources in Sri Lanka

The 26 December 2004 tsunami caused widespread destruction and contamination of coastal aquifers across southern Asia. Seawater filled domestic open dug wells and also entered the aquifers via direct infiltration during the first flooding waves and later as ponded seawater infiltrated through the permeable sands that are typical of coastal aquifers. In Sri Lanka alone, it is estimated that over 40,000 drinking water wells were either destroyed or contaminated. From February through September 2005, a team of United States, Sri Lankan, and Danish water resource scientists and engineers surveyed the coastal groundwater resources of Sri Lanka to develop an understanding of the impacts of the tsunami and to provide recommendations for the future of coastal water resources in south Asia. In the tsunami-affected areas, seawater was found to have infiltrated and mixed with fresh groundwater lenses as indicated by the elevated groundwater salinity levels. Seawater infiltrated through the shallow vadose zone as well as entered aquifers directly through flooded open wells. Our preliminary transport analysis demonstrates that the intruded seawater has vertically mixed in the aquifers because of both forced and free convection. Widespread pumping of wells to remove seawater was effective in some areas, but overpumping has led to upconing of the saltwater interface and rising salinity. We estimate that groundwater recharge from several monsoon seasons will reduce salinity of many sandy Sri Lankan coastal aquifers. However, the continued sustainability of these small and fragile aquifers for potable water will be difficult because of the rapid growth of human activities that results in more intensive groundwater pumping and increased pollution. Long-term sustainability of coastal aquifers is also impacted by the decrease in sand replenishment of the beaches due to sand mining and erosion.

A case study for demonstrating the application of U.S. EPA's monitored natural attenuation screening protocol at a hazardous waste site

Natural attenuation assessment data, collected at a Superfund site located in Louisiana, USA, are presented. The study site is contaminated with large quantities of DNAPL waste products. Source characterization data indicated that chlorinated ethene and ethane compounds are the major contaminants of concern. This case study illustrates the steps involved in implementing the U.S. EPAs [U.S. EPA, 1998. Technical protocol for evaluating natural attenuation of chlorinated solvents in ground water, by Wiedmeier, T.H., Swnason, M.A., Moutoux, D.E., Gordon, E.K., Wilson, J.T., Wilson, B.H., Kampbell, D.H., Hass, P.E., Miller, R.N., Hansen, J. E., Chapelle, F.H., Office of Research and Development, EPA/600/R-98/128] monitored natural attenuation (MNA) screening protocol at this chlorinated solvent site. In the first stage of the MNA assessment process, the field data collected from four monitoring wells located in different parts of the plume were used to complete a biodegradation scoring analysis recommended by the protocol. The analysis indicates that the site has the potential for natural attenuation. In the second stage, a detailed conceptual model was developed to identify various contaminant transport pathways and exposure points. The U.S. EPA model and BIOCHLOR was used to assess whether the contaminants are attenuating at a reasonable rate along these transport paths so that MNA can be considered as a feasible remedial option for the site. The site data along with the modeling results indicate that the chlorinated ethene and chlorinated ethane plumes are degrading and will attenuate within 1000 ft down gradient from the source, well before reaching the identified exposure point Therefore, MNA can be considered as one of the feasible remediation options for the site.

A Decomposition Method for Solving Coupled Multi–Species Reactive Transport Problems

Concerns over the problems associated with mixed waste groundwater contamination have created a need for more complex models that can represent reactive contaminant fate and transport in the subsurface. In the literature, partial differential equations describing solute transport in porous media are solved either for a single reactive species in one, two or three dimensions, or for a limited number of reactive species in one dimension. Those solutions are constrained by many simplifying assumptions. Often, it is desirable to simulate transport in two or three dimensions for a more practical system that might have multiple reactive species. This paper presents a decomposition method to solve the partial differential equations of multi–dimensional, multi–species transport problems that are coupled by linear reactions. A matrix method is suggested as a tool for describing the reaction network. In this way, the level of complexity required to solve the multi–species reactive transport problem is significantly reduced.

Authorship Matrix: A Rational Approach to Quantify Individual Contributions and Responsibilities in Multi-Author Scientific Articles

We propose a rational method for addressing an important question—who deserves to be an author of a scientific article? We review various contentious issues associated with this question and recommend that the scientific community should view authorship in terms of contributions and responsibilities, rather than credits. We propose a new paradigm that conceptually divides a scientific article into four basic elements: ideas, work, writing, and stewardship. We employ these four fundamental elements to modify the well-known International Committee of Medical Journal Editors (ICMJE) authorship guidelines. The modified ICMJE guidelines are then used as the basis to develop an approach to quantify individual contributions and responsibilities in multi-author articles. The outcome of the approach is an authorship matrix, which can be used to answer several nagging questions related to authorship.

Long-term monitoring data to describe the fate of polycyclic aromatic hydrocarbons in Deepwater Horizon oil submerged off Alabama's beaches

The 2010 Deepwater Horizon (DWH) catastrophe had considerable impact on the ∼ 50 km long sandy beach system located along the Alabama shoreline. We present a four-year dataset to characterize the temporal evolution of various polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologs trapped in the residual oil buried along the shoreline. Field samples analyzed include the first arrival oil collected from Perdido Bay, Alabama in June 2010, and multiple oil spill samples collected until August 2014. Our field data show that, as of August 2014, DWH oil is still trapped along Alabamas beaches as submerged oil, predominately in the form of surface residual oil balls (SRBs). Chemical characterization data show that various PAHs present in the spilled oil (MC252 crude) weathered by about 45% to 100% when the oil was floating over the open ocean system in the Gulf of Mexico. Light PAHs, such as naphthalenes, were fully depleted, whereas heavy PAHs, such as chrysenes, were only partially depleted by about 45%. However, the rate of PAH weathering appears to have decreased significantly once the oil was buried within the partially-closed SRB environment. Concentration levels of several heavy PAHs have almost remained constant over the past 4 years. Our data also show that evaporation was most likely the primary weathering mechanism for PAH removal when the oil was floating over the ocean, although photo-degradation and other physico-chemical processes could have contributed to some additional weathering. Chemical data presented in this study indicate that submerged oil containing various heavy PAHs (for example, parent and alkylated chrysenes) is likely to remain in the beach system for several years. It is also likely that the organisms living in these beach environments would have an increased risk of exposure to heavy PAHs trapped in the non-recoverable form of buried DWH oil spill residues.

Complexities in hindcasting models--when should we say enough is enough?

Groundwater models are routinely used in hindcasting applications to predict the past concentration levels in contaminated aquifers. These predictions are used in risk assessment and epidemiological studies, which are often completed either for resolving a court case or for developing a public-policy solution. Hindcast groundwater modeling studies utilize a variety of computer tools with complexity levels ranging from simple analytical models to detailed three-dimensional, multiphase, multispecies, reactive transport models. The aim of this study is to explore the value of using complex reactive transport models in hindcasting studies that have limited historic data. I review a chlorinated solvent exposure problem that occurred at a U.S. Marine Corp Base in Camp Lejeune, North Carolina and use it as an example to discuss the limits of hindcasting modeling exercises. The lessons learned from the study are used to reflect upon the following questions related to model complexity: How should we decide how much is enough? Who should decide when enough is enough?