Michael C. Brooks

Changes in contaminant mass discharge from DNAPL source mass depletion: Evaluation at two field sites

Changes in contaminant fluxes resulting from aggressive remediation of dense nonaqueous phase liquid (DNAPL) source zone were investigated at two sites, one at Hill Air Force Base (AFB), Utah, and the other at Ft. Lewis Military Reservation, Washington. Passive Flux Meters (PFM) and a variation of the Integral Pumping Test (IPT) were used to measure fluxes in ten wells installed along a transect down-gradient of the trichloroethylene (TCE) source zone, and perpendicular to the mean groundwater flow direction. At both sites, groundwater and contaminant fluxes were measured before and after the source-zone treatment. The measured contaminant fluxes (J; ML(-2)T(-1)) were integrated across the well transect to estimate contaminant mass discharge (M(D); MT(-1)) from the source zone. Estimated M(D) before source treatment, based on both PFM and IPT methods, were approximately 76 g/day for TCE at the Hill AFB site; and approximately 640 g/day for TCE, and approximately 206 g/day for cis-dichloroethylene (DCE) at the Ft. Lewis site. TCE flux measurements made 1 year after source treatment at the Hill AFB site decreased to approximately 5 g/day. On the other hand, increased fluxes of DCE, a degradation byproduct of TCE, in tests subsequent to remediation at the Hill AFB site suggest enhanced microbial degradation after surfactant flooding. At the Ft. Lewis site, TCE mass discharge rates subsequent to remediation decreased to approximately 3 g/day for TCE and approximately 3 g/day for DCE approximately 1.8 years after remediation. At both field sites, PFM and IPT approaches provided comparable results for contaminant mass discharge rates, and show significant reductions (>90%) in TCE mass discharge as a result of DNAPL mass depletion from the source zone.

Lime Treatment of Explosives-Contaminated Soil from Munitions Plants and Firing Ranges

Microcosms were prepared using soils from munitions plants and active firing ranges and treated with hydrated lime. The presence of particulate explosives and co-contaminants, and the concentration of soil total organic carbon (TOC) on the alkaline hydrolysis reaction were studied. Trinitrobenzene (TNB) and dinitrobenzene (DNB) were sensitive to alkaline hydrolysis under these experimental conditions. The TNT metabolites, 2A- and 4A-DNT, were also removed, although more slowly than the parent compound, and the reaction required a higher pH (>12). RDX retention in the soil was proportional to the TOC content. The degradation intermediates of the alkaline hydrolysis reaction partitioned in the soil matrix in a manner similar to the parent. Solid particles of explosives are also degraded by alkaline hydrolysis. RDX and HMX exhibited 74 and 57% removal, respectively, in 21 days. TNT, as whole and broken grains, showed 83 and 99.9% removal in 21 days, respectively. The propellants, 2,4- and 2,6-DNT, were insensitive to alkaline hydrolysis. Alkaline hydrolysis is an inexpensive and effective means of reducing the varied explosives contamination.

The uncertainty of mass discharge measurements using pumping methods under simplified conditions.

Mass discharge measurements at contaminated sites have been used to assist with site management decisions, and can be divided into two broad categories: point-scale measurement techniques and pumping methods. Pumping methods can be sub-divided based on the pumping procedures used into sequential, concurrent, and tandem circulating well categories. Recent work has investigated the uncertainty of point measurement methods, and to a lesser extent, pumping methods. However, the focus of this study was a direct comparison of uncertainty between the various pumping method approaches that have been used, as well as a comparison of uncertainty between pumping and point measurement methods. Mass discharge measurement error was investigated using a Monte Carlo modeling analysis as a function of the contaminant plume position and width, and as a function of the pumping conditions used in the different pumping tests. Results indicated that for the conditions investigated, uncertainty in mass discharge estimates based on pumping methods was 1.3 to 16 times less than point measurement method uncertainty, and that a sequential pumping approach resulted in 5 to 12 times less uncertainty than the concurrent pumping or tandem circulating well approaches. Uncertainty was also investigated as a function of the plume width relative to well spacing. For a given well spacing, uncertainty decreased for all methods as the plume width increased, and comparable levels of uncertainty between point measurement and pumping methods were obtained when three wells were distributed across the plume. A hybrid pumping technique in which alternate wells were pumped concurrently in two separate campaigns yielded similar uncertainty to the sequential pumping approach. This suggests that the hybrid approach can be used to capitalize on the advantages of sequential pumping yet minimize the overall test duration.

Screening-level estimates of mass discharge uncertainty from point measurement methods

The uncertainty of mass discharge measurements associated with point-scale measurement techniques was investigated by deriving analytical solutions for the mass discharge coefficient of variation for two simplified, conceptual models. In the first case, a depth-averaged domain was assumed, consisting of one-dimensional groundwater flow perpendicular to a one-dimensional control plane of uniformly spaced sampling points. The contaminant flux along the control plane was assumed to be normally distributed. The second case consisted of one-dimensional groundwater flow perpendicular to a two-dimensional control plane of uniformly spaced sampling points. The contaminant flux in this case was assumed to be distributed according to a bivariate normal distribution. The center point for the flux distributions in both cases was allowed to vary in the domain of the control plane as a uniform random variable. Simplified equations for the uncertainty were investigated to facilitate screening-level evaluations of uncertainty as a function of sampling network design. Results were used to express uncertainty as a function of the length of the control plane and number of wells, or alternatively as a function of the sample spacing. Uncertainty was also expressed as a function of a new dimensionless parameter, Ω, defined as the ratio of the maximum local flux to the product of mass discharge and sample density. Expressing uncertainty as a function of Ω provided a convenient means to demonstrate the relationship between uncertainty, the magnitude of a local hot spot, magnitude of mass discharge, distribution of the contaminant across the control plane, and the sampling density.

Flux-Based Site Assessment and Management

Although characterizing dense nonaqueous phase liquid (DNAPL) source zones poses significant challenges, there have been several recent improvements in characterization methods and decision making. One important improvement has been the increased use of mass flux and mass discharge information. This information can be helpful for evaluating risks, assessing the benefits of partial source depletion efforts, estimating natural attenuation rates and refining conceptual site models. Mass flux data also can lead to more cost effective remediation by targeting the areas that provide the most loading to the contaminant plume. This chapter provides an overview of uses of mass flux and mass discharge estimates, and describes the measurement methods that are available. It also provides recommendations for use and discusses the level of resolution needed when measuring mass flux and mass discharge for differing objectives. Finally, the chapter includes case studies of the uses of mass flux and mass discharge information at specific DNAPL sites, highlighting the value of the data in making site management decisions.

Source strength functions from long-term monitoring data and spatially distributed mass discharge measurements

Source strength functions (SSF), defined as contaminant mass discharge or flux-averaged concentration from dense nonaqueous phase liquid (DNAPL) source zones as a function of time, provide a quantitative model of DNAPL source-zone behavior. Such information is useful for calibration of screening-level models to assist with site management decisions. We investigate the use of historic data collected during long-term monitoring (LTM) activities at a site in Rhode Island to predict the SSF based on temporal mass discharge measurements at a fixed location, as well as SSF estimation using mass discharge measurements at a fixed time from three spatially distributed control planes. Mass discharge based on LTM data decreased from ~300 g/day in 1996 to ~70 g/day in 2012 at a control plane downgradient of the suspected DNAPL source zone, and indicates an overall decline of ~80% in 16 years. These measurements were compared to current mass discharge measurements across three spatially distributed control planes. Results indicate that mass discharge increased in the downgradient direction, and was ~6 g/day, ~37 g/day, and ~400 g/day at near, intermediate, and far distances from the suspected source zone, respectively. This behavior was expected given the decreasing trend observed in the LTM data at a fixed location. These two data sets were compared using travel time as a means to plot the data sets on a common axis. The similarity between the two data sets gives greater confidence to the use of this combined data set for site-specific SSF estimation relative to either the sole use of LTM or spatially distributed data sets.

Continuous Determination of High-Vapor-Phase Concentrations of Tetrachloroethylene Using On-Line Mass Spectrometry

A method was developed to determine the vapor concentration of tetrachloroethylene (PCE) at and below its equilibrium vapor-phase concentration, 168 000 microg/L (25 degrees C). Vapor samples were drawn by vacuum into a six-port sampling valve and injected through a jet separator into an ion trap mass spectrometer (MS). This on-line MS can continuously sample a vapor stream and provide vapor concentrations every 30 s. Calibration of the instrument was done by creating a saturated stream of PCE vapor, sampling the vapor with the on-line MS and with thermal desorption tubes, and correlating the peak area response from the MS with the vapor concentration determined by automated thermal desorption gas chromatography mass spectrometry. Dilution of the saturated stream provided lower concentrations of PCE vapor. The method was developed to monitor the vapor concentration of PCE that was sparged from a two-dimensional flow chamber and for determination of the total PCE mass removed during each sparge event. The method has potential application for analysis of gas-phase tracers.