Bentonite, especially sodium bentonite, is used extensively either by itself or as a component of soil mixtures in many geoenvironmental engineering applications, including the construction of waste-containment barriers. An important aspect of the design of such barriers is the compatibility assessment of the soil barrier with the intended waste. A series of laboratory hydraulic conductivity (K) experiments were conducted to assess the compatibility of a sodium bentonite paste with acid mine drainage (AMD). The K of the water-permeated bentonite was observed to be of the order of 2 × 109 cm/s. Permeation of the bentonite with AMD increased K slightly by almost one order of magnitude to an average value of 1 × 108 cm/s as a result of the contraction of electrical double layers surrounding clay particles. The application of a confining stress (3050 kPa) to the samples minimized the increase in K. Confining stress likely compressed the samples and reduced the size of the voids created by double-layer contraction, resulting in lower K. Effluent chemical profiles obtained during the K tests indicated the appearance of some cations and elements contained in the AMD permeant, at its original concentration (influent concentration) after a few pore volumes of AMD permeation. Iron and aluminum likely precipitated as oxyhydroxide and oxysulphate minerals. The pH of the effluent decreased from 7.6 during water permeation to 3.0 after only three pore volumes of AMD permeation, reflecting the limited capacity of the bentonite to neutralize acidic solutions. Zinc was slightly attenuated by adsorption (3.15 mequiv./100 g of dry bentonite) but was reported in the effluent, after approximately nine pore volumes. The results are relevant to the design and construction of bentonite slurry walls around acid-generating tailings and acid water containment ponds at mine sites.Key words: hydraulic conductivity, swelling, waste containment, confining stress, heavy metals, ionic strength, saturation index.
In situ chemical oxidation (ISCO) of petroleum hydrocarbons (PHCs) within groundwater is considered a proven approach to addressing PHC‐impacted groundwater in nonsaline environments. One of the most common oxidants used for oxidation of PHCs in groundwater is hydrogen peroxide (H2O2). Due to its highly reactive nature, H2O2 is often stabilized to aid in increasing its reactivity lifespan. Limited research and application of ISCO has been completed in warm, saline groundwater environments. Furthermore, even fewer studies have been completed in these environments for ISCO using stabilized H2O2. In this research, stabilized H2O2 was examined to determine its effectiveness in the treatment of PHCs and the additive methyl tert‐butyl ether (MTBE). Three stabilizers (citrate, phytate, silica [SiO2]) were tested to determine if the stabilizers could enhance and extend the treatment life of H2O2 within saline groundwater. To determine the effect of salinity on the three stabilizers, groundwater and aquifer samples were collected from two saline locations that had different salinity (total dissolved solids of about 7,000 mg/L and 18,000 mg/L). Specific target chemicals for treatment were water soluble, mobile components of gasoline including benzene, toluene, ethylbenzene, xylenes, (BTEX) and MTBE. Previous studies using unactivated persulfate indicated that the PHCs within the groundwater could be oxidized, however, only limited oxidation of the MTBE could be affected. The results of the laboratory tests indicated that greater than 95 percent of the target hydrocarbons were removed within 7 days of treatment. Microcosms with citrate‐stabilized H2O2 demonstrated a significantly faster and greater decline with most hydrocarbon concentrations reaching < 5 μg/L. The exceptions were ethylbenzene and m‐xylene, which were slightly decreased to about 30 and 20 μg/L, respectively. Initial mean concentrations of the BTEX compounds within the citrate‐stabilized microcosms were 10,554 μg/L, 9,318 μg/L, 6,859 μg/L, and 14,435 μg/L, respectively. The silicate‐stabilized H2O2 microcosms showed no significant benefit over the unstabilized control microcosms. The better performance of citrate‐stabilized microcosms was confirmed by increasing δ13C values of remaining hydrocarbons. MTBE declined from > 400 mg/L to < 100 mg/L in all microcosms, again with the best removal (> 90 percent) being measured in the citrate‐stabilized microcosms. Unfortunately, H2O2 oxidation in the microcosms also resulted in production of up to 40 mg/L TBA or approximately 10 percent of the MTBE oxidized.
A series of laboratory microcosm experiments and a field pilot test were performed to evaluate the potential for in situ chemical oxidation (ISCO) of aromatic hydrocarbons and methyl tertiary butyl ether (MTBE), a common oxygenate additive in gasoline, in saline, high temperature (more than 30 • C) groundwater. Groundwater samples from a site in Saudi Arabia were amended in the laboratory portion of the study with the chemical oxidants, sodium persulfate (Na 2 S 2 O 8 ) and sodium percarbonate (Na 2 (CO 3 ) 2 ), to evaluate the changes in select hydrocarbon and MTBE concentrations with time. Almost complete degradation of the aromatic hydrocarbons, naphthalene and trimethylbenzenes (TMBs), was found in the groundwater sample amended with persulfate, whereas the percarbonate-amended sample showed little to no degradation of the target hydrocarbon compounds in the laboratory. Isotopic analyses of the persulfate-amended samples suggested that C-isotope fractionation for xylenes occurred after approximately 30 percent reduction in concentration with a decline of about 1 percent in the 13 C values of xylenes. Based on the laboratory results, pilot-scale testing at the Saudi Arabian field site was carried out to evaluate the effectiveness of chemical oxidation using nonactivated persulfate on a high temperature, saline petroleum hydrocarbon plume. Approximately 1,750 kg of Na 2 S 2 O 8 was delivered to the subsurface using a series of injection wells over three injection events. Results obtained from the pilot test indicated that all the target compounds decreased with removal percentages varying between 86 percent for naphthalene and more than 99 percent for the MTBE and TMBs. The benzene, toluene, ethylbenzene, and xylene compounds decreased to 98 percent on average. Examination of the microbial population upgradient and downgradient of the ISCO reactive zone suggested that a bacteria population was present following the ISCO injections with sulfate-reducing bacteria (SRB) being the dominant bacteria present. Measurements of inorganic parameters during injection and postinjection indicated that the pH of the groundwater remained neutral following injections, whereas the oxidation-reduction potential remained anaerobic throughout the injection zone with time. Nitrate concentrations decreased within the injection zone, suggesting that the nitrate may have been consumed by denitrification reactions, whereas sulfate concentrations increased as expected within the reactive zone, suggesting that the persulfate produced sulfate. Overall, the injection of the oxidant persulfate was shown to be an effective approach to treat dissolved aromatic and associated hydrocarbons within the groundwater. In addition, the generation of sulfate as a byproduct was an added benefit, as the sulfate could be utilized by SRBs present within the subsurface to further biodegrade any remaining hydrocarbons. c⃝ 2015 Wiley Periodicals, Inc.
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