Gwynn R. Johnson

Amending greenroof soil with biochar to affect runoff water quantity and quality

Numbers of greenroofs in urban areas continue to grow internationally; so designing greenroof soil to reduce the amount of nutrients in the stormwater runoff from these roofs is becoming essential. This study evaluated changes in extensive greenroof water discharge quality and quantity after adding biochar, a soil amendment promoted for its ability to retain nutrients in soils and increase soil fertility. Prototype greenroof trays with and without biochar were planted with sedum or ryegrass, with barren soil trays used as controls. The greenroof trays were subjected to two sequential 7.4cm/h rainfall events using a rain simulator. Runoff from the rain events was collected and evaluated. Trays containing 7% biochar showed increased water retention and significant decreases in discharge of total nitrogen, total phosphorus, nitrate, phosphate, and organic carbon. The addition of biochar to greenroof soil improves both runoff water quality and retention.

The effect of local-scale physical heterogeneity and nonlinear, rate-limited sorption/desorption on contaminant transport in porous media.

Nonideal transport of contaminants in porous media has often been observed in laboratory characterization studies. It has long been recognized that multiple processes associated with both physical and chemical factors can contribute to this nonideal transport behavior. To fully understand system behavior, it is important to determine the relative contributions of these multiple factors when conducting contaminant transport and fate studies. In this study, the relative contribution of physical-heterogeneity-related processes versus those of nonlinear, rate-limited sorption/desorption to the observed nonideal transport of trichloroethene in an undisturbed aquifer core was determined through a series of miscible-displacement experiments. The results of experiments conducted using the undisturbed core, collected from a Superfund site in Tucson, AZ, were compared to those obtained from experiments conducted using the same aquifer material packed homogeneously. The results indicate that both physical and chemical factors, specifically preferential flow and associated rate-limited diffusive mass-transfer and rate-limited sorption/desorption, respectively, contributed to the nonideal behavior observed for trichloroethene transport in the undisturbed core. A successful prediction of trichloroethene transport in the undisturbed core was made employing a mathematical model incorporating multiple sources of nonideal transport, using independently determined model parameters to account for the multiple factors contributing to the nonideal transport behavior. The simulation results indicate that local-scale physical heterogeneity controlled the nonideal transport behavior of trichloroethene in the undisturbed core, and that nonlinear, rate-limited sorption/desorption were of secondary importance.

In-situ activation of persulfate by iron filings and degradation of 1,4-dioxane

Activation of persulfate by iron filings and subsequent degradation of 1,4-dioxane (dioxane) was studied in both batch-reactor and column systems to evaluate the potential of a persulfate-enhanced permeable reactive barrier (PRB) system for combined oxidative-reductive removal of organic contaminants from groundwater. In batch experiments, decomposition of persulfate to sulfate and degradation of dioxane both occurred rapidly in the presence of iron filings. Conversely, dioxane degradation by persulfate was considerably slower in the absence of iron filings. For the column experiments, decomposition and retardation of persulfate was observed for transport in the columns packed with iron filings, whereas no decomposition or retardation was observed for transport in columns packed with a reference quartz sand. Both sulfate production and dioxane degradation were observed for the iron-filings columns, but not for the sand column. The pH of the column effluent increased temporarily before persulfate breakthrough, and significant increases in both ferrous and ferric iron coincided with persulfate breakthrough. Multiple species of free radicals were produced from persulfate activation as determined by electron paramagnetic resonance (EPR) spectroscopy. The impact of the oxidation process on solution composition and iron-filings surface chemistry was examined using ICP-MS, SEM-EDS, and XRD analyses. A two-stage reaction mechanism is proposed to describe the oxidation process, consisting of a first stage of rapid, solution-based, radical-driven decomposition of dioxane and a second stage governed by rate-limited surface reaction. The results of this study show successful persulfate activation using iron filings, and the potential to apply an enhanced PRB method for improving in-situ removal of organic contaminants from groundwater.

Mass Removal and Low-Concentration Tailing of Trichloroethene in Freshly-Amended, Synthetically-Aged, and Field-Contaminated Aquifer Material

This study investigates the effect of contaminant aging on the sorption/desorption and transport of trichloroethene in a low organic-carbon content aquifer material, comparing mass removal and long-term, low-concentration elution tailing for field-contaminated, synthetically-aged (contact times of approximately four years), and freshly-amended aquifer material. Elution of trichloroethene exhibited extensive low-concentration tailing, despite minimal retention of trichloroethene by the aquifer material. The observed nonideal transport behavior of trichloroethene is attributed primarily to rate-limited sorption/desorption, with a smaller contribution from nonlinear sorption. It is hypothesized that interaction with physically condensed carbonaceous material, comprising 61% of the aquifer materials organic-carbon content, mediates the retention behavior of trichloroethene. The elution behavior of trichloroethene for the field-contaminated and aged treatments was essentially identical to that observed for the fresh treatments. In addition, the results of three independent mass-balance analyses, total mass eluted, solvent-extraction analysis of residual sorbed mass, and aqueous-phase concentration rebounds following stop-flow experiments, showed equivalent recoveries for the aged and fresh treatments. These results indicate that long-term contaminant aging did not significantly influence the retention and transport of trichloroethene in this low organic-carbon aquifer material.

A gas‐phase partitioning tracer method for the in situ measurement of soil‐water content

The purpose of this paper is to describe a gas-phase partitioning tracer method for the in situ measurement of soil-water content and to illustrate the application and performance of the tracer method in well-defined systems. The method is based on the use of a tracer test with nonpartitioning and partitioning tracers introduced into the system in the gas phase. Partitioning tracers dissolve into the water, which retards their gas-phase transport relative to that of the nonpartitioning tracers. Retardation of the partitioning tracers is a function of the amount of water present. The method provides an integrated field-scale value that complements smaller-scale methods, such as neutron moderation, and regional-scale methods based on remote sensing. Experiments were conducted in the laboratory and in a large weighing lysimeter to test the performance of the gas-phase partitioning tracer method. Soil-water contents estimated from the tracer tests were reasonably close to values obtained using gravimetric and time domain reflectometry measurements, indicating the tracer method has the potential to provide accurate measurements of soil-water content at the field scale.

Nonideal transport of contaminants in heterogeneous porous media: 8. Characterizing and modeling asymptotic contaminant-elution tailing for several soils and aquifer sediments

Miscible-displacement experiments were conducted to characterize long-term, low-concentration elution tailing associated with sorption/desorption processes. A variety of soils and aquifer sediments, representing a range of particle-size distributions and organic-carbon contents, were employed, and trichloroethene (TCE) was used as the model organic compound. Trichloroethene transport exhibited extensive elution tailing for all media, with several hundred to several thousand pore volumes of water flushing required to reach the detection limit. The elution tailing was more extensive for the media with higher organic-carbon contents and associated retardation factors. However, when normalized by retardation, the extent of tailing did not correlate directly to organic-carbon content. These latter results suggest that differences in the geochemical nature of organic carbon (e.g., composition, structure) among the various media influenced observed behavior. A mathematical model incorporating nonlinear, rate-limited sorption/desorption described by a continuous-distribution function was used to successfully simulate trichloroethene transport, including the extensive elution tailing.

Intercalation of Trichloroethene by Sediment-Associated Clay Minerals

The objective of this research was to examine the potential for intercalation of trichloroethene (TCE) by clay minerals associated with aquifer sediments. Sediment samples were collected from a field site in Tucson, AZ. Two widely used Montmorillonite specimen clays were employed as controls. X-ray diffraction, conducted with a controlled-environment chamber, was used to characterize smectite interlayer d-spacing for three treatments (bulk air-dry sample, sample mixed with synthetic groundwater, sample mixed with TCE-saturated synthetic groundwater). The results show that the d-spacing measured for the samples treated with TCE-saturated synthetic groundwater are larger (~26%) than those of the untreated samples for all field samples as well as the specimen clays. These results indicate that TCE was intercalated by the clay minerals, which may have contributed to the extensive elution tailing observed in prior miscible-displacement experiments conducted with this sediment.

Evaporative Mass Transfer Behavior of a Complex Immiscible Liquid

A series of laboratory experiments was conducted with a multiple-component immiscible liquid, collected from the Picillo Farm Superfund Site in Rhode Island, to examine liquid-vapor mass-transfer behavior. The immiscible liquid, which comprises solvents, oils, pesticides, PCBs, paint sludges, explosives, and other compounds, was characterized using gas chromatography and gas chromatography/mass spectrometry to determine mole fractions of selected constituents. Batch experiments were conducted to evaluate equilibrium phase-partitioning behavior. Two sets of air-stripping column studies were conducted to examine the mass-transfer dynamics of five selected target compounds present in the immiscible-liquid mixture. One set of column experiments was designed to represent a system with free-phase immiscible liquid present; the other was designed to represent a system with a residual phase of immiscible liquid. Initial elution behavior of all target components generally appeared to be ideal for both systems, as the initial vapor-phase concentrations were similar to vapor-phase concentrations measured for the batch experiment and those estimated using Raoults law (incorporating the immiscible-liquid composition data). Later-stage removal of 1,2-dichlorobenzene appeared to be rate limited for the columns containing free-phase immiscible liquid and no porous medium. Conversely, evaporative mass transfer appeared to be ideal throughout the experiment conducted with immiscible liquid distributed relatively uniformly as a residual phase within a sandy porous medium.

Nonideal transport of contaminants in heterogeneous porous media: 10. Impact of co-solutes on sorption by porous media with low organic-carbon contents

The impact of co-solutes on sorption of tetrachloroethene (PCE) by two porous media with low organic-carbon contents was examined by conducting batch experiments. The two media (Borden and Eustis) have similar physical properties, but significantly different organic-carbon (OC) contents. Sorption of PCE was nonlinear for both media, and well-described by the Freundlich equation. For the Borden aquifer material (OC=0.03%), the isotherms measured with a suite of co-solutes present (1,2-dichlorobenzene, bromoform, carbon tetrachloride, and hexachloroethane) were identical to the isotherms measured for PCE alone. These results indicate that there was no measurable impact of the co-solutes on PCE sorption for this system. In contrast to the Borden results, there was a measurable reduction in sorption of PCE by the Eustis soil (OC=0.38%) in the presence of the co-solutes. The organic-carbon fractions of both media contain hard-carbon components, which have been associated with the manifestation of nonideal sorption phenomena. The disparity in results observed for the two media may relate to relative differences in the magnitude and geochemical nature of these hard-carbon components.