Metal mobility during in situ chemical oxidation of TCE by KMnO4

The potential for trace-metal contamination of aquifers as a side effect of In Situ Chemical Oxidation (ISCO) of chlorinated solvent contamination by KMnO(4) is investigated with column experiments. The experiments investigate metal mobility during in situ chemical oxidation of TCE by KMnO(4) under conditions where pH, flow rate, KMnO(4), TCE, and trace-metal concentrations were controlled. During ISCO, the injection of MnO(4) creates oxidizing conditions, and acidity released by the reactions causes a tendency toward low pH in aquifers. In order to evaluate the role of pH buffering on metal mobility, duplicate columns were constructed, one packed with pure silica sand, and one with a mixture of silica sand and calcite. Aqueous solutions of TCE and KMnO(4) (with 1 mg/L Cu, Pb, Zn, Mo, Ni, and Cr(VI)) were allowed to mix at the inlet to the columns. After the completion of the experiments, samples of Mn oxide were removed from the columns and analyzed by analytical scanning and transmission electron microscopy. In order to relate the results of the laboratory experiments to field settings, the analyses of Mn-oxide samples from the lab experiments were compared to samples of Mn oxide collected from a field-scale chemical-oxidation experiment that were also analyzed by analytical electron microscopy as well as time-of-flight secondary-ion mass spectroscopy. The pH ranged from 2.40 in the silica sand column to 6.25 in the calcite-containing column. The data indicate that aqueous Mo, Pb, Cu and Ni concentrations are attenuated almost completely within the columns. In contrast, Zn concentrations are not significantly attenuated and Cr(VI) is transported conservatively. The results indicate that within the range 2.40 to 6.25, metal mobility is not affected by pH. Comparison of analyses of Mn-oxide from the lab and field demonstrate that a variety of metals are sequestered from solution by Mn oxide.     

Dissolution of trace metals from particles of industrial origin and its influence on the composition of rainwater

The dissolution of trace metals (Fe, Mn, Cu, Zn, Ca and Mg) from pulverized fuel ash and steel dust particles in aqueous suspensions was studied as a function of solution pH and aerosol mass loading. The rate of dissolution, the final concentration and the fraction of the metal leached increased with decreasing pH over the range of pH 2.5→ 5. The leaching of aerosol particles is an important source of trace metals in rainwater, and the results of the leaching experiments were found to be consistent with the observations of these metals in urban rainwater. Alkaline materials such as Ca and Mg leached from particles may be important in the electroneutrality balance of rainwater and they could affect the solution pH. The dissolution of metals such as Fe and Mn may provide catalysts which could be important in the aqueous oxidation of SO₂, and the leaching of Ca and Mg may have a ‘buffering’ effect in reacting cloud and aerosol droplets.     

Coupling permanganate oxidation with microbial dechlorination of tetrachloroethene.

For sites contaminated with chloroethene non-aqueous-phase liquids, designing a remediation system that couples in situ chemical oxidation (ISCO) with potassium permanganate (KMnO4) and microbial dechlorination may be complicated because of the potentially adverse effects of ISCO on anaerobic bioremediation processes. Therefore, one-dimensional column studies were conducted to understand the effect of permanganate oxidation on tetrachloroethene (PCE) dechlorination by the anaerobic mixed culture KB-1. Following the confirmation of PCE dechlorination, KMnO4 was applied to all columns at a range of concentrations and application velocities to simulate varied distances from oxidant injection. Immediately following oxidation, reductive dechlorination was inhibited; however, after passing several pore volumes of sterile growth medium through the columns after oxidation, a rebound of PCE dechlorination activity was observed in every inoculated column without the need to reinoculate. The volume of medium required for a rebound of dechlorination activity differed from 1.1 to 8.1 pore volumes (at a groundwater velocity of 4 cm/d), depending on the specific condition of oxidant application.     

Dissolution and solubility of trace metals from natural and anthropogenic aerosol particulate matter

An open flow reactor is used to simulate the dissolution process of mineral aerosol particles in atmospheric water droplets. Data on dissolution kinetic and solubility are provided for the major trace metals from two kinds of matrix: alumino-silicated and carbonaceous sample. The results emphasise that the metals contained in the carbonaceous aerosols are easier dissolved than in the alumino-silicated particles. The released concentrations are not related to the total metal composition or the origin of particles, but are directly associated with the type of liaisons whereby the metals are bound in the solid matrix. Thus, the metals coming from carbonaceous particles are adsorbed impurities or salts and hence are very soluble and with a dissolution hardly dependent on pH, whereas the metals dissolved from alumino-silicated particles are less soluble, notably the ones constitutive of the matrix network (Fe, Mn), and with a dissolution highly influenced by pH. Consequently, in the regions with an anthropogenic influence, the dissolved concentrations of metals found in the atmospheric waters are mainly governed by the elemental carbon content. Moreover, it appears that the dissolution kinetic of metals is not constant as a function of time. The dissolution rates are very rapid in the first 20 min of leaching and then they are stabilised to lower values in comparison to initial rates. By consequence, the total dissolved metal content is provided after the first 20 min of the droplet lifetime. For this reason, the effects of trace metals on the atmospheric aqueous chemistry and as atmospheric wet input to the marine biota are maximal for "aged" droplets.     

Distribution and variability of redox zones controlling spatial variability of arsenic in the Mississippi River Valley alluvial aquifer, southeastern Arkansas

Twenty one of 118 irrigation water wells in the shallow (25-30 m thick) Mississippi River Valley alluvial aquifer in the Bayou Bartholomew watershed, southeastern Arkansas had arsenic (As) concentrations (<0.5 to 77 microg/L) exceeding 10 microg/L. Sediment and groundwater samples were collected and analyzed from the sites of the highest, median, and lowest concentrations of As in groundwater in the alluvial aquifers located at Jefferson County, Arkansas. A traditional five-step sequential extraction was performed to differentiate the exchangeable, carbonate, amorphous Fe and Mn oxide, organic, and hot HNO(3)-leachable fraction of As and other compounds in sediments. The Chao reagent (0.25 M hydroxylamine hydrochloride in 0.25 M HCl) removes amorphous Fe and Mn oxides and oxyhydroxides (present as coatings on grains and amorphous minerals) by reductive dissolution and is a measure of reducible Fe and Mn in sediments. The hot HNO(3) extraction removes mostly crystalline metal oxides and all other labile forms of As. Significant total As (20%) is complexed with amorphous Fe and Mn oxides in sediments. Arsenic abundance is not significant in carbonates or organic matter. Significant (40-70 microg/kg) exchangeable As is only present at shallow depth (0-1 m below ground surface). Arsenic is positively correlated to Fe extracted by Chao reagent (r=0.83) and hot HNO(3) (r=0.85). Arsenic extracted by Chao reagent decreases significantly with depth as compared to As extracted by hot HNO(3). Fe (II)/Fe (the ratio of Fe concentration in the extracts of Chao reagent and hot HNO(3)) is positively correlated (r=0.76) to As extracted from Chao reagent. Although Fe (II)/Fe increases with depth, the relative abundance of reducible Fe decreases noticeably with depth. The amount of reducible Fe, as well as As complexed to amorphous Fe and Mn oxides and oxyhydroxides decreases with depth. Possible explanations for the decrease in reducible Fe and its complexed As with depth include historic flushing of As and Fe from hydrous ferric oxides (HFO) by microbially-mediated reductive dissolution and aging of HFO to crystalline phases. Hydrogeochemical data suggests that the groundwater in the area falls in the mildly reducing (suboxic) to relatively highly reducing (anoxic) zone, and points to reductive dissolution of HFO as the dominant As release mechanism. Spatial variability of gypsum solubility and simultaneous SO(4)(2-) reduction with co-precipitation of As and sulfide is an important limiting process controlling the concentration of As in groundwater in the area.     

Dissolution of trace metals from lava ash: influence on the composition of rainwater in the Mount Etna volcanic area

Dissolution of trace metals from lava ash of the Mount Etna volcano in aqueous suspensions is studied as a function of solution pH and aerosol mass loading. The rate of dissolution and the final concentration increase with decreasing pH. Leaching experiments are found to be consistent with the observations of these metals in rainwater of the volcanic area. Elements such as Fe and Mn are important in the aqueous oxidation of SO(2) which increases the acidity of the rainwater. Leaching of Na, Ca, K, Fe and Mg may have a buffering effect in reacting with cloud and aerosol droplets.     

DNAPL remediation with in situ chemical oxidation using potassium permanganate. II. Increasing removal efficiency by dissolving Mn oxide precipitates

In situ chemical oxidation (ISCO) schemes using MnO4- have been effective in destroying chlorinated organic solvents dissolved in ground water. Laboratory experiments and field pilot tests reveal that the precipitation of Mn oxide, one of the reaction products, causes a reduction of permeability, which can lead to flow bypassing and inefficiency of the scheme. Without a solution to this problem of plugging, it is difficult to remove DNAPL from the subsurface completely. In a companion paper, we showed with batch experiments that Mn oxide can be dissolved rapidly with certain organic acids. This study utilizes 2-D flow-tank experiments to examine the possibility of nearly complete DNAPL removal by ISCO with MnO4-, when organic acids are used to remove Mn oxide. The experiments were conducted in a small 2-D glass flow tank containing a lenticular silica-sand medium. Blue-dyed trichloroethylene (TCE) provided residual, the perched and pooled DNAPL. KMnO4 at 200 mg/l was flushed through the DNAPL horizontally. Once plugging reduced permeability and prevented further delivery of the oxidant, citric or oxalic acids were pumped into the flow tank to dissolve the Mn oxide precipitates. Organic ligands removed the Mn oxide precipitates relatively quickly, and permitted another cycle of MnO4- flooding. Cycles of MnO4-/acid flooding continued until all of the visible DNAPL was removed. The experiments were monitored with chemical analysis and visualization. A mass-balance calculation indicated that by the end of the experiments, all the DNAPL was removed. The results show also how heterogeneity adds complexity to initial redistribution of DNAPL, and to the efficiency of the chemical flooding.     

Trace metal enrichments in core sediments in Muthupet mangroves, SE coast of India: application of acid leachable technique

Core sediments from Mullipallam Creek of Muthupet mangroves on the southeast coast of India were analyzed for texture, CaCO(3), organic carbon, sulfur and acid leachable trace metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn and Cd). Textural analysis reveals a predominance of mud while CaCO(3) indicates dissolution in the upper half of the core, and reprecipitation of carbonates in reduction zones. Trace metals are diagenetically modified and anthropogenic processes control Pb and, to some extent, Ni, Zn and Fe. A distinct event is identified at 90 cm suggesting a change in deposition. Strong relationship of trace metals with Fe indicates that they are associated with Fe-oxyhydroxides. The role of carbonates in absorbing trace metals is evident from their positive relationship with trace metals. Comparison of acid leachable trace metals indicates increase in concentrations in the study area and the sediments act as a sink for trace metals contributed from multiple sources.     

Effect of four alcohols on adsorption, desorption, and movement of cadmium, nickel, and zinc through soils

Miscible-displacement experiments were conducted to compare the effects of aqueous soil solutions with ethyl alcohol, ethylene glycol, diethylene glycol, and triethylene glycol on the movement of metals through soils. Aqueous or alcohol solutions containing 1 mM each Cd, Ni, and Zn and 5 mM Ca were perfused through columns containing River Sand, Canelo loam (Canelo 1) or Mohave sandy clay loam (Mohave scl) until effluent metal concentrations (C) equaled influent concentrations (C₀) or CC₀⁻¹ = 1. In general, the order of sorption was Zn > Ni > Cd in aqueous-perfused columns, while in alcohol-perfused columns sorption of Ni Cd ≥ Zn. In comparison to aqueous solutions, alcohols reduced total metal sorption by at least 25%. Metal sorption was best correlated to cation exchange capacity of the soil, sorption of metals being greatest in the Mohave scl and least in the River Sand. After CC₀⁻¹ = 1 was reached, columns were leached with deionized water. While leaching did not affect the sorption of metals in columns which had been perfused with aqueous solvents, sorption behavior of metals changed significantly in columns which had been perfused with alcohol solvents. Leaching caused desorption of 5 to 30% of the sorbed Ni. In general, Cd was desorbed (up to 45%) from the soils tested. The exceptions were River Sand columns perfused with diethylene and triethylene glycol in which additional Cd was sorbed to the soil from the soil solution. Additional Zn was sorbed in all columns tested with the exception of the Canelo 1 column perfused with ethyl alcohol.     

Impact of injection system design on ISCO performance with permanganate--mathematical modeling results

In situ chemical oxidation (ISCO) using permanganate (MnO(4)(-)) can be a very effective technique for remediation of soil and groundwater contaminated with chlorinated solvents. However, many ISCO projects are less effective than desired because of poor delivery of the chemical reagents to the treatment zone. In this work, the numerical model RT3D was modified and applied to evaluate the effect of aquifer characteristics and injection system design on contact and treatment efficiency. MnO(4)(-) consumption was simulated assuming the natural oxidant demand (NOD) is composed of a fraction that reacts instantaneously and a fraction that slowly reacts following a 2nd order relationship where NOD consumption rate increases with increasing MnO(4)(-) concentration. MnO(4)(-) consumption by the contaminant was simulated as an instantaneous reaction. Simulation results indicate that the mass of permanganate and volume of water injected has the greatest impact on aquifer contact efficiency and contaminant treatment efficiency. Several small injection events are not expected to increase contact efficiency compared to a single large injection event, and can increase the amount of un-reacted MnO(4)(-) released down-gradient. High groundwater flow velocities can increase the fraction of aquifer contacted. Initial contaminant concentration and contaminant retardation factor have only a minor impact on volume contact efficiency. Aquifer heterogeneity can have both positive and negative impacts on remediation system performance, depending on the injection system design.     

Metal concentrations and mobility in marine sediment and groundwater in coastal reclamation areas: a case study in Shenzhen, China

The concentrations of metals in the buried marine sediment and groundwater were differently affected by land reclamation. Nine metals (V, Cr, Mn, Co, Ni, Cu, Zn, Cd and Pb) in sediment and coastal groundwater from reclamation areas in Shenzhen were examined. The gradually decreased concentrations (V, Cr, Mn, Ni, Cu, Zn) in sediment and relatively higher concentrations (V, Cr, Mn, Co, Ni, Cu and Cd) in groundwater within reclamation areas were observed. The increase of V, Cr, Mn, Ni, Cu and Cd concentrations in groundwater within reclamation areas subsequently after land reclamation should be resulted from the mobilization of these metals accumulated in the sediment. These metals appear to be easily mobilized from solid phase to solution phase after reclamation. The physico-chemical changes such as reduction in pH and salinity in water environment induced by land reclamation appear to be responsible for metal mobility in the sediment-groundwater system.     

A detailed field-based evaluation of naphthenic acid mobility in groundwater

An anaerobic plume of process-affected groundwater was characterized in a shallow sand aquifer adjacent to an oil sands tailings impoundment. Based on biological oxygen demand measurements, the reductive capacity of the plume is considered minimal. Major dissolved components associated with the plume include HCO₃, Na, Cl, SO₄, and naphthenic acids (NAs). Quantitative and qualitative NA analyses were performed on groundwater samples to investigate NA fate and transport in the subsurface. Despite subsurface residence times exceeding 20 years, significant attenuation of NAs by biodegradation was not observed based on screening techniques developed at the time of the investigation. Relative to conservative tracers (i.e., Cl), overall NA attenuation in the subsurface is limited, which is consistent with batch sorption and microcosm studies performed by other authors. Insignificant biological oxygen demand and low concentrations of dissolved As (< 10 µg L^− 1) in the plume suggest that the potential for secondary trace metal release, specifically As, via reductive dissolution reactions driven by ingress of process-affected water is minimal. It is also possible that readily leachable As is not present in significant quantities within the sediments of the study area. Thus, for similar plumes of process-affected groundwater in shallow sand aquifers which may occur as oil sands mining expands, a reasonable expectation is for NA persistence, but minimal trace metal mobilization.     

Accelerated transport of (90)Sr following a release of high ionic strength solution in vadose zone sediments

Numerical simulation of cation exchange and mineral precipitation/dissolution reactions using the multiphase reactive geochemical transport code TOUGHREACT has provided important insight into the distribution of (90)Sr among layers of geologic strata in a complex vadose zone at the U. S. Department of Energy's Idaho National Laboratory. During a transfer operation in November 1972, 70.4 m(3) of acidic, high ionic strength liquid containing 15,900 Ci of (90)Sr was released over five days into alluvial gravels 137 m above the Snake River Plain Aquifer. Sampling data from perched water zones 33 m below the release contain very high levels of (90)Sr as do soil samples obtained nearer the point of release. Use of traditional simulation approaches using laboratory-measured constant partitioning coefficients (K(d)) cannot simultaneously explain perched water and soil concentrations. To address the discrepancy, a reactive transport approach was adopted to include competitive cation exchange, dissolution/precipitation of calcite, carbon dioxide gas production and transport, and gibbsite precipitation. Simulation results using this model suggest that some of the (90)Sr could have been transported very rapidly immediately after the release with the acceleration facilitated by competition for cation exchange sites with high sodium concentrations in the released liquid and calcium dissolved from calcite, and to a lesser extent by formation of aqueous complexes with nitrate. Once the leading edge of the liquid assemblage was flushed from the alluvium, the mobility of the remaining (90)Sr decreased significantly in the absence of the competing cations. Calculations indicate that there should be a net increase in calcite, suggesting that (90)Sr could be entrained in the mineral lattice, but insufficient field data exist for confirmation. Sensitivity studies show that the cation exchange selectivity coefficients were the most sensitive individual parameters determining the (90)Sr distribution. However, the most sensitive overall quantity was the total ion exchange capacity which is a function of the moles of exchange sites per volume of pore water, the cation exchange capacity, and the total volume wetted by the infiltrating solution. In contrast, the future mobility of (90)Sr was found to be relatively insensitive to the normal range in the composition of influxing precipitation and anthropogenic waters.     

Laboratory-scale in situ chemical oxidation of a perchloroethylene pool using permanganate

In situ chemical oxidation (ISCO) is an emerging technology for the destruction of some chlorinated solvents present in subsurface environments. A laboratory investigation using a physical model was designed to assess the effectiveness of using permanganate as an oxidant to reduce the mass of a perchloroethylene (PCE) pool. The physical model was filled with silica sand overlying a silica flour base, simulating a two-dimensional saturated sand zone overlying a capillary barrier. PCE was introduced into the model so that it rested on top of the silica flour base, forming a dense nonaqueous phase liquid pool. The experimental methodology involved flushing the model with a permanganate solution for 146 days. During this period, measurements of chloride were used to assess the extent of pool oxidation. Before and after the oxidant flush, the quasi-steady state dissolution from the PCE pool was evaluated. Additionally, tracer studies were completed to assess changes in the flow field due to the oxidation process. At the termination of the experiment nine soil cores extracted from the model were used to detect the presence of MnO2 deposits and to quantify the mass of PCE remaining in the system. Excavation of the remaining material in the model revealed that the MnO2 distribution throughout the model was consistent with that observed in the cores. The oxidant flush was concluded before all of the pure phase PCE had been completely oxidized; however, approximately 45% of the PCE mass was removed, resulting in a fourfold decrease in the quasi-steady state aqueous phase mass loading of PCE from the pool. Measurements of chloride during the oxidant flush and of PCE in the soil cores suggested that the oxidation reaction occurred primarily at the upgradient edge of the PCE pool. MnO2 deposits within the model aquifer decreased the velocity of water directly above the pool, and the overall mass transfer from the remaining PCE pool. The results of this experimental study indicate that ISCO using permanganate is capable of removing substantial mass from a DNAPL pool; however, the performance of ISCO as a pool removal technology will be limited by the formation and precipitation of hydrous MnO2 that occurs during the oxidation process.     

Performance assessment of a zeolite treatment wall for removing Sr-90 from groundwater

Laboratory and modeling studies were conducted to assess the potential performance of a permeable reactive barrier constructed of a natural zeolite material at the West Valley Demonstration Project in western New York State. The results of laboratory column tests indicated that the barrier material would be effective at removing strontium from groundwater under natural gradient conditions. Two one-dimensional contaminant transport models were developed to interpret the data. A single-solute retardation factor model provided good agreement with the column test data, but time-consuming extraction and analysis of the zeolite material was required to parameterize the model. A preliminary six-solute model was also developed based on the assumption of competitive cation exchange as the primary removal mechanism. Both models yielded similar predictions of the long-term performance of the barrier, but the cation exchange model predicted higher effluent concentrations during the first 1000 pore volumes of operation. The cation exchange framework has several advantages, including the ability to calibrate the model using only data from column effluent samples, and the ability to account for site-specific differences in the groundwater cation composition. However, additional laboratory work is needed to develop a suitably robust model.     

Characteristics and applications of controlled-release KMnO4 for groundwater remediation

In situ chemical oxidation (ISCO) using potassium permanganate (KMnO4) has been widely used as a practical approach for remediation of groundwater contaminated by chlorinated solvents like trichloroethylene. The most common applications are active flushing schemes, which target the destruction of some contaminant source by injecting concentrated permanganate (MnO4(-)) solution into the subsurface over a short period of time. Despite many promising results, KMnO4 flushing is often frustrated by inefficiency associated with pore plugging by MnO2 and bypassing. Opportunities exist for the development of new ISCO systems based on KMnO4. The new scheme described in this paper uses controlled-release KMnO4 (CRP) as an active component in the well-based reactive barrier system. This scheme operates to control spreading of a dissolved contaminant plume. Prototype CRP was manufactured by dispersing fine KMnO4 granules in liquid crystal polymer resin matrix. Scanning electron microscope data verified the formation of micro-scale (ID=20-200 microm) secondary capillary permeability through which MnO4(-) is released by a reaction-diffusion process. Column and numerical simulation data indicated that the CRP could deliver MnO4(-) in a controlled manner for several years without replenishment. A proof-of-concept flow-tank experiment and model simulations suggested that the CRP scheme could potentially be developed as a practical approach for in situ remediation of contaminated aquifers. This scheme may be suitable for remediation of sites where accessibility is limited or some low-concentration contaminant plume is extensive. Development of delivery systems that can facilitate lateral spreading and mixing of MnO4(-) with the contaminant plume is warranted.     

Trace metal behaviour in the Conwy estuary,North Wales

The distribution of trace metals Zn, Ni, Mn, Fe, Cu, Pb, Cd and Cr between suspended particulate matter (SPM) and water in the Conwy estuary, North Wales, has been studied in three surveys in 1998. Dissolved Cu and Mn showed some monthly variations. Most of the dissolved trace metals displayed a negative association with salinity, indicating rivers as a major source of inputs for them. Particulate Zn, Mn and Fe showed a decreasing concentration seaward, whilst the levels of Ni, Cu, Cr and Pb increased with salinity. SPM concentration was the most important variable significantly related to trace metal concentrations in SPM, with an inverse relationship between the two parameters. This was explained by the relative enrichment of trace metals in fine particles at low SPM concentrations and relative depletion of trace metals in coarse particles at high SPM concentrations. Particulate Zn, Mn and Pb were dominated by the fraction available to acetic acid (non-detrital), whilst particulate Ni, Fe and Cr were dominated by the fraction available to nitric acid (detrital). The partition coefficient of trace metals between SPM and water declined with increasing SPM concentration, consistent with the so-called "particle concentration effect". Such a phenomenon may be explained by the presence of fine particles (including colloids) enriched with trace metals at low SPM concentrations, and the salinity-induced desorption.     

Effects of a reactive barrier and aquifer geology on metal distribution and mobility in a mine drainage impacted aquifer

The Nickel Rim aquifer has been impacted for five decades by a metal-rich plume generated from the Nickel Rim mine tailings impoundment. Metals released by the oxidation of pyrrhotite in the unsaturated zone of the tailings migrate into the downgradient aquifer, affecting both the groundwater and the aquifer solids. A reactive barrier has been installed in the aquifer to remove sulfate and metals from the groundwater. The effect of the reactive barrier on metal concentrations in the aquifer solids has not previously been studied. In this study, a series of selective extraction procedures was applied to cores of aquifer sediment, to ascertain the distribution of metals among various solid phases present in the aquifer. Extraction results were combined with groundwater chemistry, geochemical modelling and solid-phase microanalyses, to assess the potential mobility of metals under changing geochemical conditions. Reactions within the reactive barrier caused an increase in the solid-phase carbonate content downgradient from the barrier. The concentrations of poorly crystalline, oxidized phases of Mn and Fe, as well as concentrations of Cr(III) associated with oxidized Fe, and poorly crystalline Zn, are lower downgradient from the barrier, whereas total solid-phase metal concentrations remain constant. Iron and Mn accumulate as oxidized, easily extractable forms in a peat layer overlying the aquifer. Although these oxides may buffer reducing plumes, they also have the potential to release metals to the groundwater, should a reduced condition be imposed on the aquifer by remedial actions.