Laboratory-scale characterization of slow-release permanganate gel (SRP-G) for the in-situ treatment of chlorinated-solvent groundwater plumes.

Significant challenges remain for the remediation of chlorinated-solvent plumes in groundwater, such as trichloroethene (TCE) and tetrachloroethene (PCE). A novel slow-release permanganate gel (SRP-G) technique may show promise for the in-situ treatment (remediation) of chlorinated contaminant plumes in groundwater. A series of laboratory experiments were conducted to characterize the primary physical factors that influence SRP-G gelation processes to optimize SRP-G performance for plume treatment. Specifically, experiments were conducted to quantify gel zeta potential, particle size distribution, and viscosity to determine SRP-G gelation characteristics and processes. These experiments tested various concentrations of two SRP-G amendment solutions (NaMnO4 and KMnO4) prepared with 30-wt.% and 50-wt.% colloidal silica to determine such influences on zeta potential, particle size distribution, and viscosity. The results of this study show that SRP-G solutions with low zeta potential and relatively high pH favor more rapid SRP-G gelation. The concomitant interaction of the predominantly negatively charged colloidal silica particles and the positively charged dissociated cations (Na+ and K+) in the SRP-G solution had the effect of stabilizing charge imbalance via attraction of particles and thereby inducing a greater influence on the gelation process. Gel particle size distribution and changes in viscosity had a significant influence on SRP-G solution gelation. The addition of permanganate (NaMnO4 or KMnO4) increased the average particle size distribution and the viscosity of the SRP-G solution and decreased the overall gelation time. SRP-G amendments (NaMnO4 or KMnO4) prepared with 50-wt.% colloidal silica showed more effective gelation (and reduced gelation time) compared to SRP-G amendments prepared with 30-wt.% colloidal silica. Under the conditions of these experiments, it was determined that both the 7-wt.% NaMnO4 solution and 90 mg/L KMnO4 solution using 50-wt.% colloidal silica would be the optimal injection SRP-G solution concentrations for this in-situ treatment technique.

Surfactant-enhanced in-situ oxidation of DNAPL source zone: Experiments and numerical modeling.

In this study we investigate the synergetic effects of combining surfactant-enhanced dissolution with in-situ oxidation of a pool-dominated PCE DNAPL source zone entrapped in porous media. Flow cell flushing experiments packed with silica sand and natural calcareous soil were conducted with a surfactant (Tween 80) and permanganate (MnO4-) used as dissolution and oxidation agents, respectively. The resultant breakthrough curves exhibited a multiple step behavior with mass removal controlled in the latter stages by the less-accessible DNAPL mass. DNAPL spatial architecture, flow-field heterogeneity, and flushing solution all influenced the remediation effort. When taking into account both the surfactant-enhanced dissolution and permanganate oxidation processes, mass-flux reduction/mass-removal behavior relationships indicated that the inclusion of oxidation in the remediation scheme delayed the drop in mass flux from the source zone, leading to improved DNAPL removal efficiency. Numerical modeling was also performed to further evaluate the efficacy of the surfactant-enhanced chemical oxidation of DNAPL PCE with permanganate. The system of reaction equations available in the multiphase flow simulator UTCHEM were adapted to simulate the chemical oxidation process in the presence of a surfactant. The model results yield lower oxidation reaction rate constants in the presence of Tween 80, indicating that Tween 80 can interfere with the reaction rate. However, the increase in the solubility of PCE in the presence of Tween 80 more than compensates for the decrease in reaction rate constant. Overall, for Tween 80/MnO4- applied at sufficient dosages, more efficient DNAPL zone remediation was achieved compared to surfactant flushing or permanganate oxidation alone.

Enhanced-solubilization and dissolution of multicomponent DNAPL from homogeneous porous media.

The presence of multicomponent dense nonaqueous phase liquid (DNAPL) mixtures in porous media can significantly limit the effectiveness of groundwater remediation. A series of column transport and flushing experiments were conducted to quantify the impact of various enhanced flushing agents on dissolution and removal of a multicomponent DNAPL source within a macroscopically homogeneous porous medium. The columns were established with NAPL saturations consisting of an equal mole mixture of cis-1,2-dichloroethene, trichloroethene, and tetrachloroethene. The solubilization agents used included two complexing sugars - hydroxypropyl-ß-cyclodextrin (HPCD and methyl-ß-cyclodextrin (MCD); a surfactant - sodium dodecyl sulfate (SDS); and a cosolvent - ethanol (EtOH). The chemical flushing agents greatly reduced the time needed to remove each DNAPL component, compared to flushing with water alone. Initial DNAPL-component elution concentrations were successfully predicted using Raoult's Law for MCD, HPCD, and water flushing, indicating that ideal dissolution was initiated by the lower-power enhanced-solubilization agents. EtOH was most efficient at removing the contaminants in terms of normalized mass recovery but least efficient based on a mass-ratio and mole-ratio of contaminant to reagent analysis. SDS was most efficient for contaminant removal when analyzed based on mass-contaminant to mass-reagent recovered and MCD was most effective based on a moles-contaminant to moles-reagent recovered efficiency evaluation. However, in terms of mass flux reduction analysis (i.e. removal metric), SDS was least efficient for contaminant removal compared to all other enhanced-flushing agents tested, especially during the initial stages of DNAPL removal. Results from this study indicate that ideal dissolution was initiated during enhanced-solubilization and that several criteria should be used to evaluate the removal effectiveness of flushing agents for multi-component NAPL systems.

Contamination by As, Hg, and Sb in a region with geogenic As anomaly and subsequent human health risk characterization.

Arsenic (As) is among the most harmful toxic elements to human health with severe carcinogenic and non-carcinogenic effects. The present study aims to (1) characterize a site with geogenic As anomaly (Emet basin) in Kutahya, Turkey via soil (urban, agriculture, forest; n = 53 total), water (n = 11), and agricultural product (n = 19) samples; and, (2) characterize human health risks for different receptors under specific exposure scenarios. Soil As levels were very high (range, 22.4-765 mg kg-1). Previous literature suggested some evidence of Sb and Hg combined with As in mineral forms in the region; the present study found elevated Sb (up to 76.0 mg kg-1) in two regions with very high As levels, but Hg concentrations were low in the region. Soils from urban/agricultural zones (representing anthropogenic impact) did not have statistically different As levels compared with forest soils (representing low/no human impact). As water concentrations were also very high (range, 14.0-729 µg L-1), however, uptake by agricultural products was low, mostly limited to wheat (up to 0.7 mg kg-1). Exposure assessment/risk characterization showed that non-carcinogenic risk following exposure to soils was very high for children (hazard index up to 37 under reasonable maximum exposure) as well as carcinogenic risk (probability up to 1.19E-3). The risk was even higher considering intake of water, and in this case, both for children and adults (HI, 4.0-66.6; cancer risk, 1.29E-4-1.84E-2). The potential adverse outcomes of the As anomaly in the region may be grave, thus further geochemical investigation of As speciation and mobile fractions as well as gastrointestinal As bioaccessibility supplementing probabilistic human health risk characterization are recommended.

Experimental comparison of agent-enhanced flushing for the recovery of crude oil from saturated porous media.

The subsurface remediation of nonaqueous liquid (NAPL) has proven to be challenging even when implementing more aggressive enhanced-flushing techniques. The objective of this study was to evaluate the effectiveness of a combination of alkaline- and surfactant-based enhanced flushing for the removal of crude oil (medium fraction) from saturated porous media. Synchrotron X-ray microtomography (SXM) was used to perform pore-scale examination of NAPL fragmentation and changes in blob morphology, and recovery using three different advective flushing methods: surface-active agent (surfactant) flushing, alkaline flushing, and sequential alkaline-surfactant flushing. This set of experiments was conducted to understand effects on such processes (fragmentation and recovery) as a function of media composition (geochemical/mineralogical) and pH alterations due to calcium-carbonate fraction. Results showed that the sequential flushing technique (alkaline→ surfactant) yielded the highest recovery, 32% after 5 pore volumes (PV) of flushing. The crude oil (NAPL) distribution varied due to differences in porous medium mixture composition and type of fluid (i.e. surfactant vs. alkaline) used for flushing. The results of this study can be used to aid in the understanding of physical and chemical parameters/properties that control mobilization of crude oil in saturated porous media. This can help reduce time and cost during remediation of contaminated sites that contain crude oil or less dense NAPL derivatives consistent with fuel-type petroleum hydrocarbons.

Experiments and sensitivity coefficients analysis for multiphase flow model calibration of enhanced DNAPL dissolution.

Multiphase flow modeling is often used for the comparison and optimization of subsurface nonaqueous phase liquid (NAPL) remediation schemes. The calibration of such models is a challenging task due to the lack of detailed data describing the initial NAPL spatial distribution and the processes governing the fate and transport of NAPLs in porous media. In this study laboratory scale experiments were conducted to evaluate reagent-enhanced dense nonaqueous phase liquid (DNAPL) solubilization in saturated heterogeneous media. The DNAPL consisted of both pooled and residual saturation forms. To gain insight into the influence of various input parameters on effluent concentrations, the multiphase flow program was used to compute the sensitivity coefficients of key parameters, relating to the flow, flushing solution properties, soil parameters, NAPL distribution and mass transfer coefficient. The sensitivity coefficients were, in turn, used to aid in the model calibration and to underline the difficulties associated with the calibration of multiphase flow models, most notably the non-uniqueness of the calibration process when complete information is lacking. To alleviate this uncertainty and provide additional constraints, the conducted flushing experiments were jointly used to calibrate the multiphase flow model. The results of the model calibration suggest that the interphase mass transfer coefficient is dependent on the properties of the reagent aqueous solution used for DNAPL remediation, most notably the viscosity and interfacial tension.

A pore-scale investigation of heavy crude oil trapping and removal during surfactant-enhanced remediation.

The presence of nonaqueous phase liquid (NAPL) in the subsurface presents significant challenges for soil and groundwater remediation. In particular, heavy crude oil, coal tar and/or bitumen present unique difficulties for removal and cleanup due to associated high viscosities, low aqueous solubilities, and limited mobility extraction potential. Although surfactant-enhanced aquifer remediation (SEAR) techniques have shown some promise for source removal, overall remediation (mobilization) performance will depend significantly on interfacial effects between the fluid and solid phases. A pore-scale study, implementing synchrotron X-ray microtomography (SXM), was conducted to understand and quantify the trapping and mobilization mechanisms and in-situ emulsification processes of heavy crude oil distributed within increasing complexity (i.e. physical heterogeneity) unconsolidated sands during surfactant flushing events. Pore-scale imaging analyses were conducted to quantify the changes in oil blob morphology before and after surfactant flushing events to assess the primary factors controlling the recovery. Results showed relatively low (10%) net recovery from the homogeneous sand after 5 pore volumes (PVs) of surfactant flushing and may be, in part, due to the more connected ganglia (i.e. single continuous) oil-phase. Such a condition may have limited the surfactant/oil contact resulting in relatively low interfacial activity and correspondingly inefficient oil mobilization and recovery. Negligible net oil recovery was achieved from the mildly-heterogeneous-sand and is likely due to the lower associated permeability of this particular porous medium. Furthermore, the oil-phase distribution within this medium primarily consisted of small disconnected blobs more readily exposed (in contact with) the surfactant solution. For the highly-heterogeneous-sand experiments, an average of 20% heavy-oil recovery resulted after each flushing event (total of ~37% after 5 PVs) and was attributed to more efficient reduction of interfacial tension associated with the increased surfactant-oil contact. The associated higher pH sand/fine­carbonate system may have aided in maintaining a water-wet porous medium, a condition more conducive to higher oil recovery and displacement efficiency.

Characterizing and modeling of extensive atrazine elution tailing for stable manure-amended agricultural soil.

Non-ideal sorption and extensive elution tailing behavior of atrazine was evaluated for an agricultural soil with and without stable manure amendment (10% by weight). A series of laboratory experiments showed that the sorption of atrazine was described by rate-limited, nonlinear reversible processes (Freundlich isotherm) for both non-amended and amended soil. Non-ideal transport of atrazine exhibited extensive low concentration elution tailing due to the most likely organic carbon fraction in the soil. This tailing behavior was more pronounced and extensive for soil with 10% stable-manure amendment. Two-site transport modeling analyses including non-linear sorption and rate-limited sorption-desorption provided a reasonably good match to the atrazine breakthrough curves but were unable to match the long-term concentration tailing, even for non-amended soil. A mathematical model incorporating nonlinear, rate-limited sorption/desorption described by a continuous-distribution function was used to successfully simulate atrazine transport early-time breakthrough and long-term concentration tailing for both non-amended and amended soil conditions.

Impact of enhanced-flushing reagents and organic-liquid distribution on mass removal and mass-discharge reduction.

A series of column and flow-cell experiments was conducted to investigate the impact of non-uniform organic-liquid distribution on the relationship between reductions in contaminant mass discharge and reductions in source zone mass under conditions of enhanced-solubilization flushing. Trichloroethene was used as the model organic liquid, and SDS (sodium dodecyl sulfate) and ethanol were used as representative enhanced-flushing reagents. The results were compared to those of water-flood control experiments. Concentrations of trichloroethene in the effluent exhibited multi-step behavior with time, wherein multiple secondary periods of quasi steady state were observed. This non-ideal behavior was observed for both the water-flood and enhanced-flushing experiments. For all flow-cell experiments, the later stage of mass removal was controlled by the more poorly- accessible mass associated with higher-saturation zones. The profiles relating reductions in contaminant mass discharge and reductions in mass exhibited generally similar behavior for both the water-flood and enhanced-flushing experiments. This indicates that while the rates and magnitudes of mass removal are altered by the presence of a solubilization-reagent solution, the fundamental mass-removal process is not. The profiles obtained for the flow-cell systems differed from those obtained for the column systems, highlighting the impact of source-zone heterogeneity on mass-removal behavior.

Sorption and transport of trichloroethylene in caliche soil.

Sorption of TCE to the caliche soil exhibited linear isotherm at the high TCE concentrations (Co=122-1300 mg L(-1)) but Freundlich isotherm at the low concentration range (1-122 mg L(-1)). Sorption strength of the carbonate fraction of the soil was about 100-fold lower than the sorption strength of soil organic matter (SOM) in the caliche soil, indicating weak affinity of TCE for the carbonate fraction of the soil. Desorption of TCE from the caliche soil was initially rapid (7.6×10(-4) s(-1)), then continued at a 100-fold slower rate (7.7×10(-6) s(-1)). Predominant calcium carbonate fraction of the soil (96%) was responsible for the fast desorption of TCE while the SOM fraction (0.97%) controlled the rate-limited desorption of TCE. Transport of TCE in the caliche soil was moderately retarded with respect to the water (R=1.75-2.95). Flow interruption tests in the column experiments indicated that the rate-limited desorption of TCE controlled the non-ideal transport of TCE in the soil. Modeling studies showed that both linear and non-linear nonequilibrium transport models provided reasonably good match to the TCE breakthrough curves (r2=0.95-0.98). Non-linear sorption had a negligible impact on both the breakthrough curve shape and the values of sorption kinetics parameters at the high TCE concentration (Co=1300 mg L(-1)). However, rate-limited sorption/desorption processes dominated at this concentration. For the low TCE concentration case (110 mg L(-1)), in addition to the rate-limited sorption/desorption, contribution of the non-linear sorption to the values of sorption kinetics became fairly noticeable.

Monitoring the changing position of coastlines using aerial and satellite image data: an example from the eastern coast of Trabzon, Turkey.

Coastline mapping and coastline change detection are critical issues for safe navigation, coastal resource management, coastal environmental protection, and sustainable coastal development and planning. Changes in the shape of coastline may fundamentally affect the environment of the coastal zone. This may be caused by natural processes and/or human activities. Over the past 30 years, the coastal sites in Turkey have been under an intensive restraint associated with a population press due to the internal and external touristic demand. In addition, urbanization on the filled up areas, settlements, and the highways constructed to overcome the traffic problems and the other applications in the coastal region clearly confirm an intensive restraint. Aerial photos with medium spatial resolution and high resolution satellite imagery are ideal data sources for mapping coastal land use and monitoring their changes for a large area. This study introduces an efficient method to monitor coastline and coastal land use changes using time series aerial photos (1973 and 2002) and satellite imagery (2005) covering the same geographical area. Results show the effectiveness of the use of digital photogrammetry and remote sensing data on monitoring large area of coastal land use status. This study also showed that over 161 ha areas were filled up in the research area and along the coastal land 12.2 ha of coastal erosion is determined for the period of 1973 to 2005. Consequently, monitoring of coastal land use is thus necessary for coastal area planning in order to protecting the coastal areas from climate changes and other coastal processes.

Adsorption and transport of arsenate in carbonate-rich soils: coupled effects of nonlinear and rate-limited sorption.

The transport and fate of arsenate in carbonate-rich soil under alkaline conditions was investigated with multiple approaches combining batch, sequential extraction and column experiments as well as transport modeling studies. Batch experiments indicated that sorption isotherm was nonlinear over a wide range of concentration (0.1-200 mg L(-1)) examined. As(V) adsorption to the calcareous soil was initially fast but then continued at a slower rate, indicating the potential effect of rate-limited sorption on transport. Column experiments illustrated that transport of As(V) was significantly retarded compared to a non-reactive tracer. The degree of retardation decreased with increasing As(V) concentration. As(V) breakthrough curves exhibited nonideal transport behavior due to the coupled effects of nonlinear and rate-limited sorption on arsenate transport, which is consistent with the results of modeling studies. The contribution of nonlinear sorption to the arsenate retardation was negligible at low concentration but increased with increasing As(V) concentration. Sequential extraction results showed that nonspecifically sorbed (easily exchangeable, outer sphere complexes) fraction of arsenate is dominant with respect to the inner-sphere surface bound complexes of arsenate in the carbonate soil fraction, indicating high bioavailability and transport for arsenate in the carbonate-rich soils of which Fe and Al oxyhydroxide fractions are limited.