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Mark A. Widdowson

Publications and source records attributed to Mark A. Widdowson.

10 recordsLinked to original sources
USGS2014

Modeling long-term trends of chlorinated ethene contamination at a public supply well

A mass-balance solute-transport modeling approach was used to investigate the effects of dense nonaqueous phase liquid (DNAPL) volume, composition, and generation of daughter products on simulated and measured long-term trends of chlorinated ethene (CE) concentrations at a public supply well. The model was built by telescoping a calibrated regional three-dimensional MODFLOW model to the capture zone of a public supply well that has a history of CE contamination. The local model was then used to simulate the interactions between naturally occurring organic carbon that acts as an electron donor, and dissolved oxygen (DO), CEs, ferric iron, and sulfate that act as electron acceptors using the Sequential Electron Acceptor Model in three dimensions (SEAM3D) code. The modeling results indicate that asymmetry between rapidly rising and more gradual falling concentration trends over time suggests a DNAPL rather than a dissolved source of CEs. Peak concentrations of CEs are proportional to the volume and composition of the DNAPL source. The persistence of contamination, which can vary from a few years to centuries, is proportional to DNAPL volume, but is unaffected by DNAPL composition. These results show that monitoring CE concentrations in raw water produced by impacted public supply wells over time can provide useful information concerning the nature of contaminant sources and the likely future persistence of contamination.

New Jersey↗
USGS2013

Modeling the effects of naturally occurring organic carbon on chlorinated ethene transport to a public supply well

The vulnerability of public supply wells to chlorinated ethene (CE) contamination in part depends on the availability of naturally occurring organic carbon to consume dissolved oxygen (DO) and initiate reductive dechlorination. This was quantified by building a mass balance model of the Kirkwood-Cohansey aquifer, which is widely used for public water supply in New Jersey. This model was built by telescoping a calibrated regional three-dimensional (3D) MODFLOW model to the approximate capture zone of a single public supply well that has a history of CE contamination. This local model was then used to compute a mass balance between dissolved organic carbon (DOC), particulate organic carbon (POC), and adsorbed organic carbon (AOC) that act as electron donors and DO, CEs, ferric iron, and sulfate that act as electron acceptors (EAs) using the Sequential Electron Acceptor Model in three dimensions (SEAM3D) code. SEAM3D was constrained by varying concentrations of DO and DOC entering the aquifer via recharge, varying the bioavailable fraction of POC in aquifer sediments, and comparing observed and simulated vertical concentration profiles of DO and DOC. This procedure suggests that approximately 15% of the POC present in aquifer materials is readily bioavailable. Model simulations indicate that transport of perchloroethene (PCE) and its daughter products trichloroethene (TCE), cis -dichloroethene ( cis -DCE), and vinyl chloride (VC) to the public supply well is highly sensitive to the assumed bioavailable fraction of POC, concentrations of DO entering the aquifer with recharge, and the position of simulated PCE source areas in the flow field. The results are less sensitive to assumed concentrations of DOC in aquifer recharge. The mass balance approach used in this study also indicates that hydrodynamic processes such as advective mixing, dispersion, and sorption account for a significant amount of the observed natural attenuation in this system.

New Jersey↗
USGS2013

Modeling the long-term fate of agricultural nitrate in groundwater in the San Joaquin Valley, California

Nitrate contamination of groundwater systems used for human water supplies is a major environmental problem in many parts of the world. Fertilizers containing a variety of reduced nitrogen compounds are commonly added to soils to increase agricultural yields. But the amount of nitrogen added during fertilization typically exceeds the amount of nitrogen taken up by crops. Oxidation of reduced nitrogen compounds present in residual fertilizers can produce substantial amounts of nitrate which can be transported to the underlying water table. Because nitrate concentrations exceeding 10 mg/L in drinking water can have a variety of deleterious effects for humans, agriculturally derived nitrate contamination of groundwater can be a serious public health issue. The Central Valley aquifer of California accounts for 13 percent of all the groundwater withdrawals in the United States. The Central Valley, which includes the San Joaquin Valley, is one of the most productive agricultural areas in the world and much of this groundwater is used for crop irrigation. However, rapid urbanization has led to increasing groundwater withdrawals for municipal public water supplies. That, in turn, has led to concern about how contaminants associated with agricultural practices will affect the chemical quality of groundwater in the San Joaquin Valley. Crop fertilization with various forms of nitrogen-containing compounds can greatly increase agricultural yields. However, leaching of nitrate from soils due to irrigation has led to substantial nitrate contamination of shallow groundwater. That shallow nitrate-contaminated groundwater has been moving deeper into the Central Valley aquifer since the 1960s. Denitrification can be an important process limiting the mobility of nitrate in groundwater systems. However, substantial denitrification requires adequate sources of electron donors in order to drive the process. In many cases, dissolved organic carbon (DOC) and particulate organic carbon (POC) are the primary electron donors driving active denitrification in groundwater. The purpose of this chapter is to use a numerical mass balance modeling approach to quantitatively compare sources of electron donors (DOC, POC) and electron acceptors (dissolved oxygen, nitrate, and ferric iron) in order to assess the potential for denitrification to attenuate nitrate migration in the Central Valley aquifer.

California↗
USGS2012

Potentially bioavailable natural organic carbon and hydrolyzable amino acids in aquifer sediments

This study evaluated the relationship between concentrations of operationally defined potentially bioavailable organic -carbon (PBOC) and hydrolyzable amino acids (HAAs) in sediments collected from a diverse range of chloroethene--contaminated sites. Concentrations of PBOC and HAA were measured using aquifer sediment samples collected at six selected study sites. Average concentrations of total HAA and PBOC ranged from 1.96 ± 1.53 to 20.1 ± 25.6 mg/kg and 4.72 ± 0.72 to 443 ± 65.4 mg/kg, respectively. Results demonstrated a statistically significant positive relationship between concentrations of PBOC and total HAA present in the aquifer sediment (p < 0.05). Higher levels of HAA were consistently observed at sites with greater levels of PBOC and first-order decay rates. Because amino acids are known to be readily biodegradable carbon compounds, this relationship suggests that the sequential chemical extraction procedure used to measure PBOC is a useful indicator of bioavailable carbon in aquifer sediments. This, in turn, is consistent with the interpretation that PBOC measurements can be used for estimating the amount of natural organic carbon available for driving the reductive dechlorination of chloroethenes in groundwater systems.

Ground Water Monitoring and Remediation↗
USGS2012

Threshold amounts of organic carbon needed to initiate reductive dechlorination in groundwater systems

Aquifer sediment and groundwater chemistry data from 15 Department of Defense facilities located throughout the United States were collected and analyzed with the goal of estimating the amount of natural organic carbon needed to initiate reductive dechlorination in groundwater systems. Aquifer sediments were analyzed for hydroxylamine and NaOH-extractable organic carbon, yielding a probable underestimate of potentially bioavailable organic carbon (PBOC). Aquifer sediments were also analyzed for total organic carbon (TOC) using an elemental combustion analyzer, yielding a probable overestimate of bioavailable carbon. Concentrations of PBOC correlated linearly with TOC with a slope near one. However, concentrations of PBOC were consistently five to ten times lower than TOC. When mean concentrations of dissolved oxygen observed at each site were plotted versus PBOC, it showed that anoxic conditions were initiated at approximately 200 mg/kg of PBOC. Similarly, the accumulation of reductive dechlorination daughter products relative to parent compounds increased at a PBOC concentration of approximately 200 mg/kg. Concentrations of total hydrolysable amino acids (THAA) in sediments also increased at approximately 200 mg/kg, and bioassays showed that sediment CO 2 production correlated positively with THAA. The results of this study provide an estimate for threshold amounts of bioavailable carbon present in aquifer sediments (approximately 200 mg/kg of PBOC; approximately 1,000 to 2,000 mg/kg of TOC) needed to support reductive dechlorination in groundwater systems.

Remediation Journal↗
USGS2010

Internal inconsistencies in dispersion-dominated models that incorporate chemical and microbial kinetics

Current understanding of transport processes in aquifers is limited by lack of precise point chemical concentration measurements. Recently, however, some careful measurements of vertical chemical concentration profiles have been made at several locations around the world that appear to support a consistent picture concerning the persistence of large vertical concentration gradients in aquifers and, by implication, the existence of very small vertical transverse dispersivities. These data were obtained in aquifers supporting microbial activity. Data analysis using a mathematical model which considers microbial degradation coupled to nutrient and oxygen transport indicates that a vertical transverse dispersivity on the order of 0.1 cm or less is consistent with the concentration gradients that were measured. The existence of such large gradients and low dispersivities is not consistent with the use of two-dimensional vertically averaged (areal) models as currently applied, especially if one is interested in the development of transport models with predictive capability beyond that associated with standard calibration and extrapolation. Even three-dimensional models with large vertical transverse dispersivities compared to those measured will produce results inconsistent with measurements. Microbial-chemical activity is very sensitive to concentration distributions. Smearing of the oxygen profile can result in the prediction of aerobic activity where, in fact, none exists.

Water Resources Research↗
USGS2007

Estimating cleanup times for groundwater contamination remediation strategies

This article presents the Natural Attenuation Software (NAS), available as a free download from Virginia Polytechnic University, which can help remedial project managers and their contractors estimate the time of groundwater remediation through consideration of such natural attenuation processes as advection, dispersion, sorption, source zone depletion, and biodegradation. NAS consists of a combination of computational tools implemented in three main interactive modules. The article discusses testing and evaluation of NAS along with expected benefits of the software tool.

Journal - American Water Works Association↗
USGS2007

A framework for assessing the sustainability of monitored natural attenuation

The sustainability of monitored natural attenuation (MNA) over time depends upon (1) the presence of chemical/biochemical processes that transform wastes to innocuous byproducts, and (2) the availability of energy to drive these processes to completion. The presence or absence of contaminant-transforming chemical/biochemical processes can be determined by observing contaminant mass loss over time and space (mass balance). The energy available to drive these processes to completion can be assessed by measuring the pool of metabolizable organic carbon available in a system, and by tracing the flow of this energy to available electron acceptors (energy balance). For the special case of chlorinated ethenes in ground-water systems, for which a variety of contaminant-transforming biochemical processes exist, natural attenuation is sustainable when the pool of bioavailable organic carbon is large relative to the carbon flux needed to drive biodegradation to completion. These principles are illustrated by assessing the sustainability of MNA at a chlorinated ethene-contaminated site in Kings Bay, Georgia. Approximately 1,000 kilograms of perchloroethene (PCE) was released to a municipal landfill in the 1978-1980 timeframe, and the resulting plume of chlorinated ethenes migrated toward a nearby housing development. A numerical model, built using the sequential electron acceptor model code (SEAM3D), was used to quantify mass and energy balance in this system. The model considered the dissolution of non-aqueous phase liquid (NAPL) as the source of the PCE, and was designed to trace energy flow from dissolved organic carbon to available electron acceptors in the sequence oxygen > chlorinated ethenes > ferric iron > sulfate > carbon dioxide. The model was constrained by (1) comparing simulated and measured rates of ground-water flow, (2) reproducing the observed distribution of electron-accepting processes in the aquifer, (3) comparing observed and measured concentrations of chlorinated ethenes, and (4) reproducing the observed production and subsequent dilution of dissolved chloride, a final degradation product of chloroethene biodegradation. Simulations using the constrained model indicated that an average flux of 5 milligrams per liter per day of organic carbon (CH2O) per model cell (25 square meters) is required to support the short-term sustainability of MNA. Because this flux is small relative to the pool of renewable organic carbon (about 4.7 x 107 milligrams [mg] per model cell) present in the soil zone and non-renewable carbon (about 6.9 x 108 mg per model cell) in an organic-rich sediment layer overlying the aquifer, the long-term sustainability of MNA is similarly large. This study illustrates that the short- and long-term sustainability of MNA can be assessed by: 1. Estimating the time required for contaminants to dissolve/disperse/degrade under ambient hydrologic conditions (time of remediation). 2. Quantifying the organic carbon flux to the system needed to consume competing electron acceptors (oxygen) and direct electron flow toward chloroethene degradation (short-term sustainability). 3. Comparing the required flux of organic carbon to the pool of renewable and non-renewable organic carbon given the estimated time of remediation (long-term sustainability). These are general principles that can be used to assess the sustainability of MNA in any hydrologic system.

Circular↗
USGS2003

Methodology for estimating times of remediation associated with monitored natural attenuation

Natural attenuation processes combine to disperse, immobilize, and biologically transform anthropogenic contaminants, such as petroleum hydrocarbons and chlorinated ethenes, in ground-water systems. The time required for these processes to lower contaminant concentrations to levels protective of human health and the environment, however, varies widely between different hydrologic systems, different chemical contaminants, and varying amounts of contaminants. This report outlines a method for estimating timeframes required for natural attenuation processes, such as dispersion, sorption, and biodegradation, to lower contaminant concentrations and mass to predetermined regulatory goals in groundwater systems. The time-of-remediation (TOR) problem described in this report is formulated as three interactive components: (1) estimating the length of a contaminant plume once it has achieved a steady-state configuration from a source area of constant contaminant concentration, (2) estimating the time required for a plume to shrink to a smaller, regulatoryacceptable configuration when source-area contaminant concentrations are lowered by engineered methods, and (3) estimating the time needed for nonaqueous phase liquid (NAPL) contaminants to dissolve, disperse, and biodegrade below predetermined levels in contaminant source areas. This conceptualization was used to develop Natural Attenuation Software (NAS), an interactive computer aquifers. NAS was designed as a screening tool and requires the input of detailed site information about hydrogeology, redox conditions, and the distribution of contaminants. Because NAS is based on numerous simplifications of hydrologic, microbial, and geochemical processes, the program may introduce unacceptable errors for highly heterogeneous hydrologic systems. In such cases, application of the TOR framework outlined in this report may require more detailed, site-specific digital modeling. The NAS software may be downloaded from the Web site http://www.cee.vt.edu/NAS/ Application of NAS illustrates several general characteristics shared by all TOR problems. First, the distance of stabilization of a contaminant plume is strongly dependent on the natural attenuation capacity of particular ground-water systems. The time that it takes a plume to reach a steady-state configuration, however, is independent of natural attenuation capacity. Rather, the time of stabilization is most strongly affected by the sorptive capacity of the aquifer, which is dependent on the organic matter content of the aquifer sediments, as well as the sorptive properties of individual contaminants. As a general rule, a high sorptive capacity retards a plume.s growth or shrinkage, and increases the time of stabilization. Finally, the time of NAPL dissolution depends largely on NAPL mass, composition, geometry, and hydrologic factors, such as ground-water flow rates. An example TOR analysis for petroleum hydrocarbon NAPL was performed for the Laurel Bay site in South Carolina. About 500 to 1,000 pounds of gasoline leaked into the aquifer at this site in 1991, and the NAS simulations suggested that TOR would be on the order of 10 years for soluble and poorly sorbed compounds, such as benzene and methyl tertiary-butyl ether (MTBE). Conversely, TOR would be on the order of 40 years for less soluble, more strongly sorbed compounds, such as toluene, ethylbenzene, and xylenes (TEX). These TOR estimates are roughly consistent with contaminant concentrations observed over 10 years of monitoring at this site where benzene and MTBE concentrations were observed to decrease rapidly and are approaching regulatory maximum concentration limits, whereas toluene, ethylbenzene, and xylene concentrations decreased at a slower rate and have remained relatively high. An example TOR analysis for petroleum hydrocarbon NAPL was performed for the Laurel Bay site in South Carolina.

South Carolina↗