Niels Hartog

The impact of low-temperature seasonal aquifer thermal energy storage (SATES) systems on chlorinated solvent contaminated groundwater: Modeling of spreading and degradation

Groundwater systems are increasingly used for seasonal aquifer thermal energy storage (SATES) for periodic heating and cooling of buildings. Its use is hampered in contaminated aquifers because of the potential environmental risks associated with the spreading of contaminated groundwater, but positive side effects, such as enhanced contaminant remediation, might also occur. A first reactive transport study is presented to assess the effect of SATES on the fate of chlorinated solvents by means of scenario modeling, with emphasis on the effects of transient SATES pumping and applicable kinetic degradation regime. Temperature effects on physical, chemical, and biological reactions were excluded as calculations and initial simulations showed that the small temperature range commonly involved (ΔT<15 °C) only caused minor effects. The results show that a significant decrease of the contaminant mass and (eventually) plume volume occurs when degradation is described as sediment-limited with a constant rate in space and time, provided that dense non-aqueous phase liquid (DNAPL) is absent. However, in the presence of DNAPL dissolution, particularly when the dissolved contaminant reaches SATES wells, a considerably larger contaminant plume is created, depending on the balance between DNAPL dissolution and mass removal by degradation. Under conditions where degradation is contaminant-limited and degradation rates depend on contaminant concentrations in the aquifer, a SATES system does not result in enhanced remediation of a contaminant plume. Although field data are lacking and existing regulatory constraints do not yet permit the application of SATES in contaminated aquifers, reactive transport modeling provides a means of assessing the risks of SATES application in contaminated aquifers. The results from this study are considered to be a first step in identifying the subsurface conditions under which SATES can be applied in a safe or even beneficial manner.

Synergistic effects of bioremediation and electrokinetics in the remediation of petroleum-contaminated soil.

The present study evaluated the coupling interactions between bioremediation (BIO) and electrokinetics (EK) in the remediation of total petroleum hydrocarbons (TPH) by using bio-electrokinetics (BIO-EK) with a rotatory 2-D electric field. The results demonstrated an obvious positive correlation between the degradation extents of TPH and electric intensity both in the EK and BIO-EK tests. The use of BIO-EK showed a significant improvement in degradation of TPH as compared to BIO or EK alone. The actual degradation curve in BIO-EK tests fitted well with the simulated curve obtained by combining the degradation curves in BIO- and EK-only tests during the first 60 d, indicating a superimposed effect of biological degradation and electrochemical stimulation. The synergistic effect was particularly expressed during the later phase of the experiment, concurrent with changes in the microbial community structure. The community composition changed mainly according to the duration of the electric field, leading to a reduction in diversity. No significant spatial shifts in microbial community composition and bacterial numbers were detected among different sampling positions. Soil pH was uniform during the experimental process, soil temperature showed no variations between the soil chambers with and without an electric field.

Kinetic reaction modeling framework for identifying and quantifying reductant reactivity in heterogeneous aquifer sediments.

Water-sediment interactions triggered by the injection of oxidized aqueous solutions into anoxic groundwater systems usually modify both the aquifer matrix and control the final aqueous composition. The identification and quantification of these reactions in complex heterogeneous systems remains a challenge for the analysis and prediction of water quality changes. Driven by the proposed injection of large quantities of oxic water into a deep anoxic heterogeneous pyritic aquifer; this study was undertaken to quantify the reactivity of aquifer sediments with respect to oxidant consumption and to characterize the variability of the reaction rates across different lithological units. A total of 53 samples were incubated for periods of 14, 37, and 50 days, during which the gas-phase was continuously monitored and the aqueous composition analyzed. A geochemical modeling framework was developed that incorporated a mixed set of equilibrium and kinetic reactions and supported the interpretation and quantification of the geochemical controls. The good agreement between simulated and experimental results of O2 consumption, CO2 production, pH, major ions, and trace metals suggests that the framework was able to successfully quantify reaction rates of competing redox and buffering reactions for the different lithological aquifer material.

Evaluation of the kinetic oxidation of aqueous volatile organic compounds by permanganate

The use of permanganate solutions for in-situ chemical oxidation (ISCO) is a well-established groundwater remediation technology, particularly for targeting chlorinated ethenes. The kinetics of oxidation reactions is an important ISCO remediation design aspect that affects the efficiency and oxidant persistence. The overall rate of the ISCO reaction between oxidant and contaminant is typically described using a second-order kinetic model while the second-order rate constant is determined experimentally by means of a pseudo first order approach. However, earlier studies of chlorinated hydrocarbons have yielded a wide range of values for the second-order rate constants. Also, there is limited insight in the kinetics of permanganate reactions with fuel-derived groundwater contaminants such as toluene and ethanol. In this study, batch experiments were carried out to investigate and compare the oxidation kinetics of aqueous trichloroethylene (TCE), ethanol, and toluene in an aqueous potassium permanganate solution. The overall second-order rate constants were determined directly by fitting a second-order model to the data, instead of typically using the pseudo-first-order approach. The second-order reaction rate constants (M(-1) s(-1)) for TCE, toluene, and ethanol were 8.0×10(-1), 2.5×10(-4), and 6.5×10(-4), respectively. Results showed that the inappropriate use of the pseudo-first-order approach in several previous studies produced biased estimates of the second-order rate constants. In our study, this error was expressed as a function of the extent (P/N) in which the reactant concentrations deviated from the stoichiometric ratio of each oxidation reaction. The error associated with the inappropriate use of the pseudo-first-order approach is negatively correlated with the P/N ratio and reached up to 25% of the estimated second-order rate constant in some previous studies of TCE oxidation. Based on our results, a similar relation is valid for the other volatile organic compounds studied.

Oxidation of volatile organic vapours in air by solid potassium permanganate

Volatile organic compounds (VOCs) may frequently contaminate groundwater and pose threat to human health when migrating into the unsaturated soil zone and upward to the indoor air. The kinetic of chemical oxidation has been investigated widely for dissolved VOCs in the saturated zone. But, so far there have been few studies on the use of in situ chemical oxidation (ISCO) of vapour phase contaminants. In this study, batch experiments were carried out to evaluate the oxidation of trichloroethylene (TCE), ethanol, and toluene vapours by solid potassium permanganate. Results revealed that solid potassium permanganate is able to transform the vapour of these compounds into harmless oxidation products. The degradation rates for TCE and ethanol were higher than for toluene. The degradation process was modelled using a kinetic model, linear in the gas concentration of VOC [ML(-3)] and relative surface area of potassium permanganate grains (surface area of potassium permanganate divided by gas volume) [L(-1)]. The second-order reaction rate constants for TCE, ethanol, and toluene were found to be equal to 2.0×10(-6) cm s(-1), 1.7×10(-7) cm s(-1), and 7.0×10(-8) cm s(-1), respectively.

Oxidation of trichloroethylene, toluene, and ethanol vapors by a partially saturated permeable reactive barrier

The mitigation of volatile organic compound (VOC) vapors in the unsaturated zone largely relies on the active removal of vapor by ventilation. In this study we considered an alternative method involving the use of solid potassium permanganate to create a horizontal permeable reactive barrier for oxidizing VOC vapors. Column experiments were carried out to investigate the oxidation of trichloroethylene (TCE), toluene, and ethanol vapors using a partially saturated mixture of potassium permanganate and sand grains. Results showed a significant removal of VOC vapors due to the oxidation. We found that water saturation has a major effect on the removal capacity of the permeable reactive layer. We observed a high removal efficiency and reactivity of potassium permanganate for all target compounds at the highest water saturation (Sw=0.6). A change in pH within the reactive layer reduced oxidation rate of VOCs. The use of carbonate minerals increased the reactivity of potassium permanganate during the oxidation of TCE vapor by buffering the pH. Reactive transport of VOC vapors diffusing through the permeable reactive layer was modeled, including the pH effect on the oxidation rates. The model accurately described the observed breakthrough curve of TCE and toluene vapors in the headspace of the column. However, miscibility of ethanol in water in combination with produced water during oxidation made the modeling results less accurate for ethanol. A linear relationship was found between total oxidized mass of VOC vapors per unit volume of permeable reactive layer and initial water saturation. This behavior indicates that pH changes control the overall reactivity and longevity of the permeable reactive layer during oxidation of VOCs. The results suggest that field application of a horizontal permeable reactive barrier can be a viable technology against upward migration of VOC vapors through the unsaturated zone.

Evaluation of a horizontal permeable reactive barrier for preventing upward diffusion of volatile organic compounds through the unsaturated zone.

Permeable reactive barriers are commonly used to treat contaminant plumes in the saturated zone. However, no known applications of horizontal permeable reactive barriers (HPRBs) exist for oxidizing volatile organic compounds (VOCs) in the unsaturated zone. In this study, laboratory column experiments were carried out to investigate the ability of a HPRB containing solid potassium permanganate, to oxidize the vapors of trichloroethylene (TCE), toluene, and ethanol migrating upward from a contaminated saturated zone. Results revealed that an increase in initial water saturation and HPRB thickness strongly affected the removal efficiency of the HPRB. Installing the HPRB relatively close to the water table was more effective due to the high background water content and enhanced diffusion of protons and/or hydroxides away from the HPRB. Inserting the HPRB far above the water table caused rapid changes in pH within the HPRB, leading to lower oxidation rates. The pH effects were included in a reactive transport model, which successfully simulated the TCE and toluene experimental observations. Simulations for ethanol were not affected by pH due to condensation of water during ethanol oxidation, which caused some dilution in the HRPB.

The transport behaviour of elemental mercury DNAPL in saturated porous media: Analysis of field observations and two-phase flow modelling

Mercury is a contaminant of global concern. The use of elemental mercury in various (former) industrial processes, such as chlorine production at chlor-alkali plants, is known to have resulted in soil and groundwater contaminations worldwide. However, the subsurface transport behaviour of elemental mercury as an immiscible dense non-aqueous phase liquid (DNAPL) in porous media has received minimal attention to date. Even though, such insight would aid in the remediation effort of mercury contaminated sites. Therefore, in this study a detailed field characterization of elemental mercury DNAPL distribution with depth was performed together with two-phase flow modelling, using STOMP. This is to evaluate the dynamics of mercury DNAPL migration and the controls on its distribution in saturated porous media. Using a CPT-probe mounted with a digital camera, in-situ mercury DNAPL depth distribution was obtained at a former chlor-alkali-plant, down to 9 m below ground surface. Images revealing the presence of silvery mercury DNAPL droplets were used to quantify its distribution, characteristics and saturation, using an image analysis method. These field-observations with depth were compared with results from a one-dimensional two-phase flow model simulation for the same transect. Considering the limitations of this approach, simulations reasonably reflected the variability and range of the mercury DNAPL distribution. To further explore the impact of mercurys physical properties in comparison with more common DNAPLs, the migration of mercury and PCE DNAPL in several typical hydrological scenarios was simulated. Comparison of the simulations suggest that mercurys higher density is the overall controlling factor in controlling its penetration in saturated porous media, despite its higher resistance to flow due to its higher viscosity. Based on these results the hazard of spilled mercury DNAPL to cause deep contamination of groundwater systems seems larger than for any other DNAPL.

Bias by the inappropriate use of the pseudo-first order approach to estimate second-order reaction rate constants : Reply to the commentary by Tratnyek (this issue)

We thank Dr. Tratnyek (2015–in this issue) for taking an interest in our recent research on the determination of kinetic rate constants for the oxidation of several volatile organic compounds (Mahmoodlu et al., 2014). His comments provide a valuable perspective on the relevance of our results and we appreciate the opportunity to elaborate on the key aspects raised and to emphasize their importance, particularly so for the bias in second-order rate constants estimated with inappropriate use of the pseudo-first order approach. To determine second-order rate constants experimentally, a pseudo first-order approach is routinely used experimentally and described in many chemistry textbooks (e.g. Atkins and de Paula, 2006). In this approach, one of two reactants is supplied in excess to support the assumption that its concentration change during the experiment is negligible. In the commentary, it is rightfully stressed that our study clarifies how the error in the estimated second-order rate constant decreases with increasing amounts of the actual stoichiometric excess used. Although theoretically this error never actually reaches zero, we did not mean to question the general applicability of the pseudo-first order approach. A negative bias of less than 5% in the estimate for a stoichiometric excess ratio (P/N) of over 40 (Fig. 4 in Mahmoodlu et al. (2014)) might indeed be considered acceptable by some practitioners. However, as shown, previously published pseudo-first order based estimates of the second-order rate constant for the oxidation of TCE by permanganate appear to be negatively biased by up to 20% with respect to our recalculated estimates. This bias is unnecessary, and does no service to the concept of a rate “constant”. Many other studies have presented pseudo-first order based estimates, but did not present the raw experimental data to allow the recalculation of the second-order rate constants. Fig. 1 in the commentary presents a renewed summary of published estimates for second-order rate constants for the oxidation of TCE by permanganate as if these were all equally valid, regardless of whether the “sufficient excess” assumption was appropriate for all included pseudo-first order estimates. This goes against the key point in Mahmoodlu et al. (2014) which stresses that bias in the estimates of second-order rate constants is introduced by the inappropriate use of the pseudo-first order approach. Perhaps we should have further emphasized that studies that summarize second-order rate constants without considering these biased estimates (Waldemer and Tratnyek, (2006)) unnecessarily exaggerate the

Infiltration and Distribution of Elemental Mercury DNAPL in Water-Saturated Porous Media : Experimental and Numerical Investigation

Liquid elemental mercury occurrence in the subsurface as dense non-aqueous phase liquid (DNAPL) is reported worldwide in proximity of several industrial facilities, such as chlor-alkali plants. Insight into Hg0 DNAPL infiltration behavior is lacking and, to date, there are no experimental observations of its infiltration and distribution in water-saturated porous media, except for capillary pressure-saturation column experiments. To better understand the processes governing elemental mercury DNAPL flow behavior, a series of flow container experiments were performed using mercury DNAPL (in sands and glass beads) and tetrachloroethylene (PCE) (in sands). While liquid Hg0 was not able to infiltrate in the sand-filled container due to an overall lower permeability of the sample and a defect of the setup, in the glass beads experiment mercury DNAPL infiltration occurred. Dual gamma ray measurements showed that, in glass beads, liquid Hg0 preferentially migrated towards higher porosity zones. As for PCE, infiltration and distribution of Hg0 DNAPL are strongly affected by the heterogeneities within the porous formation. However, compared to other DNAPLs, liquid Hg0 shows a strong attenuation potential of gamma rays. Finally, numerical simulations of the glass beads experiment showed an overall good agreement with the experimental results, highlighting that, among the factors influencing the prediction of liquid Hg0 migration in water-saturated porous media, the most critical are (i) the knowledge of the inflow rate, (ii) the reliable estimation of the porous formation permeability, and (iii) the accurate representation of the correlation between retention properties and intrinsic permeability.