Application of an Adapted Version of MT3DMS for Modeling Back‐Diffusion Remediation Timeframes

Simulation of back‐diffusion remediation timeframe for thin silt/clay layers, or when contaminant degradation is occurring, typically requires the use of a numerical model. Given the centimeter‐scale vertical grid spacing required to represent diffusion‐dominated transport, simulation of back‐diffusion in a 3‐D model may be computationally prohibitive. Use of a local 1‐D model domain approach for simulating back‐diffusion is demonstrated to have advantages but is limited to only some applications. Incorporation of a local domain approach for simulating back‐diffusion in a new model, In Situ Remediation‐MT3DMS (ISR‐MT3DMS) is validated based on a benchmark with MT3DMS and comparisons with a highly discretized finite difference numerical model. The approach used to estimate the vertical hydrodynamic dispersion coefficient is shown to have a significant influence on the simulated flux into and out of silt/clay layers in early time periods. Previously documented back‐diffusion at a Florida site is modeled for the purpose of evaluating the sensitivity of the back‐diffusion controlled remediation timeframe to various site characteristics. A base case simulation with a clay lens having a thickness of 0.2 m and a length of 100 m indicates that even after 99.96 percent aqueous TCE removal from the clay lens, the down‐gradient concentrations still exceed the MCL in groundwater monitoring wells. This shows that partial mass reduction from a NAPL source zone via in situ treatment may have little benefit for the long‐term management of contaminated sites, given that back‐diffusion will sustain a groundwater plume for a long period of time. Back‐diffusion model input parameters that have the greatest influence on remediation timeframe and thus may warrant more attention during field investigations, include the thickness of silt/clay lenses, retardation coefficient representing sorbed mass in silt/clay, and the groundwater velocity in adjacent higher permeability zones. Therefore, pump‐and‐treat systems implemented for the purpose of providing containment may have an additional benefit of reducing back‐diffusion remediation timeframe due to enhanced transverse advective fluxes at the sand/clay interface. Remediation timeframes are also moderately sensitive to the length of the silt/clay layers and transverse vertical dispersivity, but are less sensitive to degradation rates within silt/clay, contaminant solubility, contact time, tortuosity coefficient, and monitoring well‐screen length for the scenarios examined. ©2015 Wiley Periodicals, Inc.     

DNAPL Source Depletion: 2. Attainable Goals and Cost–Benefit Analyses

It is difficult to quantify the range in source strength reduction (MdR) that may be attainable from in situ remediation of a dense nonaqueous‐phase liquid (DNAPL) site given that available studies typically report only the median MdR without providing insights into site complexity, which is often a governing factor. An empirical study of the performance of in situ remediation at a wide range of DNAPL‐contaminated sites determined MdRs for in situ bioremediation (EISB), in situ chemical oxidation (ISCO), and thermal treatment remedies. Median MdR, geometric mean MdR, and lower/upper 95 percent confidence interval for the mean were: 49x, 105x, 20x/556x, respectively, for EISB; 9x, 21x, and 4x/110x for ISCO; and 19x, 31x, and 6x/150x for thermal treatment. Lower MdR values were determined for large, complex sites and for sites with DNAPL pool‐dominated source zones. A feasibility analysis of partial DNAPL depletion is described for a pool‐dominated source zone. Back‐diffusion from low‐hydraulic conductivity units within a pool‐dominated source zone is shown to potentially sustain a secondary source for more than 1,000 years, indicating that aggressive source treatment may not reduce the remediation timeframe. Estimated plume response demonstrates there may be no reduction in cost associated with aggressive treatment, and little difference in risk reduction associated with the various alternatives. Monitored natural attenuation (MNA) for the source zone is shown to be a reasonable alternative for the pool‐dominated source zone considered in this example. It is demonstrated that pool‐dominated source zones with a large range in initial DNAPL mass (250 to 1,500 kg) may correspond to a narrow range in source strength (20 to 30 kg/year). This demonstrates that measured source strength is nonunique with respect to DNAPL mass in the subsurface and, thus, source strength should not be used as the sole basis for predicting how much DNAPL mass remains or must be removed to achieve a target goal. If aggressive source zone treatment is to be implemented due to regulatory requirements, strategic pump‐and‐treat is shown to be most cost effective. These remedial decisions are shown to be insensitive to a range of possible DNAPL pool conditions. At sites with an existing pump‐and‐treat system, a significant increase in mass removal and source strength reduction may be achieved for a low incremental cost by strategic placement of extraction wells and pumping rate selection. © 2014 Wiley Periodicals, Inc.     

Inhomogeneity of methane emissions from a dairy waste lagoon

Methane (CH₄) is the dominant greenhouse gas emitted by animal agriculture manure. Since the gas is relatively insoluble in water, it is concentrated in discrete bubbles that rise through waste lagoons and burst at the surface. This results in lagoon emissions that are inhomogeneous in both space and time. Emissions from a midwestern dairy waste lagoon were measured over 2 weeks to evaluate the spatial homogeneity of the source emissions and to compare two methods for measuring this inhomogeneous emission. Emissions were determined using an inverse dispersion model based on CH₄ concentrations measured both by a single scanning tunable diode laser (TDL) aimed at a series of reflectors and by flame ionization detection (FID) gas chromatography on line-sampled air. Emissions were best estimated using scanned TDL concentrations over relatively short optical paths that collectively span the entire cross-wind width of the source, so as to provide both the best capture of discrete plumes from the bursting bubbles on the lagoon surface and the best detection of CH₄ background concentrations. The lagoon emissions during the study were spatially inhomogeneous at hourly time scales. Partitioning the inhomogeneous source into two source regions reduced the estimated emissions of the overall lagoon by 57% but increased the variability. Consequently, it is important to assess the homogeneity of a source prior to measurements and final emissions calculation.

Implications: Plans for measuring methane emissions from waste lagoons must take into account the spatial inhomogeneity of the source strength. The assumption of emission source homogeneity for a low-solubility gas such as CH₄ emitted from an animal waste lagoon can result in significant emission overestimates. The entire breadth and length of the area source must be measured, preferably with multiple optical paths, for the detection of discrete plumes from the different emitting regions and for determining the background concentration. Other gases with similarly poor solubility in water may also require partitioning of the lagoon source area.     

Estimating chemical biotransformation rates from food web concentrations

Biotransformation is widely recognized as the most important and most uncertain determinant of bioaccumulation. A step-wise method for estimating organism-specific biotransformation half-lives from field observations and using established food web modeling is developed. As a proof of concept, the method is applied to the case of nine polycyclic aromatic hydrocarbons (PAHs) in a well-studied food web in Bohai Bay, China. The estimated half-lives are in good agreement with the existing literature. The proposed biotransformation estimation method, through data mining, for sufficiently defined ecosystems, may greatly reduce the necessary animal testing involved in chemical assessments by providing useful guidance to experimentalists and regulators.     

Protection from wintertime rainfall reduces nutrient losses and greenhouse gas emissions during the decomposition of poultry and horse manure-based amendments

Manure-based soil amendments (herein “amendments”) are important fertility sources, but differences among amendment types and management can significantly affect their nutrient value and environmental impacts. A 6-month in situ decomposition experiment was conducted to determine how protection from wintertime rainfall affected nutrient losses and greenhouse gas (GHG) emissions in poultry (broiler chicken and turkey) and horse amendments. Changes in total nutrient concentration were measured every 3 months, changes in ammonium (NH₄⁺) and nitrate (NO₃^?) concentrations every month, and GHG emissions of carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O) every 7–14 days. Poultry amendments maintained higher nutrient concentrations (except for K), higher emissions of CO₂ and N₂O, and lower CH₄ emissions than horse amendments. Exposing amendments to rainfall increased total N and NH₄⁺ losses in poultry amendments, P losses in turkey and horse amendments, and K losses and cumulative N₂O emissions for all amendments. However, it did not affect CO₂ or CH₄ emissions. Overall, rainfall exposure would decrease total N inputs by 37% (horse), 59% (broiler chicken), or 74% (turkey) for a given application rate (wet weight basis) after 6 months of decomposition, with similar losses for NH₄⁺ (69–96%), P (41–73%), and K (91–97%). This study confirms the benefits of facilities protected from rainfall to reduce nutrient losses and GHG emissions during amendment decomposition.

Implications: The impact of rainfall protection on nutrient losses and GHG emissions was monitored during the decomposition of broiler chicken, turkey, and horse manure-based soil amendments. Amendments exposed to rainfall had large ammonium and potassium losses, resulting in a 37–74% decrease in N inputs when compared with amendments protected from rainfall. Nitrous oxide emissions were also higher with rainfall exposure, although it had no effect on carbon dioxide and methane emissions. Overall, this work highlights the benefits of rainfall protection during amendment decomposition to reduce nutrient losses and GHG emissions.     

Herbicide incorporation by irrigation and tillage impact on runoff loss

Runoff from farm fields is a common source of herbicide residues in surface waters. Incorporation by irrigation has the potential to reduce herbicide runoff risks. To assess impacts, rainfall was simulated on plots located in a peanut (Arachis hypogaea L.) field in Georgia's Atlantic Coastal Plain region after pre-emergence application of metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-[(1S)-2-methoxy-1-methylethyl]-acetamide) and pendimethalin (N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitro-benzenamine). Runoff, sediment, and herbicide loss as function of strip tillage (ST) versus conventional tillage (CT) were compared with and without irrigation (12.5 mm) after application of an herbicide tank mixture. For the CT system, metolachlor runoff was reduced 2x and pendimethalin 1.2x when compared with the non-irrigated treatment. The difference in irrigated and non-irrigated metolachlor means was significant (P = 0.05). Irrigation reduced metolachlor runoff by 1.3x in the ST system, but there was a 1.4x increase for pendimethalin. Overall results indicated that irrigation incorporation reduces herbicide runoff with the greatest impact when CT is practiced and products like metolachlor, which have relatively low K(oc) and high water solubility, are used. The lower ST system response was likely due to a combination of spray interception and retention by the ST system cover crop mulch and higher ST soil organic carbon content and less total runoff. During the study, the measured K(oc) of both herbicides on runoff sediment was found to vary with tillage and irrigation after herbicide application. Generally, K(oc) was higher for ST sediment and when irrigation incorporation was used with the CT system. These results have significant implications for simulation model parametization.     

Analysis of energy use in a sample of Chinese villages

This paper summarises the methodology and results of work involved in the investigation of energy demand in six Chinese villages included in the SUCCESS Project. The procedures used to collect data associated with local energy demand are explained and the approach to data analysis is explained. Results are provided in terms for delivered energy consumption, as an indicator of energy demand; primary energy consumption, as an indicator of energy resource depletion; and carbon dioxide emissions, as an indicator of global climate change. Similarities and differences between results for this sample of villages are considered. The important causes of differences in results are investigated.     

Propanil in a Manitoba soil: an interactive spreadsheet model based on conventional chemical kinetics

An interactive spreadsheet model has been created for quantitative predictions of propanil sorption and reaction in a slurried Manitoba clay soil. Based on experimental values for the numbers of empty and filled sorption sites as reactants and products, the reaction mechanism has been described with conventional chemical kinetics. The on line HPLC μ extraction method revealed labile sorption, intraparticle diffusion, and a chemical reaction. Laidler's integral rate law for second order kinetics describes the labile sorption. Desorption, intraparticle diffusion, and the chemical reaction are all described by first order kinetics. The time dependent effects of initial concentration and amount of slurried soil can be predicted for sorption, intraparticle diffusion, and the amount of reaction product. Suggested applications include storm runoff and inputs for fate and transport hydrology models.     

Sustainable remediation panel—Measuring the social and economic benefits of a sustainable remediation project

Remediation developed a Sustainable Remediation Panel in the Summer 2009 issue, which featured the Sustainable Remediation Forum White Paper. The panel is composed of leaders in the field of sustainable remediation who have volunteered to provide their opinions on difficult subjects related to the topic of how to integrate sustainability principles into the remediation practice. The panel's opinions are provided in a question‐and‐answer format, whereby selected experts provide an answer to a question. This issue's question is provided below, followed by opinions from five experts in the remediation field.

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