Remediation of groundwater contaminated with DNAPLs by biodegradable oil emulsion

Emulsion-based remediation with biodegradable vegetable oils was investigated as an alternative technology for the treatment of subsurface DNAPLs (dense non-aqueous phase liquids) such as TCE (trichloroethylene) and PCE (perchloroethylene). Corn and olive oil emulsions obtained by homogenization at 8000rpm for 15min were used. The emulsion droplets prepared with corn and olive oil gave a similar size distribution (1-10microm) and almost all of initially injected oil, >90%, remained in a dispersed state. In batch experiments, 2% (v/v) oil emulsion could adsorb up to 11,000ppm of TCE or 18,000ppm of PCE without creating a free phase. Results of one-dimensional column flushing studies indicated that contaminants with high aqueous solubility could be efficiently removed by flushing with vegetable oil emulsions. Removal efficiencies exceeded 98% for TCE and PCE with both corn and olive oil emulsions. The results of this study show that flushing with biodegradable oil emulsion can be used for the remediation of groundwater contaminated by DNAPLs.     

The effect of ionic strength and hardness of water on the non-ionic surfactant-enhanced remediation of perchloroethylene contamination

The objective of this study is to evaluate the perchloroethylene (PCE) removal by an aqueous surfactant solutions based on influential factors (ionic strength, hardness) of various groundwaters and surface waters contaminated with PCE. The experimental methods used in this study were separatory funnel experiments and batch experiments. Separatory funnel experiments were performed to determine which surfactants are good solubilizers for PCE. Batch experiments were performed to evaluate the effect of ions in sampled water for PCE removal. The results of separatory funnel experiments indicated that the surfactant polyoxyethylene (20) sorbitan monostearate (Tween 60) showed to be a predominant solubilizer for the removal of PCE (87.3%). Separatory funnel experiments also showed that the hydrophilic-lipophilic balance (HLB) number and the chemical structure of the surfactants were good indicators of surfactant effectiveness for removal of PCE from water. The results of batch experiments showed that non-ionic surfactants are affected by the ionic strength of sampled water. The % of PCE removal of the Tween 60 surfactant solution was measured to be 88.3% by batch experiments. This result was affected by the characteristics of the surfactant (HLB, chemical structures) and the ionic strength of water. Therefore, the ionic strength of contaminated water, HLB and chemical structures of surfactants must be considered in surfactant-enhanced remediation.     

Application of surfactant enhanced permanganate oxidation and bidegradation of trichloroethylene in groundwater

The industrial solvent trichloroethylene (TCE) is among the most ubiquitous chlorinated solvents found in groundwater contamination. The main objectives of this study were to evaluate the feasibility of using non-ionic surfactant Simple Green™ (SG) to enhance the oxidative dechlorination of TCE by potassium permanganate (KMnO₄) employing a continuous stir batch reactor system (CSBR) and column experiments. The effect of using surfactant SG to enhance the biodegradation of TCE via aerobic cometabolism was also examined. Results from CSBR experiments revealed that combination of KMnO₄ with surfactant SG significantly enhanced contaminant removal, particularly when the surfactant SG concentrated at its CMC. TCE degradation rates ranged from 74.1% to 85.7% without addition of surfactant SG while TCE degradation rates increased to ranging from 83.8% to 96.3% with presence of 0.1 wt% SG. Furthermore, results from column experiments showed that TCE was degraded from 38.1 μM to 6.2 μM in equivalent to 83.7% of TCE oxidation during first 560 min reaction. This study has also demonstrated that the addition of surfactant SG is a feasible method to enhance bioremediation efficiency for TCE contaminated groundwater. The complete TCE degradation was detected after 75 days of incubation with both 0.01 and 0.1 wt% of surfactant SG addition. Results revealed that surfactant enhanced chemical oxidation and bioremediation technology is one of feasible approaches to clean up TCE contaminated groundwater.     

Reactivity of Fe(II)/cement systems in dechlorinating chlorinated ethylenes

Ferrous iron (Fe(II)) in combination with Portland cement is effective in reductively dechlorinating chlorinated organics and can be used to achieve immobilization and degradation of contaminants simultaneously. Reactivities of chlorinated ethylenes (perchloroethylene (PCE), trichloroethylene (TCE), 1,1-dichloroethylene (1,1-DCE), vinyl chloride (VC)) in Fe(II)/cement systems were characterized using batch slurry reactors. Reduction kinetics of the chlorinated ethylenes were sufficiently fast to be utilized for the proposed treatment scheme, and were described by a pseudo-first-order rate law. The order of reactivity of the chlorinated ethylenes was TCE>1,1-DCE>PCE>VC. Reduction of TCE and PCE mainly yielded acetylene, implying that the transformation of the two compounds occurred principally via reductive beta-elimination pathways. Transformation of 1,1-DCE and VC gave rise to primarily ethylene, implying that major degradation pathways were a reductive alpha-elimination for the former and a hydrogenolysis for the latter. The reactivity of the Fe(II)/cement systems in dechlorinating TCE was proportional to Fe(II) dose when the Fe(II)/cement mass ratio varied between 5.6 and 22.3%. The Fe(II)/cement systems with a higher Fe(II) loading were less extensively affected by pH in reductive reactions for TCE than in the previous experiments with PCE or chlorinated methanes. Amendment of Fe(II)/cement systems with Fe(III) addition was found effective in increasing the reactivity in the previous study, but the current findings indicated that the extent to which the reaction rate increased by the amendment might be dependent on the source of the cement and/or the compounds tested.     

Competitive immobilization of multiple component chlorinated solvents by cyclodextrin derivatives

Immobilization of chlorinated solvents with hydropropyl and methyl cyclodextrins (CDs) was observed by head-space analysis to obtain the stability constants in single and multiple component systems. In each single component system, the highest stability constant was 0.299 mM(-1) for perchloroethylene (PCE) by methyl-beta-cyclodextrin (M-beta-CD), 0.136 mM(-1) for trichloroethylene (TCE) by M-beta-CD, 0.106 mM(-1) for cis-dichloroethylene (cis-DCE) by hydropropyl-alpha-cyclodextrin, and 0.090 mM(-1) for trans-dichloroethylene (trans-DCE) by M-beta-CD. When HP-beta-CD and M-beta-CD were used, the stability constants of PCE and TCE increased and those of DCEs decreased in a multiple component system. Differences in stability constants of single and multiple component systems thus should be important parameters when cyclodextrins are applied to solubilization of multiple chlorinated solvents.     

Boosting sensitivity of organic vapor detection with silicone block polyimide polymers

We demonstrate that silicone block polyimide polymers have an unusually high sensitivity to nonpolar organic vapors, including chlorinated organic solvent vapors. When 0.18-5.34-microm-thick films of silicone block polyimide polymers were deposited onto 10-MHz thickness shear mode (TSM) oscillators, these films were implemented to detect parts-per-billion concentrations of trichloroethylene (TCE) with a detection sensitivity of 0.5-23.5 Hz per 500 ppb of vapor. With a film thickness of 3.4 microm (91.5-kHz frequency shift upon film deposition), optimized for the minimal sensor noise of 0.04 Hz, the calculated detection limit of sensor response (S/N = 3) was 3 ppb of TCE. Detection limits for other chlorinated organic solvent vapors, such as perchloroethylene (PCE), cis-1,2-dichloroethylene (DCE), trans-1,2-DCE, 1,1-DCE, and vinyl chloride (VC) were 0.6, 6, 6, 11, and 13 ppb, respectively. Assuming only the mass-loading response when deposited onto the TSM devices, silicone block polyimide polymers have partition coefficients of over 200 000 to parts-per-billion concentrations of TCE that make them at least 100 times more sensitive than other known polymers for TCE detection. We observed that unlike conventional polyimides, water sensitivity of the new hybrid polyimides is suppressed because of the silicone soft block. Water sensitivity is comparable with the sensor response to nonpolar organic vapors. The high sensitivity and long-term stability of these sensor materials make them attractive for ultrasensitive practical sensors.     

Ex-situ bioremediation of chlorobenzenes in soil

Chlorinated benzenes, including chlorobenzene (CB) and 1,2-dichlorobenzene (DCB) are widely used as chemical intermediates and solvents across industry. Soil contaminated with these compounds was treated in a pilot-scale trial in 6 m3 cells. Air was drawn through each cell and exhausted via an activated carbon (GAC) filter system. The trial objective was to stimulate native microflora with nutrients and varying levels of organic amendments (0%, 12% and 35%). Initial soil DCB concentrations varied from <1 to 6 mg/kg in the three cells with an average of 2 mg/kg. Approximately 90% of the DCB mass present in the soil was removed over a period of 2-3 weeks. Up to 100-fold increases in total heterotrophs (THP), CB+ and DCB+ degraders were observed. Residual concentrations of chlorinated benzenes were generally below detection limits (0.2 mg/kg). Adding organic matter did not enhance the removal of CB and DCB under the trial conditions, which were set up to minimize losses from volatilization. Biodegradation estimation calculations indicated that <5% of the chlorinated benzenes were removed by volatilization and 90% removed by biodegradation. Laboratory shake flask trials confirmed that the soils in the pilot-scale treatment contained a microbial consortium capable of mineralizing CB and DCB. This consortium was capable of mineralizing both CB and DCB with up to 50% of carbon added as chlorinated benzene substrate being recovered as CO2 and up to 44% of organic chlorine being released as chloride ion in mineralization tests, further confirming these chlorinated benzenes were biodegraded. The study confirms that vented ex-situ biotreatment processes for chlorinated benzenes can be achieved without excessive losses from volatilization and that naturally occurring microflora can be readily stimulated with aeration and nutrients.     

Design and construction techniques for permeable reactive barriers.

Adequate site characterization, bench-scale column testing, and hydrogeologic modeling formed the basis for the design and construction of permeable reactive barriers for groundwater remediation at various sites, such as Dover Air Force Base, DE and Naval Air Station, Moffett Field, CA. Dissolved chlorinated solvents, such as perchloroethylene (PCE) and trichloroethylene (TCE), have been the focus at many sites because the passive nature of the reactive barrier operation makes such barriers particularly useful for treating groundwater contaminants that can persist in the aquifer for several years. A combination of conventional and innovative site characterization, design, and construction techniques were used at these sites to increase the potential cost effectiveness of field application.     

Laboratory tests for reactive barrier design

Owing to limitations of pump-and-treat, several technologies are being investigated for groundwater treatment. One of the most promising is the treatment of contaminants through the use of reactive barriers installed in situ, especially in the case of aquifers contaminated with chlorinated solvents. This work presents results of batch and column tests with metallic iron and some chlorinated solvents (1,2-DCA, 1,1,2-TCA and TCE). Such tests provided means to evaluate the degradation rates of these compounds and their byproducts. It is concluded that the reductive dechlorination with metallic iron can have different results, depending on the type of contaminant. Some contaminants may not present any degradation, or they have a half-life time so high that the use of the reactive barrier technology may not be practical. Furthermore, the formation of chlorinated byproducts, eventually more toxic than the original contaminant and that are not degradable using this same technology, emphasises that the treatment of aquifers should be sequential.     

The mechanism and applicability of in situ oxidation of trichloroethylene with Fenton's reagent

Fenton's reagent is the result of reaction between hydrogen peroxide (H(2)O(2)) and ferrous iron (Fe(2+)), producing the hydroxyl radical (-*OH). The hydroxyl radical is a strong oxidant capable of oxidizing various organic compounds. The mechanism of oxidizing trichloroethylene (TCE) in groundwater and soil slurries with Fenton's reagent and the feasibility of injecting Fenton's reagent into a sandy aquifer were examined with bench-scale soil column and batch experiment studies. Under batch experimental conditions and low pH values ( approximately 3), Fenton's reagent was able to oxidize 93-100% (by weight) of dissolved TCE in groundwater and 98-102% (by weight) of TCE in soil slurries. Hydrogen peroxide decomposed rapidly in the test soil medium in both batch and column experiments. Due to competition between H(2)O(2) and TCE for hydroxyl radicals in the aqueous solutions and soil slurries, the presence of TCE significantly decreased the degradation rate of H(2)O(2) and was preferentially degraded by hydroxyl radicals. In the batch experiments, Fenton's reagent was able to completely dechlorinate the aqueous-phase TCE with and without the presence of soil and no VOC intermediates or by-products were found in the oxidation process. In the soil column experiments, it was found that application of high concentrations of H(2)O(2) with addition of no Fe(2+) generated large quantities of gas in a short period of time, sparging about 70% of the dissolved TCE into the gaseous phase with little or no detectable oxidation taking place. Fenton's reagent completely oxidized the dissolved phase TCE in the soil column experiment when TCE and Fenton's regent were simultaneously fed into the column. The results of this study showed that the feasibility of injecting Fenton's reagent or H(2)O(2) as a Fenton-type oxidant into the subsurface is highly dependent on the soil oxidant demand (SOD), presence of sufficient quantities of ferrous iron in the application area, and the proximity of the injection area to the zone of high aqueous concentration of the target contaminant. Also, it was found that in situ application of H(2)O(2) could have a gas-sparging effect on the dissolved VOC in groundwater, requiring careful attention to the remedial system design.     

Complete removal of chlorinated aromatic compounds from oils by channel-type gamma-cyclodextrin assembly

This paper describes the complete removal of chlorinated aromatic compounds from insulating oil by a channel-type gamma-cyclodextrin (gamma-CD) assembly as a new adsorbent. Using this type of adsorbent (50-60 wt % of oil), 1,2,4- and 1,3,5-trichlorobenzenes, 2- and 4-chlorobiphenyls (2- and 4-MCBs), 4,4'-dichlorobiphenyl (4,4'-DiCB), and 3,4,4'-trichlorobiphenyl (3,4,4'-TrCB), whose initial concentrations were 100 ppm, were completely removed from the insulating oil. Competitive adsorption experiments using a mixture of 2-MCB and 4-MCB or a mixture of 4-MCB, 4,4'-DiCB, and 3,4,4'-TrCB revealed that selective adsorption based on the shape and size of the chlorinated aromatics was achieved by the channel-type gamma-CD assembly, implying that inclusion into the cavity of the channel-type gamma-CD was responsible for the removal of chlorinated aromatics from insulating oil. It was also found that more than 70% of adsorbed chlorinated aromatics was easily recovered from the channel-type gamma-CD by simply washing with n-hexane, and chlorinated aromatics were completely removed from the insulating oil even by the regenerated adsorbent, indicating that the gamma-CD assembly can be easily regenerated and recycled.     

Chemical oxidation of chlorinated non-aqueous phase liquid by hydrogen peroxide in natural sand systems

This study explored the Fenton-like oxidation of trichloroethylene (TCE) existing as dense non-aqueous phase liquid (DNAPL) in natural silica sand (iron=0.04 g/kg) and the sand from an aquifer (iron=2.01 g/kg). Glass bead containing no iron mineral was used as the control. Batch oxidation experiments were conducted to assess interactions between oxidant and TCE DNAPL. Column experiments were performed to evaluate dynamics of TCE and H(2)O(2) during oxidation. The pH was not altered. In the batch system, a single application of 3% H(2)O(2) to the aquifer sand oxidized 40% of the added TCE DNAPL in 1 h, which was four times of that by dissolution with the gas purge procedure. This demonstrated the ability of mineral-catalyzed Fenton-like reaction to directly oxidize TCE in non-aqueous liquid. In the column experiments, after passing 7 pore volumes (PVs) of 1.5 and 3% H(2)O(2) solution, the residual TCE in aquifer sand column was 12.0 and 2.6% of the initial added, respectively. On the other hand, 28.4% of the added TCE still remained in the silica sand column by 7 PVs of 3% H(2)O(2). The distribution of TCE in column and effluent indicated the occurring of direct oxidation of TCE DNAPL and the increased solubilization, which probably due to size reduction of DNAPL droplets, followed by water-phased TCE oxidation.     

Effects of pure and dyed PCE on physical and interfacial properties of remedial solutions

Hydrophobic dyes have been used to visually distinguish dense non-aqueous phase liquid (DNAPL) contaminants from background aqueous phases and soils. The objective of this study was to evaluate the effects of a dyed DNAPL, 0.5 g Oil-Red-O/l of PCE, on the physical properties of remedial solutions: water, co-solvents (50, 70, and 90% (v/v) ethanol), and surfactants (4% (w) sodium dihexyl sulfosuccinate). This study compared the densities, viscosities, and interfacial tensions (IFTs) of the remedial solutions in contact with both dyed and undyed PCE. The presence of the dye in PCE substantially alters the IFTs of water and ethanol solutions, while there is no apparent difference in IFTs of surfactant solutions. The remedial solutions saturated with PCE showed higher viscosities and densities than pure remedial solutions. Solutions with high ethanol content exhibited the largest increases in liquid density. Because physical properties affect the flow of the remedial solutions in porous media, experiments using dyed DNAPLs should assess the influence of dyes on fluid and interfacial properties prior to remediation process analysis.     

Some Properties of an Ethoxylated Castor Oil and Ethoxylated Oleyl Alcohol

Abstract

Ethoxylated derivates have been used as surfactants for some years. In this work, ethoxylated castor oil and ethoxylated oleyl alcohol alone and/or their I:I mixtures were used as surfactants in oil/water type of emulsion systems.

The physicochemical properties of ethoxylated castor oil (Simulsol OL 50) and ethoxylated oleyl alcohol (Simulsol 98) have been investigated.

Both of these materials have properties associated with non-ionic surfactants, although considerably soluble in water, the compounds have slight solubility in nonpolar solvents.

Surface tensions of aqueous solutions were measured over a temperature range of 20°C to 40°C. CMC were determined by surface tension measurements. pH, refractive index, conductivity and density of the two surfactants were also determined.     

Application of H2O2 lifetime as an indicator of TCE Fenton-like oxidation in soils

Hydrogen peroxide decomposition and trichloroethylene (TCE) oxidation kinetics were studied through batch slurry experiments, performed on two TCE contaminated soils (a sandy soil and a clay soil), characterized by different texture and organic fraction; besides, experiments were also performed on sandy soil columns, in order to more closely reproduce the typical conditions of an in situ treatment. The results of the batch tests indicated that hydrogen peroxide lifetime was correlated to the oxidation efficiency; namely, complete TCE oxidation was achieved only for the conditions characterized by longer hydrogen peroxide lifetime, that was obtained by addition of a proper stabilizer (KH(2)PO(4)). The soil properties were also observed to influence both hydrogen peroxide decomposition and TCE oxidation kinetics, probably as a consequence of the different TOC content. The soil column experiments, performed on 10, 20, and 30 cm long columns, indicated that hydrogen peroxide decomposition, which was almost complete at 30 cm depth, was on the contrary negligible when the stabilizer was added. In agreement with this observation, the performance of TCE oxidation were greatly improved in the latter case. Based upon the collected results, it can be concluded that hydrogen peroxide experiments may be useful, at least in the first screening phase of the design activity, for selecting, among the different operating conditions, those that may be potentially more effective for the oxidation treatment.     

Some Properties of an Ethoxylated Castor Oil and Ethoxylated Oleyl Alcohol

Ethoxylated derivates have been used as surfactants for some years. In this work, ethoxylated castor oil and ethoxylated oleyl alcohol alone and/or their I:I mixtures were used as surfactants in oil/water type of emulsion systems.

The physicochemical properties of ethoxylated castor oil (Simulsol OL 50) and ethoxylated oleyl alcohol (Simulsol 98) have been investigated.

Both of these materials have properties associated with non-ionic surfactants, although considerably soluble in water, the compounds have slight solubility in nonpolar solvents.

Surface tensions of aqueous solutions were measured over a temperature range of 20°C to 40°C. CMC were determined by surface tension measurements. pH, refractive index, conductivity and density of the two surfactants were also determined.     

Removal of trichloroethylene in reduced soil columns

A continuous soil column experiment was conducted to investigate reductive dechlorination of trichloroethylene (TCE) in soil system reductively manipulated by three types of reductants (Fe(II), dithionite, and Fe(II) + dithionite (combined treatment of Fe(II) and dithionite)). The soil column reduced by Fe(II) + dithionite has the greatest bed volumes (51.8) treated to breakthrough indicating that the combined treatment of Fe(II) and dithionite is more effective for the reductive dechlorination of TCE in the reduced soil column than the separate treatment of Fe(II) or dithionite. The measured bed volumes to breakthrough in control and treated soil columns were similar to the estimated bed volumes based on the result of batch kinetic experiment, differing by a factor of 0.96-1.02. The relative concentration of bromide (non-reactive tracer) reached the approximate value of 1 between 0.87 and 1.03 bed volume. C2 hydrocarbons (acetylene, ethylene, and ethane) were observed as transformation products in the effluents of soil columns treated by the reductants. However, no chlorinated intermediates were observed at the concentrations above detection limits throughout the experiment. Chloride was observed in the effluents of soil columns reduced by dithionite and Fe(II) + dithionite.     

Resonance-enhanced multiphoton ionization for real-time monitoring of trichloroethylene formed by degradation of tetrachloroethylene using zero-valent zinc

Resonance-enhanced multiphoton ionization (REMPI) is investigated as a potential technique for real-time monitoring of selected volatile organochloride compounds (VOCs). In a proof-of-concept experiment, the progress of the reductive-degradation of tetrachloroethylene (PCE) to trichloroethylene (TCE) by zero-valent zinc was monitored by REMPI measurements performed in the headspace above the PCE solution. Two-photon resonant REMPI spectra of TCE and PCE were recorded over the wavelength range 305-320 nm. The concentrations of PCE and TCE in the headspace were monitored by measurement of the ionization signal with 315.64- and 310.48-nm excitation for PCE and TCE, respectively. Calibration curves yielded a linear range of more than 2 orders of magnitude for both compounds. The REMPI headspace results agreed well with the solution-phase results from gas chromatography analysis, which was used for independent verification of the progress of the reaction.     

Remediation of TCE-contaminated groundwater using nanocatalyst and bacteria

The objective of this study was to develop and evaluate the remediation of trichloroethene (TCE)-contaminated groundwater using both a nanocatalyst (bio-Zn-magnetite) and bacterium (similar to Clostridium quinii) in anoxic environments. Of the 7 nanocatalysts tested, bio-Zn-magnetite showed the highest TCE dechlorination efficiency, with an average of ca. 90% within 8 days in a batch experiment. The column tests confirmed that the application of bio-Zn-magnetite in combination with the bacterium achieved high degradation efficiency (ca. 90%) of TCE within 5 days compared to the nanocatalyst only, which degraded only 30% of the TCE. These results suggest that the application of a nanocatalyst and the bacterium have potential for the remediation of TCE-contaminated groundwater in subsurface environments.