Phenol Molecular Sheets Woven by Water Cavities in Hydrophobic Slit Nanospaces.

Despite extensive research over the last several decades, the microscopic characterization of topological phases of adsorbed phenol from aqueous solutions in carbon micropores (pore size < 2.0 nm), which are believed to exhibit a solid and quasi-solid character, has not been reported. Here, we present a combined experimental and molecular level study of phenol adsorption from neutral water solutions in graphitic carbon micropores. Theoretical and experimental results show high adsorption of phenol and negligible coadsorption of water in hydrophobic graphitic micropores (super-sieving effect). Graphic processing unit-accelerated molecular dynamics simulation of phenol adsorption from water solutions in a realistic model of carbon micropores reveal the formation of two-dimensional phenol crystals with a peculiar pattern of hydrophilic-hydrophobic stripes in 0.8 nm supermicropores. In wider micropores, disordered phenol assemblies with water clusters, linear chains, and cavities of various sizes are found. The highest surface density of phenol is computed in 1.8 nm supermicropores. The percolating water cluster spanning the entire pore space is found in 2.0 nm supermicropores. Our findings open the door for the design of better materials for purification of aqueous solutions from nonelectrolyte micropollution.

Comparison of Alcian blue and total carbohydrate assays for quantitation of transparent exopolymer particles (TEP) in biofouling studies.

Transparent exopolymer particles (TEP) and their precursors are gel-like acidic polysaccharide particles. Both TEP precursors and TEP have been identified as causal factors in fouling of desalination and water treatment systems. For comparison between studies, it is important to accurately measure the amount and fouling capacity of both components. However, the accuracy and recovery of the currently used Alcian blue based TEP measurement of different surrogates and different size fractions are not well understood. In this study, we compared Alcian blue based TEP measurements with a total carbohydrate assay method. Three surrogates; xanthan gum, pectin and alginic acid; were evaluated at different salinities. Total carbohydrate concentrations of particulates (>0.4 µm) and their precursors (<0.4 µm, >10 kDa) varied depending on water salinity and method of recovery. As xanthan gum is the most frequently used surrogate in fouling studies, TEP concentration is expressed as xanthan gum equivalents (mg XGeq/L) in this study. At a salinity of 35 mg/L sea salt, total carbohydrate assays showed a much higher particulate TEP fraction for alginic acid (38%) compared to xanthan gum (9%) and pectin (12%). The concentrations of particulate TEP therefore may only represent ∼10% of the total mass; while precursor TEP represents ∼80% of the total TEP. This highlights the importance of reporting both particulate and precursor TEP for membrane biofouling studies. The calculated concentrations of TEP and their precursors in seawater samples are also highly dependent on type of surrogate and resulting calibration factor. A linear correlation between TEP recovery and calibration factor was demonstrated in this study for all three surrogates. The relative importance and accuracy of measurement method, particulate size, surrogate type, and recovery are described in detail in this study.

Reconciling PM10 analyses by different sampling methods for Iron King Mine tailings dust.

The overall project objective at the Iron King Mine Superfund site is to determine the level and potential risk associated with heavy metal exposure of the proximate population emanating from the site's tailings pile. To provide sufficient size-fractioned dust for multi-discipline research studies, a dust generator was built and is now being used to generate size-fractioned dust samples for toxicity investigations using in vitro cell culture and animal exposure experiments as well as studies on geochemical characterization and bioassay solubilization with simulated lung and gastric fluid extractants. The objective of this study is to provide a robust method for source identification by comparing the tailing sample produced by dust generator and that collected by MOUDI sampler. As and Pb concentrations of the PM10 fraction in the MOUDI sample were much lower than in tailing samples produced by the dust generator, indicating a dilution of Iron King tailing dust by dust from other sources. For source apportionment purposes, single element concentration method was used based on the assumption that the PM10 fraction comes from a background source plus the Iron King tailing source. The method's conclusion that nearly all arsenic and lead in the PM10 dust fraction originated from the tailings substantiates our previous Pb and Sr isotope study conclusion. As and Pb showed a similar mass fraction from Iron King for all sites suggesting that As and Pb have the same major emission source. Further validation of this simple source apportionment method is needed based on other elements and sites.

Solar-driven membrane distillation demonstration in Leupp, Arizona.

The Navajo Nation is the largest and one of the driest Native American reservations in the US. The population in the Navajo Nation is sporadically distributed over a very large area making it extremely ineffective to connect homes to a centralized water supply system. Owing to this population distribution and the multi decadal drought prevailing in the region, over 40% of the 300,000 people living on Navajo Tribal Lands lack access to running potable water. For many people the only alternative is hauling water from filling stations, resulting in economic hardship and limited supply. A solution to this problem is a de-centralized off-grid water source. The University of Arizona and US Bureau of Reclamation's Solar Membrane Distillation (SMD), stand-alone, pilot desalination system on the Navajo Reservation will provide an off-grid source of potable water; the pilot will serve as a proximal water source, ease the financial hardships caused by the drought, and provide a model for low-cost water treatment systems in arid tribal lands. Bench-scale experiments and an earlier field prototype plant showed viable operation of a solar heated, membrane distillation (MD) system, but further optimization is required. The objectives of the Navajo pilot study are to i) demonstrate integration of solar collectors and membrane distillation, ii) optimize operational parameters, iii) demonstrate and monitor technology performance during extended duration operation, and iv) facilitate independent system operation by the Navajo Water Resources Department, including hand-over of a comprehensive operations manual for implementation of subsequent SMD systems. The Navajo SMD system is designed as a perennial installation that includes remote communication of research data and full automation for remote, unmanned operation.

Windblown Dust Deposition Forecasting and Spread of Contamination around Mine Tailings.

Wind erosion, transport and deposition of windblown dust from anthropogenic sources, such as mine tailings impoundments, can have significant effects on the surrounding environment. The lack of vegetation and the vertical protrusion of the mine tailings above the neighboring terrain make the tailings susceptible to wind erosion. Modeling the erosion, transport and deposition of particulate matter from mine tailings is a challenge for many reasons, including heterogeneity of the soil surface, vegetative canopy coverage, dynamic meteorological conditions and topographic influences. In this work, a previously developed Deposition Forecasting Model (DFM) that is specifically designed to model the transport of particulate matter from mine tailings impoundments is verified using dust collection and topsoil measurements. The DFM is initialized using data from an operational Weather Research and Forecasting (WRF) model. The forecast deposition patterns are compared to dust collected by inverted-disc samplers and determined through gravimetric, chemical composition and lead isotopic analysis. The DFM is capable of predicting dust deposition patterns from the tailings impoundment to the surrounding area. The methodology and approach employed in this work can be generalized to other contaminated sites from which dust transport to the local environment can be assessed as a potential route for human exposure.

Laboratory dust generation and size-dependent characterization of metal and metalloid-contaminated mine tailings deposits.

The particle size distribution of mine tailings material has a major impact on the atmospheric transport of metal and metalloid contaminants by dust. Implications to human health should be assessed through a holistic size-resolved characterization involving multidisciplinary research, which requires large uniform samples of dust that are difficult to collect using conventional atmospheric sampling instruments. To address this limitation, we designed a laboratory dust generation and fractionation system capable of producing several grams of dust from bulk materials. The equipment was utilized in the characterization of tailings deposits from the arsenic and lead-contaminated Iron King Superfund site in Dewey-Humboldt, Arizona. Results show that metal and metalloid contaminants are more concentrated in particles of < 10 µm aerodynamic diameter, which are likely to affect surrounding communities and ecosystems. In addition, we traced the transport of contaminated particles from the tailings to surrounding soils by identifying Pb and Sr isotopic signatures in soil samples. The equipment and methods developed for this assessment ensure uniform samples for further multidisciplinary studies, thus providing a tool for comprehensive representation of emission sources and associated risks of exposure.

Solar membrane distillation: desalination for the Navajo Nation.

Provision of clean water is among the most serious, long-term challenges in the world. To an ever increasing degree, sustainable water supply depends on the utilization of water of impaired initial quality. This is particularly true in developing nations and in water-stressed areas such as the American Southwest. One clear example is the Navajo Nation. The reservation covers 27,000 square miles, mainly in northeastern Arizona. Low population density coupled with water scarcity and impairment makes provision of clean water particularly challenging. The Navajos rely primarily on ground water, which is often present in deep aquifers or of brackish quality. Commonly, reverse osmosis (RO) is chosen to desalinate brackish ground water, since RO costs are competitive with those of thermal desalination, even for seawater applications. However, both conventional thermal distillation and RO are energy intensive, complex processes that discourage decentralized or rural implementation. In addition, both technologies demand technical experience for operation and maintenance, and are susceptible to scaling and fouling unless extensive feed pretreatment is employed. Membrane distillation (MD), driven by vapor pressure gradients, can potentially overcome many of these drawbacks. MD can operate using low-grade, sub-boiling sources of heat and does not require extensive operational experience. This presentation discusses a project on the Navajo Nation, Arizona (Native American tribal lands) that is designed to investigate and deploy an autonomous (off-grid) system to pump and treat brackish groundwater using solar energy. Βench-scale, hollow fiber MD experiment results showed permeate water fluxes from 21 L/m2·d can be achieved with transmembrane temperature differences between 40 and 80˚C. Tests run with various feed salt concentrations indicate that the permeate flux decreases only about 25% as the concentration increases from 0 to 14% (w/w), which is four times seawater salt concentration. The quality of the permeate water remains constant at about 1 mg/L regardless of the changes in the influent salt concentration. A nine-month MD field trial, using hollow fiber membranes and completely off-the-shelf components demonstrated that a scaled-up solar-driven MD system was practical and economically viable. Based on these results, a pilot scale unit will be constructed and deployed on the tribal lands.

Scoping candidate minerals for stabilization of arsenic-bearing solid residuals.

Arsenic Crystallization Technology (ACT) is a potentially eco-friendly, effective technology for stabilization of arsenic-bearing solid residuals (ABSRs). The strategy is to convert ABSRs generated by water treatment facilities into minerals with a high arsenic capacity and long-term stability in mature, municipal solid waste landfills. Candidate minerals considered in this study include scorodite, arsenate hydroxyapatites, ferrous arsenates (symplesite-type minerals), tooeleite, and arsenated-schwertmannite. These minerals were evaluated as to ease of synthesis, applicability to use of iron-based ABSRs as a starting material, and arsenic leachability. The Toxicity Characteristic Leaching Procedure (TCLP) was used for preliminary assessment of candidate mineral leaching. Minerals that passed the TCLP and whose synthesis route was promising were subjected to a more aggressive leaching test using a simulated landfill leachate (SLL) solution. Scorodite and arsenate hydroxyapatites were not considered further because their synthesis conditions were not found to be favorable for general application. Tooeleite and silica-amended tooeleite showed high TCLP arsenic leaching and were also not investigated further. The synthesis process and leaching of ferrous arsenate and arsenated-schwertmannite were promising and of these, arsenated-schwertmannite was most stable during SLL testing. The latter two candidate minerals warrant synthesis optimization and more extensive testing.

Microscale speciation of arsenic and iron in ferric-based sorbents subjected to simulated landfill conditions.

During treatment for potable use, water utilities generate arsenic-bearing ferric wastes that are subsequently dispatched to landfills. The biogeochemical weathering of these residuals in mature landfills affects the potential mobilization of sorbed arsenic species via desorption from solids subjected to phase transformations driven by abundant organic matter and bacterial activity. Such processes are not simulated with the toxicity characteristic leaching procedure (TCLP) currently used to characterize hazard. To examine the effect of sulfate on As retention in landfill leachate, columns of As(V) loaded amorphous ferric hydroxide were reacted biotically at two leachate sulfate concentrations (0.064 mM and 2.1 mM). After 300 days, ferric sorbents were reductively dissolved. Arsenic released to porewaters was partially coprecipitated in mixed-valent secondary iron phases whose speciation was dependent on sulfate concentration. As and Fe XAS showed that, in the low sulfate column, 75-81% of As(V) was reduced to As(III), and 53-68% of the Fe(III) sorbent was transformed, dominantly to siderite and green rust. In the high sulfate column, Fe(III) solids were reduced principally to FeS(am), whereas As(V) was reduced to a polymeric sulfide with local atomic structure of realgar. Multienergy micro-X-ray fluorescence (ME-µXRF) imaging at Fe and As K-edges showed that As formed surface complexes with ferrihydrite > siderite > green rust in the low sulfate column; while discrete realgar-like phases formed in the high sulfate systems. Results indicate that landfill sulfur chemistry exerts strong control over the potential mobilization of As from ferric sorbent residuals by controlling secondary As and Fe sulfide coprecipitate formation.

Effect of silicic acid on arsenate and arsenite retention mechanisms on 6-L ferrihydrite: A spectroscopic and batch adsorption approach.

The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite-water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7-9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In-situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms inner-sphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8 - 9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As(III)-Fe bond distances of ~2.92-2.94 and 3.41-3.44 Å, respectively. The As-Fe bond distances in both arsenate and arsenite EXAFS spectra remained unchanged in the presence of Si, suggesting that whereas Si diminishes arsenite adsorption preferentially, it has a negligible effect on As-Fe bonding mechanisms.

Toward identifying the next generation of superfund and hazardous waste site contaminants.

BACKGROUND: This commentary evolved from a workshop sponsored by the National Institute of Environmental Health Sciences titled "Superfund Contaminants: The Next Generation" held in Tucson, Arizona, in August 2009. All the authors were workshop participants. OBJECTIVES: Our aim was to initiate a dynamic, adaptable process for identifying contaminants of emerging concern (CECs) that are likely to be found in future hazardous waste sites, and to identify the gaps in primary research that cause uncertainty in determining future hazardous waste site contaminants. DISCUSSION: Superfund-relevant CECs can be characterized by specific attributes: They are persistent, bioaccumulative, toxic, occur in large quantities, and have localized accumulation with a likelihood of exposure. Although still under development and incompletely applied, methods to quantify these attributes can assist in winnowing down the list of candidates from the universe of potential CECs. Unfortunately, significant research gaps exist in detection and quantification, environmental fate and transport, health and risk assessment, and site exploration and remediation for CECs. Addressing these gaps is prerequisite to a preventive approach to generating and managing hazardous waste sites. CONCLUSIONS: A need exists for a carefully considered and orchestrated expansion of programmatic and research efforts to identify, evaluate, and manage CECs of hazardous waste site relevance, including developing an evolving list of priority CECs, intensifying the identification and monitoring of likely sites of present or future accumulation of CECs, and implementing efforts that focus on a holistic approach to prevention.

Evaluating the Mobility of Arsenic in Synthetic Iron-containing Solids Using a Modified Sequential Extraction Method.

Many water treatment technologies for arsenic removal that are used today produce arsenic-bearing residuals which are disposed in non-hazardous landfills. Previous works have established that many of these residuals will release arsenic to a much greater extent than predicted by standard regulatory leaching tests (e.g. the toxicity characteristic leaching procedure, TCLP) and, consequently, require stabilization to ensure benign behavior after disposal. In this work, a four-step sequential extraction method was developed in an effort to determine the proportion of arsenic in various phases in untreated as well as stabilized iron-based solid matrices. The solids synthesized using various potential stabilization techniques included: amorphous arsenic-iron sludge (ASL), reduced ASL via reaction with zero valent iron (RASL), amorphous ferrous arsenate (PFA), a mixture of PFA and SL (M1), crystalline ferrous arsenate (HPFA), and a mixture of HPFA and SL (M2). The overall arsenic mobility of the tested samples increased in the following order: ASL > RASL > PFA > M1 > HPFA > M2.

Effect of ferrous iron on arsenate sorption to amorphous ferric hydroxide.

Amorphous ferric hydroxide (AFH) sorbents are commonly used for removal of arsenate from water. When disposed in microbially active, reducing environments, such as landfills, Fe(II) will be generated by reductive dissolution of the AFH surface and arsenate will be desorbed. However, the observed ratio of arsenate (and, in fact, total arsenic) to total iron in the leachate is not consistent with the original ratio of arsenate to iron on the AFH. Work to determine if ferrous iron re-adsorption to the AFH can partially explain this inconsistency is described. As pH increases above 7, Fe(II) increasingly sorbs onto the AFH surface. This sorption is largely independent of ionic strength and somewhat irreversible at high pH. In contrast, arsenate partitioning to AFH decreases with increasing pH. However, over the pH range from 5 to 9, the presence of Fe(II) sorbed to the AFH surface increases the capacity for arsenate sorption. In addition, when no Fe(II) is present, arsenate binding is largely to surface sites inaccessible to Fe(II) binding. The results are also consistent with Fe(II) sorption to AFH sites, otherwise unfavorable to arsenate binding and transformation of those sites into arsenate-amenable binding sites.

Fate of polybrominated diphenyl ethers during wastewater treatment/polishing and sludge stabilization/disposal.

Large quantities of polybrominated diphenyl ethers (PBDEs) have been used as flame retardants in clothing and plastic products since the 1970s. A small fraction of the PBDEs in manufactured products subsequently enters municipal wastewater. Nevertheless, the resistance of these compounds to chemical and biochemical transformations provides opportunities for accumulation in sediments that are in contact with wastewater effluent and agricultural soils that are amended with biosolids derived from wastewater treatment. Balances developed for PBDE congeners indicate that conventional wastewater treatment processes and soil infiltration of treated wastewater in recharge operations do not discriminate significantly among the major congeners in commercially available PBDE products. Accumulation of PBDEs at near part-per-million levels was measured in the surface sediments at the Sweetwater Recharge Facility in Tucson, Arizona, during 10-15 years of operation. Half-lives for loss of major PBDE congeners from sediments were decades or longer. Local agricultural soils amended with biosolids over a 20-year period showed similar accumulation of PBDEs. The widespread use of PBDEs in commercial products, compound persistence, and toxicity indicate that additional effort is warranted to better understand fate-determining processes for PBDEs in the environment.

Changes in estrogen/anti-estrogen activities in ponded secondary effluent.

Total estrogenic activity, measured using the yeast estrogen screen reporter gene bioassay, decreased from 60 pM (equivalent 17alpha-ethinylestradiol concentration) to an estimated 1.4 pM during a 24-hour period in which secondary effluent was held in a shallow infiltration basin. Over the same period, anti-estrogenic activity, measured as an equivalent concentration of tamoxifen, increased from 35 to 260 nM, suggesting that antagonists produced during secondary effluent storage played a role in the apparent loss of estrogenic activity. Androgenic activity, measured over the same 24-hour period using the yeast androgen screen, was near or below the method detection limit (0.7 pM as testosterone). However, the same pond samples were clearly anti-androgenic. When whole-sample extracts were separated via adsorption and stepwise elution in alcohol/water solutions consisting of 20, 40 and 100% ethanol, the sum of estrogenic activities in derived fractions was always lower than the measured estrogenic activity in the whole-sample extracts. Summed anti-estrogenic activities in the same fractions, however, always exceeded values for corresponding whole-sample extracts. Results reinforce the importance of sample preparation steps (concentration of organics followed by estrogen/anti-estrogen separation) when measuring endocrine-related activities in chemically complex samples such as wastewater effluent. The potential complexity of relationships among estrogens, anti-estrogens and matrix organics suggests that additive models are of questionable validity for estimating whole-sample estrogenic activity from measurements involving sample fractions.

Leaching of arsenic from granular ferric hydroxide residuals under mature landfill conditions.

Most arsenic bearing solid residuals (ABSR) from water treatment will be disposed in nonhazardous landfills. The lack of an appropriate leaching test to predict arsenic mobilization from ABSR creates a need to evaluate the magnitude and mechanisms of arsenic release under landfill conditions. This work studies the leaching of arsenic and iron from a common ABSR, granular ferric hydroxide, in a laboratory-scale column that simulates the biological and physicochemical conditions of a mature, mixed solid waste landfill. The column operated for approximately 900 days and the mode of transport as well as chemical speciation of iron and arsenic changed with column age. Both iron and arsenic were readily mobilized under the anaerobic, reducing conditions. During the early stages of operation, most arsenic and iron leaching (80% and 65%, respectively) was associated with suspended particulate matter, and iron was lost proportionately faster than arsenic. In later stages, while the rate of iron leaching declined, the arsenic leaching rate increased greater than 7-fold. The final phase was characterized by dissolved species leaching. Future work on the development of standard batch leaching tests should take into account the dominant mobilization mechanisms identified in this work: solid associated transport, reductive sorbent dissolution, and microbially mediated arsenic reduction.

Destruction of gas-phase trichloroethylene in a modified fuel cell.

A conventional fuel cell was used as a catalytic reactor to treat soil vapor extraction (SVE) gases contaminated with trichloroethylene (TCE). The SVE gases are fed to the cathode side of the fuel cell, where TCE is reduced to ethane and hydrochloric acid. The results obtained suggest that TCE reduction occurs by a catalytic reaction with hydrogen that is re-formed on the cathode's surface beyond a certain applied cell potential. Substantial conversion of TCE is obtained, even when competing oxygen reduction occurs in the cathode. The process has been modeled successfully by conceptualizing the flow passage in the fuel cell as a plug flow reactor.

Effect of pH, competitive anions and NOM on the leaching of arsenic from solid residuals.

Implementation of the new arsenic MCL in 2006 will lead to the generation of an estimated 6 million pounds of arsenic-bearing solid residuals (ABSRs) every year, which will be disposed predominantly in non-hazardous landfills. The Toxicity Characteristic Leaching Procedure (TCLP) is typically used to assess whether a waste is hazardous and most solid residuals pass the TCLP. However, recent research shows the TCLP significantly underestimates arsenic mobilization in landfills. A variety of compositional dissimilarities between landfill leachates and the TCLP extractant solution likely play a role. Among the abiotic factors likely to play a key role in arsenic remobilization/leaching from solid sorbents are pH, and the concentrations of natural organic matter (NOM) and anions like phosphate, bicarbonate, sulfate and silicate. This study evaluates the desorption of arsenic from actual treatment sorbents, activated alumina (AA) and granular ferric hydroxide (GFH), which are representative of those predicted for use in arsenic removal processes, and as a function of the specific range of pH and concentrations of the competitive anions and NOM found in landfills. The influence of pH is much more significant than that of competing anions or NOM. An increase in one unit of pH may increase the fraction of arsenic leached by 3-4 times. NOM and phosphate replace arsenic from sorbent surface sites up to three orders of magnitude more than bicarbonate, sulfate and silicate, on a per mole basis. Effects of anions are neither additive nor purely competitive. Leaching tests, which compare the fraction of arsenic mobilized by the TCLP vis-a-vis an actual or more realistic synthetic landfill leachate, indicate that higher pH, and greater concentrations of anions and NOM are all factors, but of varying significance, in causing higher extraction in landfill and synthetic leachates than the TCLP.

Fenton-driven chemical regeneration of MTBE-spent GAC.

Methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) was chemically regenerated utilizing the Fenton mechanism. Two successive GAC regeneration cycles were performed involving iterative adsorption and oxidation processes: MTBE was adsorbed to the GAC, oxidized, re-adsorbed, oxidized, and finally re-adsorbed. Oxidant solutions comprised of hydrogen peroxide (H2O2) (1.7-2.0%) and FeSO4 x 7H2O (3 g/L) (pH 2.5), were recirculated through the GAC column (30% bed expansion). The regeneration efficiency after two full cycles of treatment was calculated to be 91%. The cost of H2O2 was 0.59 dollars/kg GAC (0.27 dollars/lb) per regeneration cycle. There was no loss of sorptive capacity. Small reductions in carbon surface area and pore volume were measured. The lack of carbon deterioration under aggressive oxidative conditions was attributed to the oxidation of the target contaminants relative to the oxidation of carbon surfaces. The reaction byproducts from MTBE oxidation, tertiary butanol and acetone, were also degraded and did not accumulate significantly on the GAC. Excessive accumulation of Fe on the GAC and consequent interference with MTBE sorption and carbon regeneration was controlled by monitoring and adjusting Fe in the oxidative solution.