The 21st century water quality challenges for managed aquifer recharge: towards a risk-based regulatory approach.

Sustained environmental and human health protection is threatened by ~350,000 chemicals available in global markets, plus new biological entities including coronaviruses. These water-quality hazards challenge the proponents of managed aquifer recharge (MAR) who seek to ensure the integrity of groundwater. A risk-based regulatory framework accounting for groundwater quality changes, adoption in subsurface attenuation zones, and use of advanced monitoring methods is required to support confidence in the sustainability of MAR.

La protection durable de l'environnement et de la santé humaine est menacée par ~350,000 substances chimiques disponibles sur les marchés mondiaux, à quoi s'ajoutent de nouvelles entités biologiques, incluant les coronavirus. Ces risques sur la qualité de l'eau sont un défi pour les partisans de la recharge raisonnée des aquifères (RRA) qui cherchent à assurer l'intégrité des eaux souterraines. Un cadre réglementaire basé sur les risques, tenant compte des changements de qualité des eaux souterraines, de l'adoption de zones d'atténuation souterraine, de l'utilisation de méthodes de contrôle avancées, est nécessaire pour soutenir la confiance dans la durabilité de la RRA.

La sostenibilidad del medio ambiente y la protección de la salud humana se ve amenazada por unas 350,000 sustancias químicas disponibles en los mercados mundiales, además de nuevas entidades biológicas como el coronavirus. Estos peligros para la calidad del agua suponen un desafío para los defensores de la recarga gestionada de acuíferos (MAR), que pretenden garantizar la integridad de las aguas subterráneas. Se necesita un marco normativo basado en el riesgo que tenga en cuenta los cambios en la calidad de las aguas subterráneas, la incorporación a las zonas de atenuación del subsuelo y el uso de métodos avanzados de control para respaldar la confianza en la sostenibilidad de la recarga acuífera gestionada.

A proteção sustentável do meio ambiente e da saúde humana está ameaçada por cerca de 350,000 produtos químicos disponíveis nos mercados globais, além de novas entidades biológicas, incluindo coronavírus. Esses riscos de qualidade da água desafiam os proponentes da recarga gerenciada de aquíferos (RGA) que buscam garantir a integridade das águas subterrâneas. Uma estrutura regulatória baseada em risco que considere as mudanças na qualidade das águas subterrâneas, a adoção em zonas de atenuação do subsolo e o uso de métodos avançados de monitoramento são necessários para apoiar a confiança na sustentabilidade da RGA.

Impact of an historic underground gas well blowout on the current methane chemistry in a shallow groundwater system.

Blowouts present a small but genuine risk when drilling into the deep subsurface and can have an immediate and significant impact on the surrounding environment. Nevertheless, studies that document their long-term impact are scarce. In 1965, a catastrophic underground blowout occurred during the drilling of a gas well in The Netherlands, which led to the uncontrolled release of large amounts of natural gas from the reservoir to the surface. In this study, the remaining impact on methane chemistry in the overlying aquifers was investigated. Methane concentrations higher than 10 mg/L (n = 12) were all found to have δ13C-CH4 values larger than -30‰, typical of a thermogenic origin. Both δ13C-CH4 and δD-CH4 correspond to the isotopic composition of the gas reservoir. Based on analysis of local groundwater flow conditions, this methane is not a remnant but most likely the result of ongoing leakage from the reservoir as a result of the blowout. Progressive enrichment of both δ13C-CH4 and δD-CH4 is observed with increasing distance and decreasing methane concentrations. The calculated isotopic fractionation factors of εC = 3 and εD = 54 suggest anaerobic methane oxidation is partly responsible for the observed decrease in concentrations. Elevated dissolved iron and manganese concentrations at the fringe of the methane plume show that oxidation is primarily mediated by the reduction of iron and manganese oxides. Combined, the data reveal the long-term impact that underground gas well blowouts may have on groundwater chemistry, as well as the important role of anaerobic oxidation in controlling the fate of dissolved methane.

Isolation and characterization of heavy polycyclic aromatic hydrocarbon-degrading bacteria adapted to electrokinetic conditions.

Polycyclic aromatic hydrocarbon (PAH)-degrading bacteria capable of growing under electrokinetic conditions were isolated using an adjusted acclimation and enrichment procedure based on soil contaminated with heavy PAHs in the presence of an electric field. Their ability to degrade heavy PAHs under an electric field was individually investigated in artificially contaminated soils. The results showed that strains PB4 (Pseudomonas fluorescens) and FB6 (Kocuria sp.) were the most efficient heavy PAH degraders under electrokinetic conditions. They were re-inoculated into a polluted soil from an industrial site with a PAH concentration of 184.95 mg kg(-1). Compared to the experiments without an electric field, the degradation capability of Pseudomonas fluorescens and Kocuria sp. was enhanced in the industrially polluted soil under electrokinetic conditions. The degradation extents of total PAHs were increased by 15.4 and 14.0% in the electrokinetic PB4 and FB6 experiments (PB4 + EK and FB6 + EK) relative to the PB4 and FB6 experiments without electrokinetic conditions (PB4 and FB6), respectively. These results indicated that P. fluorescens and Kocuria sp. could efficiently degrade heavy PAHs under electrokinetic conditions and have the potential to be used for the electro-bioremediation of PAH-contaminated soil, especially if the soil is contaminated with heavy PAHs.

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.

Anaerobic degradation of benzene and other aromatic hydrocarbons in a tar-derived plume: Nitrate versus iron reducing conditions.

The anaerobic degradation of aromatic hydrocarbons in a plume originating from a Pintsch gas tar-DNAPL zone was investigated using molecular, isotopic- and microbial analyses. Benzene concentrations diminished at the relatively small meter scale dimensions of the nitrate reducing plume fringe. The ratio of benzene to toluene, ethylbenzene, xylenes and naphthalene (BTEXN) in the fringe zone compared to the plume zone, indicated relatively more loss of benzene in the fringe zone than TEXN. This was substantiated by changes in relative concentrations of BTEXN, and multi-element compound specific isotope analysis for δ2H and δ13C. This was supported by the presence of (abcA) genes, indicating the presumed benzene carboxylase enzyme in the nitrate-reducing plume fringe. Biodegradation of most hydrocarbon contaminants at iron reducing conditions in the plume core, appears to be quantitatively of greater significance due to the large volume of the plume core, rather than relatively faster biodegradation under nitrate reducing conditions at the smaller volume of the plume fringe. Contaminant concentration reductions by biodegradation processes were shown to vary distinctively between the source, plume (both iron-reducing) and fringe (nitrate-reducing) zones of the plume. High anaerobic microbial activity was detected in the plume zone as well as in the dense non aqueous phase liquid (DNAPL) containing source zone. Biodegradation of most, if not all, other water-soluble Pintsch gas tar aromatic hydrocarbon contaminants occur at the relatively large dimensions of the anoxic plume core. The highest diversity and concentrations of metabolites were detected in the iron-reducing plume core, where the sum of parent compounds of aromatic hydrocarbons was greater than 10 mg/L. The relatively high concentrations of metabolites suggest a hot spot for anaerobic degradation in the core of the plume downgradient but relatively close to the DNAPL containing source zone.

Field Testing of a Novel Drilling Technique to Expand Well Diameters at Depth in Unconsolidated Formations.

Larger well diameters allow higher groundwater abstraction rates. But particularly for the construction of wells at greater depth, it may be more cost-efficient to only expand the borehole in the target aquifer. However, current drilling techniques for unconsolidated formations are limited by their expansion factors (<2) and diameters (<1000 mm). Therefore, we developed a new technique aiming to expand borehole diameters at depth in a controlled manner using a low-pressure water jet perpendicular to the drilling direction and extendable by means of a pivoting arm. During a first field test, the borehole diameter was expanded 2.6-fold from 600 to 1570 mm at a depth of 53.5 to 68 m and equipped with a well screen to create an expanded diameter gravel well (EDGW). In keeping with the larger diameter, the volume flux per m screen length was two times higher than conventional 860 mm diameter wells at the site in the subsequent 3 year production period. Although borehole clogging was slower on a volumetric basis and similar when normalized to borehole wall area, rehabilitation of particle clogging at the borehole wall was more challenging due to the thickness of the gravel pack. While jetting the entire borehole wall before backfilling holds promise to remove filter cake and thus limit particle clogging, we found that a second borehole (expanded 4.1-fold to 2460 mm) collapsed during jetting. Overall, the EDGW technique has potential to make the use of deeper unconsolidated aquifers economically (more) feasible, although further understanding of the borehole stability and rehabilitation is required to assess its wider applicability.

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.

Impact of groundwater flow on methane gas migration and retention in unconsolidated aquifers.

Methane leaking at depth from hydrocarbon wells poses an environmental and safety hazard. However, determining the occurrence and magnitude of gas migration at ground surface is challenging, as part of the leaking gas is retained during upward migration. We investigated migration through unconsolidated sedimentary aquifers using a two-phase, two-component (water and methane) flow and transport model constructed in DuMux. A sensitivity analysis for migration through a 60 m thick sandy aquifer showed that retention by dissolution can be significant even with low groundwater Darcy velocities of 1 m.yr-1. Retention was negligible in the absence of groundwater flow. Besides groundwater velocity, both hydrogeological (permeability, entry pressure, pore-size distribution, and residual gas saturation) and leakage conditions (depth, magnitude and spatial dimensions) determined model outcomes. Additional simulations with interbedded finer grained sediments resulted in substantial lateral spreading of migrating gas. This delayed upward migration and enhanced retention in overlying sandy units where groundwater velocities are highest. Overall, the results of this study show that for unconsolidated aquifer systems and the most commonly observed leakage rates (0.1-10 m3.d-1), significant amounts of migrating methane can be retained due to dissolution into laterally flowing groundwater. Consequently, resulting atmospheric methane emissions above such leaks may be delayed with decades after the onset of leakage, significantly reduced, or prevented entirely.

Occurrence and fate of methane leakage from cut and buried abandoned gas wells in the Netherlands.

Methane leakage caused by well integrity failure was assessed at 28 abandoned gas wells and 1 oil well in the Netherlands, which have been plugged, cut and buried to below the ground surface (≥3 mbgl). At each location, methane concentrations were thoroughly scanned at the surface. A static chamber setup was used to measure methane flow rates from the surface as well as from 1 m deep holes drilled using a hand auger. An anomalously high flow rate from 1 m depth combined with isotopic confirmation of a thermogenic origin revealed ongoing leakage at 1 of the 29 wells (3.4%), that had gone undetected by surficial measurements. Gas fluxes at the other sites were due to shallow production of biogenic methane. Detailed investigation at the leaking well (MON-02), consisting of 28 flux measurements conducted in a 2 × 2 m grid from holes drilled to 1 and 2 m depth, showed that flux magnitude was spatially heterogeneous and consistently larger at 2 m depth compared to 1 m. Isotopic evidence revealed oxidation accounted for roughly 25% of the decrease in flux towards the surface. The estimated total flux from the well (443 g CH4 hr-1) was calculated by extrapolation of the individual flow rate measurements at 2 m depth and should be considered an indicative value as the validity of the estimate using our approach requires confirmation by modelling and/or experimental studies. Together, our findings show that total methane emissions from leaking gas wells in the Netherlands are likely negligible compared to other sources of anthropogenic methane emissions (e.g. <1% of emissions from the Dutch energy sector). Furthermore, subsurface measurements greatly improve the likelihood of detecting leakage at buried abandoned wells and are therefore essential to accurately assess their greenhouse gas emissions and explosion hazards.

The impact of water saturation on the infiltration behaviour of elemental mercury DNAPL in heterogeneous porous media.

Industrial use has led to the presence of liquid elemental mercury (Hg0) worldwide in the subsurface as Dense NonAqueous Phase Liquid (DNAPL), resulting in long lasting sources of contamination, which cause harmful effects on human health and detrimental consequences on ecosystems. However, to date, insight into the infiltration behaviour of elemental mercury DNAPL is lacking. In this study, a two-stage flow container experiment of elemental mercury DNAPL infiltration into a variably water saturated stratified sand is described. During the first stage of the experiment, 16.3 ml of liquid Hg0 infiltrated and distributed into an initially partially water saturated system. Afterwards, during the second stage of the experiment, consisting of the simulation of a "rain event" to assess whether the elemental mercury already infiltrated could be mobilized due to local increases in water saturation, a significant additional infiltration of 4.7 ml of liquid mercury occurred from the remaining DNAPL source. The experiment showed that, under conditions similar to those found in the field, Hg0 DNAPL infiltration is likely to occur via fingers and is strongly controlled by porous medium structure and water saturation. Heterogeneities within the porous medium likely determined preferential pathways for liquid Hg0 infiltration and distribution, as also suggested by dual gamma ray measurements. Overall, this study highlights that the infiltration behaviour of mercury DNAPL is strongly impacted by water saturation. In the field, this may result in a preferential infiltration of Hg0 DNAPL in wetter areas or in its mobilization due to wetting during a rain event, as indicated by this study, or a groundwater table rise. This should be considered when assessing the likely distribution pathways of historic mercury DNAPL contamination as well as the remediation efforts.

Infiltration behaviour of elemental mercury DNAPL in fully and partially water saturated porous media.

Mercury is a contaminant of global concern due to its harmful effects on human health and for the detrimental consequences of its release in the environment. Sources of liquid elemental mercury are usually anthropogenic, such as chlor-alkali plants. To date insight into the infiltration behaviour of liquid elemental mercury in the subsurface is lacking, although this is critical for assessing both characterization and remediation approaches for mercury DNAPL contaminated sites. Therefore, in this study the infiltration behaviour of elemental mercury in fully and partially water saturated systems was investigated using column experiments. The properties affecting the constitutive relations governing the infiltration behaviour of liquid Hg0, and PCE for comparison, were determined using Pc(S) experiments with different granular porous media (glass beads and sands) for different two- and three-phase configurations. Results showed that, in water saturated porous media, elemental mercury, as PCE, acted as a non-wetting fluid. The required entry head for elemental mercury was higher (from about 5 to 7 times). However, due to the almost tenfold higher density of mercury, the required NAPL entry heads of 6.19cm and 12.51cm for mercury to infiltrate were 37.5% to 20.7% lower than for PCE for the same porous media. Although Leverett scaling was able to reproduce the natural tendency of Hg0 to be more prone than PCE to infiltrate in water saturated porous media, it considerably underestimated Hg0 infiltration capacity in comparison with the experimental results. In the partially water saturated system, in contrast with PCE, elemental mercury also acted as a nonwetting fluid, therefore having to overcome an entry head to infiltrate. The required Hg0 entry heads (10.45 and 15.74cm) were considerably higher (68.9% and 25.8%) than for the water saturated porous systems. Furthermore, in the partially water saturated systems, experiments showed that elemental mercury displaced both air and water, depending on the initial water distribution within the pores. This indicates that the conventional wettability hierarchy, in which the NAPL has an intermediate wetting state between the air and the water phases, is not valid for liquid elemental mercury. Therefore, for future modelling of elemental mercury DNAPL infiltration behaviour in variably water saturated porous media, a different formulation of the governing constitutive relations will be required.

Analytical model for the design of in situ horizontal permeable reactive barriers (HPRBs) for the mitigation of chlorinated solvent vapors in the unsaturated zone.

In this work we introduce a 1-D analytical solution that can be used for the design of horizontal permeable reactive barriers (HPRBs) as a vapor mitigation system at sites contaminated by chlorinated solvents. The developed model incorporates a transient diffusion-dominated transport with a second-order reaction rate constant. Furthermore, the model accounts for the HPRB lifetime as a function of the oxidant consumption by reaction with upward vapors and its progressive dissolution and leaching by infiltrating water. Simulation results by this new model closely replicate previous lab-scale tests carried out on trichloroethylene (TCE) using a HPRB containing a mixture of potassium permanganate, water and sand. In view of field applications, design criteria, in terms of the minimum HPRB thickness required to attenuate vapors at acceptable risk-based levels and the expected HPRB lifetime, are determined from site-specific conditions such as vapor source concentration, water infiltration rate and HPRB mixture. The results clearly show the field-scale feasibility of this alternative vapor mitigation system for the treatment of chlorinated solvents. Depending on the oxidation kinetic of the target contaminant, a 1m thick HPRB can ensure an attenuation of vapor concentrations of orders of magnitude up to 20years, even for vapor source concentrations up to 10g/m3. A demonstrative application for representative contaminated site conditions also shows the feasibility of this mitigation system from an economical point of view with capital costs potentially somewhat lower than those of other remediation options, such as soil vapor extraction systems. Overall, based on the experimental and theoretical evaluation thus far, field-scale tests are warranted to verify the potential and cost-effectiveness of HPRBs for vapor mitigation control under various conditions of application.

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.

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 mercury's 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 mercury's 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.

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.

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.

Cork stoppers as an effective sorbent for water treatment: the removal of mercury at environmentally relevant concentrations and conditions.

The technical feasibility of using stopper-derived cork as an effective biosorbent towards bivalent mercury at environmentally relevant concentrations and conditions was evaluated in this study. Only 25 mg/L of cork powder was able to achieve 94 % of mercury removal for an initial mercury concentration of 500 µg/L. It was found that under the conditions tested, the efficiency of mercury removal expressed as equilibrium removal percentage does not depend on the amount of cork or its particle size, but is very sensitive to initial metal concentration, with higher removal efficiencies at higher initial concentrations. Ion exchange was identified as one of the mechanisms involved in the sorption of Hg onto cork in the absence of ionic competition. Under ionic competition, stopper-derived cork showed to be extremely effective and selective for mercury in binary mixtures, while in complex matrices like seawater, moderate inhibition of the sorption process was observed, attributed to a change in mercury speciation. The loadings achieved are similar to the majority of literature values found for other biosorbents and for other metals, suggesting that cork stoppers can be recycled as an effective biosorbent for water treatment. However, the most interesting result is that equilibrium data show a very rare behaviour, with the isotherm presenting an almost square convex shape to the concentration axis, with an infinite slope for an Hg concentration in solution around 25 µg/L.

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.

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.

Characterization of a heterogeneous DNAPL source zone in the Borden aquifer using partitioning and interfacial tracers: residual morphologies and background sorption.

A partitioning interwell tracer test (PITT) was performed in the Borden sand aquifer to characterize an aged heterogeneous DNAPL source zone. This zone evolved during 5 years of natural groundwater flow following the infiltration of 50 L chlorinated solvents DNAPL. To assess the lateral variability of remaining DNAPL mass and morphology, four sweepzones were analyzed. The low saturation residual nature of the source zone required correction of tracer breakthrough data for natural background sorption. Corrected estimates of the DNAPL percentage remaining (total 13.2-16.6%), average saturation (0.05-0.18%) and distribution across the sweepzones were in good agreement with previous findings based on detailed transect monitoring, core analyses and ground-penetrating radar reflection. Using a newly defined metric "average spherical radius equivalent (ASRE)", sweepzone estimates of the average size of DNAPL presence indicated the dominance of single pore DNAPL blobs and suggested the absence of DNAPL pools. Tracer tests indicated that DNAPL presence in the most DNAPL depleted sweepzone was potentially overestimated due to increased sediment sorption by residualized Sudan IV that was added to the DNAPL infiltrate. As hydrophobic compounds are normally present in spent solvent DNAPL, this suggests that additional sorption needs to be considered when using PITTs to characterize aged DNAPL source zones.