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The article discuses the Chapter 13 debtors efforts for trustee avoidance of to resolve the concerning issue, Topics discussed include the U.S. court case In re Dickson, rules for petitions for bankruptcy, laws defined by the U.S. bankruptcy code for Chapter 13 debtors, and falling rates of bankruptcy claims in the country.

Catalyzed H 2 O 2 propagations (CHP) is characterized by the most robust reactivity of any of the in situ chemical oxidation (ISCO) technologies because it generates the strong oxidant hydroxyl radical along with nucleophiles + reductants, such as superoxide radical. The most common groundwater contaminants, trichloroethylene (TCE) and perchloroethylene (PCE), were used as model contaminants in evaluating the effect of hydrogen peroxide (H 2 O 2 ) dosage on contaminant destruction kinetics. Both TCE and PCE degradation rates increased with H 2 O 2 dosages up to 0.1 M, and then decreased with higher H 2 O 2 dosages. Parallel reactions conducted with the addition of the hydroxyl radical scavenger 2-propanol and the hydroxyl radical-specific probe nitrobenzene confirmed that hydroxyl radical is primarily responsible for TCE and PCE degradation; however, 5-20% of their degradation was attributed to a non-hydroxyl radical mechanism. Reactions conducted with the superoxide probe tetranitromethane showed that superoxide generation rates increased with increasing H 2 O 2 doses. These results were confirmed by electron spin resonance spectroscopy. Therefore, the non-hydroxyl radical pathway for TCE and PCE degradation at H 2 O 2 ≥0.5 M was likely via nucleophilic attack by superoxide. The results of this research demonstrate that contaminants present in the aqueous phase that are reactive with hydroxyl radical require only low doses of H 2 O 2 (≤0.1 M), but subsurface systems contaminated with species not reactive with hydroxyl radical (e.g., carbon tetrachloride) require H 2 O 2 concentrations ≥0.5 M., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The effect of six water quality constituents on wastewater effluent disinfection by tin oxide anodes (TOAs) was investigated in single cell laboratory reactors. Several concentrations of suspended solids, chemical oxygen demand (COD), alkalinity, ammonia-nitrogen, nitrite-nitrogen, and nitrate-nitrogen were added to media containing 10 6 total coliform bacteria mL -1 . Current was applied through the TOAs, and coliform bacteria viability was analyzed over time. Over 99.9% inactivation of coliform bacteria was found over 15 min in TOA reactors. Concentrations of the six water quality constituents typical of concentrations found in wastewaters had no effect on TOA disinfection efficacy. The results of this research demonstrate that TOAs, which could potentially be powered by solar panels, have potential as a sustainable disinfection process compared to chlorine, ozone, and ultraviolet light.

Sodium persulfate has become the most popular oxidant source for the in situ chemical oxidation (ISCO) treatment of organic contaminants in the subsurface. The most common persulfate activators, iron chelates and base, are often ineffective in initiating the generation of reactive oxygen species in field applications. In this study, glucose was investigated as a persulfate activator in systems containing varying concentrations of sodium hydroxide using nitrobenzene as a hydroxyl radical probe and hexachloroethane as a reductant + nucleophile probe. Glucose activation of persulfate increased as a function of sodium hydroxide addition, but was still effective at circumneutral pH regimes. Use of central composite rotatable experimental designs showed that hydroxyl radical and reductant + nucleophile generation rates increased as a function of persulfate at near-neutral pH regimes. Glucose activation of persulfate has the advantages over other activation pathways of more options and flexibility for effective process chemistry and of minimizing or eliminating the mass of sodium hydroxide added to the subsurface. The results of this research can be applied in the field by first evaluating glucose activation compared to base and iron chelate activation of persulfate in laboratory treatability studies., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The activation of peroxymonosulfate by iron (II), iron (III), and iron (III)-EDTA for in situ chemical oxidation (ISCO) was compared using nitrobenzene as a hydroxyl radical probe, anisole as a hydroxyl radical+sulfate radical probe, and hexachloroethane as a reductant+nucleophile probe. In addition, activated peroxymonosulfate was investigated for the treatment of the model groundwater contaminants perchloroethylene (PCE) and trichloroethylene (TCE). The relative activities of hydroxyl radical and sulfate radical in the degradation of the probe compounds and PCE and TCE were isolated using the radical scavengers tert-butanol and isopropanol. Iron (II), iron (III), and iron (III)-EDTA effectively activated peroxymonosulfate to generate hydroxyl radical and sulfate radical, but only a minimal flux of reductants or nucleophiles. Iron (III)-EDTA was a more effective activator than iron (II) and iron (III), and also provided a non-hydroxyl radical, non-sulfate radical degradation pathway. The contribution of sulfate radical relative to hydroxyl radical followed the order of anisole>>TCE>PCE >>nitrobenzene; i.e., sulfate radical was less dominant in the oxidation of more oxidized target compounds. Sulfate radical is often assumed to be the primary oxidant in activated peroxymonosulfate and persulfate systems, but the results of this research demonstrate that the reactivity of sulfate radical with the target compound must be considered before drawing such a conclusion., (Published by Elsevier B.V.)

Total oxidant demand (TOD) is a parameter that is often measured during in situ chemical oxidation (ISCO) treatability studies. The importance of TOD is based on the concept that the oxidant demand created by soil organic matter and other reduced species must be overcome before contaminant oxidation can proceed. TOD testing was originally designed for permanganate ISCO, but has also recently been applied to activated persulfate ISCO. Recent studies have documented that phenoxides activate persulfate; because soil organic matter is rich in phenolic moieties, it may activate persulfate rather than simply exerting TOD. Therefore, the generation of reactive oxygen species was investigated in three soil horizons of varied soil organic carbon content over 5-day TOD testing. Hydroxyl radical may have been generated during TOD exertion, but was likely scavenged by soil organic matter. A high flux of reductants + nucleophiles (e.g. alkyl radicals + superoxide) was generated as TOD was exerted, resulting in the rapid destruction of the probe compound hexachloroethane and the common groundwater contaminant trichloroethylene (TCE). The results of this research document that, unlike permanganate TOD, contaminant destruction does occur as TOD is exerted in persulfate ISCO systems and is promoted by the activation of persulfate by soil organic matter. Future treatability studies for persulfate ISCO should consider contaminant destruction as TOD is exerted, and the potential for persulfate activation by soil organic matter., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

In situ chemical oxidation (ISCO) has become a widely used technology for the remediation of soil and groundwater. Although peroxymonosulfate is not a common oxidant source for ISCO, its chemical structure is similar to the ISCO reagents hydrogen peroxide and persulfate, suggesting that peroxymonosulfate may have the beneficial properties of each of these oxidants. Peroxymonosulfate activation in the presence of subsurface minerals was examined as a basis for ISCO, and possible reactive species (hydroxyl radical, sulfate radical, and reductants+nucleophiles) generated in the mineral-activated peroxymonosulfate systems were investigated. Rates of peroxymonosulfate decomposition and generation rates of reactive species were studied in the presence of three iron oxides, one manganese oxide, and three soil fractions. The iron oxide hematite-activated peroxymonosulfate system most effectively degraded the hydroxyl radical probe nitrobenzene. Reductants+nucleophiles were not generated in mineral-activated peroxymonosulfate systems. Use of the probe compound anisole in conjunction with scavengers demonstrated that both sulfate radical and hydroxyl radical are generated in mineral-activated peroxymonosulfate systems. In order to confirm the activation of peroxymonosulfate by subsurface minerals, one natural soil and associated two soil fractions were evaluated as peroxymonosulfate catalysts. The natural soil did not effectively promote the generation of oxidants; however, the soil organic matter was found to promote the generation of reductants + nucleophiles. The results of this research show that peroxymonosulfate has potential as an oxidant source for ISCO applications, and would be most effective in treating halogenated contaminants when soil organic matter is present in the subsurface., (Copyright © 2016. Published by Elsevier B.V.)

Antibiotics that enter the environment can present human and ecological health risks. An understanding of antibiotic hydrolysis rates is important for predicting their environmental persistence as biologically active contaminants. In this study, hydrolysis rates and Arrhenius constants were determined as a function of pH and temperature for two amphenicol (chloramphenicol and florfenicol) and two macrolide (spiramycin and tylosin) antibiotics. Antibiotic hydrolysis rates in pH 4-9 buffer solutions at 25°C, 50°C, and 60°C were quantified, and degradation products were characterized. All of the antibiotics tested remained stable and exhibited no observable hydrolysis under ambient conditions typical of aquatic ecosystems. Acid- and base-catalyzed hydrolysis occurred at elevated temperatures (50-60°C), and hydrolysis rates increased considerably below pH 5 and above pH 8. Hydrolysis rates also increased approximately 1.5- to 2.9-fold for each 10°C increase in temperature. Based on the degradation product masses found, the functional groups that underwent hydrolysis were alkyl fluoride, amide, and cyclic ester (lactone) moieties; some of the resultant degradation products may remain bioactive, but to a lesser extent than the parent compounds. The results of this research demonstrate that amphenicol and macrolide antibiotics persist in aquatic systems under ambient temperature and pH conditions typical of natural waters. Thus, these antibiotics may present a risk in aquatic ecosystems depending on the concentration present., (Copyright © 2015. Published by Elsevier Ltd.)

Catalyzed H2O2 propagations (CHP) was studied to treat 1,1,1-trichloroethane (TCA) and 1,1-dichloroethane (DCA) dense nonaqueous phase liquids (DNAPLs) and to elucidate the reactive oxygen species responsible for their destruction. A TCA DNAPL was rapidly destroyed by CHP at a rate 3.5 times greater than its maximum rate of dissolution. Using systems that generate a single reactive oxygen species, the species responsible for TCA DNAPL destruction was found to be superoxide. Both hydroxyl radical and superoxide were responsible for the destruction of the DCA DNAPL. Both compounds were destroyed at equal rates in a mixed TCA/DCA DNAPL, which suggests that the rate of treatment is limited by a surface phenomenon at the DNAPL-water interface. The optimum pH for the destruction of TCA and DCA DNAPLs was near the pKa of 4.8 for perhydroxyl radical-superoxide systems. The results of this research demonsrate that TCA and DCA DNAPLs are effectively destroyed by CHP and that superoxide generation is necessary for effective TCA DNAPL destruction, while both hydroxyl radical and superoxide are necessary for effective DCA DNAPL destruction.

An understanding of antibiotic hydrolysis rates is important for predicting their environmental persistence. Hydrolysis rates and Arrhenius constants were determined as a function of pH and temperature for three common β-lactam antibiotics, ampicillin, cefalotin, and cefoxitin. Antibiotic hydrolysis rates at pH4-9 at 25 °C, 50 °C, and 60 °C were quantified, and degradation products were identified. The three antibiotics hydrolyzed under ambient conditions (pH7 and 25 °C); half-lives ranged from 5.3 to 27 d. Base-catalyzed hydrolysis rates were significantly greater than acid-catalyzed and neutral pH hydrolysis rates. Hydrolysis rates increased 2.5- to 3.9-fold for a 10 °C increase in temperature. Based on the degradation product masses found, the likely functional groups that underwent hydrolysis were lactam, ester, carbamate, and amide moieties. Many of the proposed products resulting from the hydrolysis of ampicillin, cefalotin, and cefoxitin likely have reduced antimicrobial activity because many products contained a hydrated lactam ring. The results of this research demonstrate that β-lactam antibiotics hydrolyze under ambient pH and temperature conditions. Degradation of β-lactam antibiotics will likely occur over several weeks in most surface waters and over several days in more alkaline systems., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The impacts of four common animal husbandry antibiotics (ampicillin, florfenicol, sulfamethazine, and tylosin) on anaerobic digestion (AD) treatment efficiency and the potential for antibiotic degradation during digestion were evaluated. Sulfamethazine and ampicillin exhibited no impact on total biogas production up to 280 and 350 mg/L, respectively, although ampicillin inhibited biogas production rates during early stages of AD. Tylosin reduced biogas production by 10-38% between 130 and 913 mg/L. Florfenicol reduced biogas by ≈ 5%, 40% and 75% at 6.4, 36 and 210 mg/L, respectively. These antibiotic concentrations are higher than commonly seen for mixed feedlot manure, so impacts on full scale AD should be minimal. Antibiotic degradation products were found, confirming AD effectively degraded ampicillin, florfenicol, and tylosin, although some products were persistent throughout the process. Contamination of AD solid and liquid effluents with sulfamethazine and antibiotic transformation products from florfenicol and tylosin could present an environmental concern., (Published by Elsevier Ltd.)

The water quality parameters nitrate-nitrogen, dissolved organic carbon, and suspended solids were correlated with photodegradation rates of the herbicides atrazine and 2,4-D in samples collected from four sites in the Columbia River Basin, Washington, USA. Surface water samples were collected in May, July, and October 2010 and analyzed for the water quality parameters. Photolysis rates for the two herbicides in the surface water samples were then evaluated under a xenon arc lamp. Photolysis rates of atrazine and 2,4-D were similar with rate constants averaging 0.025 h(-1) for atrazine and 0.039 h(-1) for 2,4-D. Based on multiple regression analysis, nitrate-nitrogen was the primary predictor of photolysis for both atrazine and 2,4-D, with dissolved organic carbon also a predictor for some sites. However, at sites where suspended solids concentrations were elevated, photolysis rates of the two herbicides were controlled by the suspended solids concentration. The results of this research provide a basis for evaluating and predicting herbicide photolysis rates in shallow surface waters., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The activation of persulfate by phenols was investigated to further the understanding of persulfate chemistry for in situ chemical oxidation (ISCO). Phenol (pKa = 10.0) activated persulfate at pH 12 but not at pH 8, suggesting activation occurred only via the phenoxide form. Evaluation of the phenoxide activation mechanism was complicated by the concurrent activation of persulfate by hydroperoxide anion, which is generated by the base catalyzed hydrolysis of persulfate. Therefore, phenoxide activation was investigated using pentachlorophenoxide at pH 8.3, midway between the pKa of pentachlorophenol (pKa = 4.8) and that of hydrogen peroxide (pKa = 11.8). Of the two possible mechanisms for phenoxide activation of persulfate (reduction or nucleophilic attack) the results were consistent with reduction of persulfate by phenoxide with oxidation of the phenoxide. The concentration of phenoxide required for maximum persulfate activation was low (1 mM). The results of this research document that phenoxides activate persulfate via reduction; phenolic moieties ubiquitous to soil organic matter in the subsurface may have a significant role in the activation of persulfate during its injection into the subsurface for ISCO. Furthermore, the results provide the foundation for activation of persulfate by other organic anions without the toxicity of phenols, such as keto acids.

The use of tin oxide anodes (TOAs) has been proposed for the disinfection of wastewater effluents and concurrent treatment of emerging contaminants. The common water quality constituents suspended solids, chemical oxygen demand (COD), alkalinity, ammonia-nitrogen, nitrite-nitrogen, and nitrate-nitrogen were investigated for their effect on oxidation performance by TOAs. Relative oxidant generation rates were not affected by increasing concentrations of suspended solids, COD, alkalinity, ammonia-nitrogen, or nitrate-nitrogen. Although nitrite-nitrogen did compete for oxidants generated by TOAs, nitrite is not usually present in oxygenated effluents. Chemical oxygen demand, ammonia, and nitrite were oxidized in the TOA systems, primarily through a non-hydroxyl radical mechanism. This research demonstrates that a majority of the common water quality constituents did not negatively affect TOA oxidation performance. Tin oxide anodes represent a potentially low cost and low maintenance option for single-step disinfection and treatment of emerging contaminants in wastewater effluents.

The potential for 13 naturally occurring minerals to mediate the decomposition of persulfate and generate a range of reactive oxygen species was investigated to provide fundamental information on activation mechanisms when persulfate is used for in situ chemical oxidation (ISCO). Only four of the minerals (cobaltite, ilmenite, pyrite, and siderite) promoted the decomposition of persulfate more rapidly than persulfate-deionized water control systems. The other nine minerals decomposed persulfate at the same rate or more slowly than the control systems. Mineral-mediated persulfate activation was conducted with the addition of one of three probe compounds to detect the generation of reactive oxygen species: anisole (sulfate+hydroxyl radical), nitrobenzene (hydroxyl radical), and hexachloroethane (reductants and nucleophiles). The reduced mineral pyrite promoted rapid generation of sulfate+hydroxyl radical. However, the remainder of the minerals provided minimal potential for the generation of reactive oxygen species. The results of this research demonstrate that the majority of naturally occurring trace minerals do not activate persulfate to generate reactive oxygen species, and other mechanisms of activation are necessary to promote contaminant destruction in the subsurface during persulfate ISCO., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Rapid hydrogen peroxide decomposition is the primary limitation of catalyzed H(2)O(2) propagations in situ chemical oxidation (CHP ISCO) remediation of the subsurface. Two stabilizers of hydrogen peroxide, citrate and phytate, were investigated for their effectiveness in one-dimensional columns of iron oxide-coated and manganese oxide-coated sand. Hydrogen peroxide (5%) with and without 25 mM citrate or phytate was applied to the columns and samples were collected at 8 ports spaced 13 cm apart. Citrate was not an effective stabilizer for hydrogen peroxide in iron-coated sand; however, phytate was highly effective, increasing hydrogen peroxide residuals two orders of magnitude over unstabilized hydrogen peroxide. Both citrate and phytate were effective stabilizers for manganese-coated sand, increasing hydrogen peroxide residuals by four-fold over unstabilized hydrogen peroxide. Phytate and citrate did not degrade and were not retarded in the sand columns; furthermore, the addition of the stabilizers increased column flow rates relative to unstabilized columns. These results demonstrate that citrate and phytate are effective stabilizers of hydrogen peroxide under the dynamic conditions of one-dimensional columns, and suggest that citrate and phytate can be added to hydrogen peroxide before injection to the subsurface as an effective means for increasing the radius of influence of CHP ISCO., (Copyright © 2011. Published by Elsevier B.V.)

Deicers currently used for aircraft deicing, including ethylene glycol and propylene glycol, pose significant threats to surface waters, as a result of high biochemical oxygen demand (BOD) and toxicity to aquatic organisms. Oxidized starch may provide a less toxic deicer with lower BOD. The freezing point depression of starch formulations oxidized using hydrogen peroxide and catalysts (i.e., catalyzed hydrogen peroxide [H2O2] propagations-CHP) was 28 degrees C, and viscosities similar to those of commercial deicers were achieved after post-treatment with granular activated carbon. The most effective oxidized starch formulation exerted a 5-day BOD up to 6 times lower than glycol deicers (103 versus 400 to 800 g O2/L). Toxicity to Ceriodaphnia dubia for this formulation (48-hour lethal concentration, 50% [LC50] of 2.73 g/L) was greater than pure propylene glycol (13.1 g/ L), but lower than propylene glycol deicer formulations (1.02 g/L). Organic acids were identified by gas chromatography/mass spectrometry as the primary constituents in the oxidized starch solution. The proposed deicing system would provide effective deicing while exerting minimal environmental effects (e.g., lower toxicity to aquatic organisms and lower BOD). Furthermore, these deicers could be made from waste starch, promoting sustainability.

Two surface soils contaminated with polychlorinated biphenyls (PCBs) collected from Superfund sites in the New England region of the United States, Fletcher Paints and Merrimack Industrial Metals, were evaluated for field treatment at the bench level using catalyzed H(2)O(2) propagations (CHP-modified Fenton's reagent). The two soils were first evaluated for the potential for in situ treatment based on two criteria: (1) temperature (< 40 °C after CHP reagent addition), and (2) hydrogen peroxide longevity (> 24h). In situ CHP remediation was more applicable to the Fletcher soil, while the Merrimack soil was better suited to ex situ treatment based on temperature increases and hydrogen peroxide lifetimes. Using the highest hydrogen peroxide concentrations appropriate for in situ treatment in each soil, PCB destruction was 94 % in the Fletcher soil but only 48% in the Merrimack soil. However, 98% PCB destruction was achieved in the Merrimack soil using conditions more applicable to ex situ treatment (higher hydrogen peroxide concentrations with temperatures > 40 °C). Analysis of degradation products by gas chromatography/mass spectroscopy showed no detectable chlorinated degradation products, suggesting that the products of PCB oxidation were rapidly dechlorinated and degraded. The results of this research document that the two PCB-contaminated soils studied can be effectively treated using aggressive CHP conditions, and that such a detailed bench study provides important information before implementing field treatment., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

The possibility of simultaneous activity of superoxide-mediated transformations and heterotrophic aerobic bacterial metabolism was investigated in catalyzed H(2)O(2) propagations (CHP; i.e., modified Fenton's reagent) systems containing Escherichia coli. Two probe compounds were used: glucose for the detection of heterotrophic metabolism of E. coli, and tetrachloromethane (CCl(4)) for the detection of superoxide generated in a MnO(2)-catalyzed CHP system. In the MnO(2)-catalyzed CHP system without bacteria, only CCl(4) loss was observed; in contrast, only glucose degradation occurred E. coli systems without CHP reagents. In combined microbial-MnO(2) CHP reactions, loss of both probes was observed. Glucose assimilation decreased and CCl(4) transformation increased as a function of H(2)O(2) concentration. Central composite rotatable experimental designs were used to determine that the conditions providing maximum simultaneous abiotic-biotic reactions were a biomass level of 10(9)CFU/mL, 0.5mM H(2)O(2), and 0.5 g MnO(2). These results demonstrate that bacterial metabolism can occur in the presence of superoxide-mediated transformations. Such coexisting reactions may occur when H(2)O(2) is injected into MnO(2)-rich regions of the subsurface as a microbial oxygen source or for in situ oxidation; however, process control of such coexisting transformations may be difficult to achieve in the subsurface due to heterogeneity. Alternatively, hybrid abiotic reduction-biotic oxidation systems could be used for the treatment of industrial effluents or dilute solvent wastes that contain traces of highly halogenated compounds., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Base is the most commonly used activator of persulfate for the treatment of contaminated groundwater by in situ chemical oxidation (ISCO). A mechanism for the base activation of persulfate is proposed involving the base-catalyzed hydrolysis of persulfate to hydroperoxide anion and sulfate followed by the reduction of another persulfate molecule by hydroperoxide. Reduction by hydroperoxide decomposes persulfate into sulfate radical and sulfate anion, and hydroperoxide is oxidized to superoxide. The base-catalyzed hydrolysis of persulfate was supported by kinetic analyses of persulfate decomposition at various base:persulfate molar ratios and an increased rate of persulfate decomposition in D(2)O vs H(2)O. Stoichiometric analyses confirmed that hydroperoxide reacts with persulfate in a 1:1 molar ratio. Addition of hydroperoxide to basic persulfate systems resulted in rapid decomposition of the hydroperoxide and persulfate and decomposition of the superoxide probe hexachloroethane. The presence of superoxide was confirmed with scavenging by Cu(II). Electron spin resonance spectroscopy confirmed the generation of sulfate radical, hydroxyl radical, and superoxide. The results of this research are consistent with the widespread reactivity reported for base-activated persulfate when it is used for ISCO.

Persulfate dynamics in the presence of subsurface minerals was investigated as a basis for understanding persulfate activation for in situ chemical oxidation (ISCO). The mineral-mediated decomposition of persulfate and generation of oxidants and reductants was investigated with four iron and manganese oxides and two clay minerals at both low pH (<7) and high pH (>12). The manganese oxide birnessite was the most effective initiator of persulfate for degrading the oxidant probe nitrobenzene, indicating that oxidants are generated at both low and high pH regimes. The iron oxide goethite was the most effective mineral for degrading the reductant probe hexachloroethane. A natural soil and two soil fractions were used to confirm persulfate activation by synthetic minerals. The soil and soil fractions did not effectively promote the generation of oxidants or reductants. However, soil organic matter was found to promote reductant generation at high pH. The results of this research demonstrate that synthetic iron and manganese oxides can activate persulfate to generate reductants and oxidants; however, iron and manganese oxides in the natural soil studied do not show the same reactivity, most likely due to the lower masses of the metal oxides in the soil relative to the masses studied in isolated mineral systems., (2010. Published by Elsevier B.V.)

Highly halogenated organic compounds, which include polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins (PCDDs) formed during the synthesis of pentachlorophenol and chlorophenoxy herbicides, are often found as contaminants in less toxic nonaqueous media, such as waste oil, oily sludges, or biosolids. Superoxide is highly reactive with halogenated compounds when both are dissolved in nonaqueous media; however, superoxide is most economically generated in water, where it is unreactive with most organic compounds. Superoxide reactivity was investigated in organic solvent-water systems as a basis for treating halogenated contaminants in less toxic nonaqueous media. Such a process could potentially render a contaminated oil or sludge nonhazardous, providing a mechanism for waste volume reduction. Increasing amounts of water added to acetone and dimethyl sulfoxide systems decreased the activity of superoxide in the solvent, but enough activity remained for effective treatment. Superoxide was then generated in the aqueous phase of two-phase water-organic solvent systems, and significant superoxide activity was achieved in the organic media with the addition of phase transfer catalysts (PTCs) to transfer superoxide into the nonaqueous phase. The results of this research demonstrate that superoxide, which can be generated in water electrochemically or through the catalytic decomposition of peroxygens, has the potential to be transferred to oils, sludges, and other less toxic nonaqueous media to destroy highly refractory contaminants such as PCBs, PCDDs, and other halogenated contaminants.

Sorption of hydrophobic contaminants to soils and subsurface solids is a significant limitation for the in situ chemical oxidation (ISCO) remediation of contaminated sites. A recently developed ISCO reagent, activated persulfate, was investigated for its potential to provide enhanced treatment of sorbed contaminants, a phenomenon that has previously been observed in catalyzed H(2)O(2) propagations (CHP; modified Fenton's reagent). Perchloroethylene (PCE) and hexachlorocyclopentadiene (HCCP) were sorbed to diatomaceous earth and treated with CHP, iron (II)-citrate-activated persulfate, and base-activated persulfate. Gas-purge desorption was used to measure the maximum natural rate of desorption of the compounds. Enhanced treatment of both sorbed probe compounds was observed in CHP reactions, with PCE and HCCP destruction occurring more rapidly than their respective rates of gas-purge desorption. However, probe compound loss in both formulations of activated persulfate was equal or less than the rates of gas-purge desorption, indicating that enhanced treatment of the sorbed contaminants did not occur in the persulfate reactions. Activated persulfate treatment is likely ineffective for hydrophobic compounds that are sorbed to soils and subsurface solids, and is probably more effective for compounds that are not limited by desorption.

Superoxide is unreactive in deionized water, but aqueous systems containing added solvents, including H2O2 at >100 mM, show significantly increased reactivity of superoxide with oxidized organic compounds such as highly chlorinated aliphatics. The potential for solid surfaces to similarly increase the reactivity of superoxide in water was investigated. Heterogeneous birnessite (gamma-MnO2)-catalyzed decomposition of H2O2 promoted the degradation of the superoxide probe hexachloroethane (HCA) at H202 concentrations as low as 7.5 mM, while no measurable HCA degradation was found in parallel homogeneous iron(III)-EDTA-H2O2 systems at H2O2 concentrations <100 mM. Electron spin resonance spectroscopy confirmed that superoxide was the dominant reactive species generated in the birnessite-catalyzed decomposition of H2O2. Increased superoxide reactivity was also found in aqueous superoxide-glass bead heterogeneous systems, and the rates of HCA degradation increased as a function of the surface area of the glass beads. The results of this research show that, similar to the addition of solvents, the presence of surfaces also enhances the reactivity of superoxide in water, possibly by altering the superoxide solvation shell. On the basis of these findings, superoxide generated in catalyzed H2O2 propagations (CHP; modified Fenton's reagent) used for in situ chemical oxidation (ISCO) may have greater reactivity with highly oxidized contaminants than previously thought.

Dimensionally stable anodes (DSAs) demonstrate potential for the electrochemical treatment of industrial waste streams and disinfection of effluent. Oxidation by laboratory-prepared tin oxide DSAs was compared with that of commercially available ruthenium oxide, iridium oxide, and mixed metal oxide DSAs, using hexanol as a probe molecule. The performance of the four anodes was similar in two-chamber reactors, in which the anode cell was separated from the cathode cell by a Nafion membrane, which allows transmission of current between the chambers, but not passage of chemical constituents. The anodes were then evaluated in single-cell reactors, which are more representative of potential treatment and disinfection applications. However, in the single-cell reactors, the tin oxide anodes were significantly more effective at oxidation and generated higher quality cyclic voltammograms than the other DSAs. These results suggest that tin oxide anodes have greater potential than the three commercially available DSAs tested for industrial waste stream treatment and effluent disinfection.

The stabilization of hydrogen peroxide was investigated as a basis for enhancing its downgradient transport and contact with contaminants during catalyzed H(2)O(2) propagations (CHP) in situ chemical oxidation (ISCO). Stabilization of hydrogen peroxide was investigated in slurries containing four characterized subsurface solids using phytate, citrate, and malonate as stabilizing agents after screening ten potential stabilizers. The extent of hydrogen peroxide stabilization and the most effective stabilizer were solid-specific; however, phytate was usually the most effective stabilizer, increasing the hydrogen peroxide half-life to as much as 50 times. The degree of stabilization was nearly as effective at 10 mM concentrations as at 250 mM or 1 M concentrations. The effect of stabilization on relative rates of hydroxyl radical activity varied between the subsurface solids, but citrate and malonate generally had a greater positive effect than phytate. The effect of phytate, citrate, and malonate on the relative rates of superoxide generation was minimal to somewhat negative, depending on the solid. The results of this research demonstrate that the stabilizers phytate, citrate, and malonate can significantly increase the half-life of hydrogen peroxide in the presence of subsurface solids during CHP reactions while maintaining a significant portion of the reactive oxygen species activity. Use of these stabilizers in the field will likely improve the delivery of hydrogen peroxide and downgradient treatment during CHP ISCO.

The enhanced treatment of sorbed contaminants has been documented in modified Fenton's reactions; contaminants are desorbed and degraded more rapidly than they desorb by fill-and-draw or gas-purge desorption. The reactive species responsible for this process was investigated using dodecane as a model sorbent. Hydroxyl radical, hydroperoxide anion, and superoxide radical anion were generated separately to evaluate their roles in enhanced dodecane desorption. Dodecane desorption from silica sand over 180 minutes was negligible in gas-purge systems and in the hydroxyl radical and hydroperoxide anion systems. In contrast, enhanced desorption of dodecane occurred in superoxide systems, with >80% desorption over 180 minutes. Scavenging of superoxide eliminated the enhanced desorption of dodecane in both superoxide and modified Fenton's systems, confirming that superoxide is the desorbing agent in modified Fenton's reactions. Conditions that promote superoxide generation in Fenton's reactions may enhance their effectiveness for in situ subsurface remediation of sorbed hydrophobic contaminants.

The pyrolusite (beta-MnO2)-mediated oxidation of 2,4,6-trichlorophenol (TCP) under nonaqueous conditions was investigated to assess the potential for abiotic transformations of chlorophenols and their transformation pathways when they are released to soils and the vadose zone. Lower rates of TCP oxidation were found at lower relative humidities, but the rates were still relatively high under near-dry conditions, with 86% of the TCP transformed within 24 h at less than 2% relative humidity. The rates of TCP transformation and soluble manganese formation at less than 2% relative humidity were not affected by atmospheric oxygen content. The manganese oxide-mediated oxidation of TCP resulted in the formation of 2,6-dichloro-1,4-benzoquinone and dimers, including polychlorinated phenoxyphenols and at least one tetrachlorodibenzo-p-dioxin. The products are consistent with the proposed mechanism in which some of the TCP is transformed into trichlorophenoxy radicals that attack TCP and its transformation products. The present results demonstrate that naturally occurring manganese oxides have the potential to oxidize industrial compounds such as TCP; however, the transformation products may be more toxic and persistent than the parent compound.

The destruction of a carbon tetrachloride DNAPL and a chloroform DNAPL was investigated in reactions containing 0.5 mL of DNAPL and a solution of modified Fenton's reagent (2M H2O2 and 5mM iron(III)-chelate). Carbon tetrachloride and chloroform masses were followed in the DNAPLs, the aqueous phases, and the off gasses. In addition, the rate of DNAPL destruction was compared to the rate of gas-purge dissolution. Carbon tetrachloride DNAPLs were rapidly destroyed by modified Fenton's reagent at 6.5 times the rate of gas purge dissolution, with 74% of the DNAPL destroyed within 24h. Use of reactions in which a single reactive oxygen species (hydroxyl radical, hydroperoxide anion, or superoxide radical anion) was generated showed that superoxide is the reactive species in modified Fenton's reagent responsible for carbon tetrachloride DNAPL destruction. Chloroform DNAPLs were also destroyed by modified Fenton's reagent, but at a rate slower than the rate of gas purge dissolution. Reactions generating a single reactive oxygen species demonstrated that chloroform destruction was the result of both superoxide and hydroxyl radical activity. Such a mechanism of chloroform DNAPL destruction is in agreement with the slow but relatively equal reactivity of chloroform with both superoxide and hydroxyl radical. The results of this research demonstrate that modified Fenton's reagent can rapidly and effectively destroy DNAPLs of contaminants characterized by minimal reactivity with hydroxyl radical, and should receive more consideration as a DNAPL cleanup technology.

The displacement of sorbed metals during the treatment of soils and groundwater with modified Fenton's reagent was investigated using five common metal contaminants (cadmium, copper, lead, nickel, and zinc) and kaolinite as a model sorbent. Modified Fenton's conditions included three H(2)O(2) concentrations (0.9, 1.8, 2.7 M) and two catalysts: soluble iron (III) at pH 3 and iron (III)-NTA chelate at pH 6. Iron (III)-catalyzed Fenton's reactions released significant amounts of zinc, cadmium, and copper. Modified Fenton's reactions catalyzed by iron (III)-NTA released zinc, cadmium, copper, and lead, and resulted in greater amounts of metals release than the iron (III)-catalyzed reactions. Metals release may have been mediated by transient oxygen species, such as superoxide, generated by propagation reactions, which become dominant at the relatively high hydrogen peroxide concentrations used. Metals release from kaolinite was undetectable when sufficiently low hydrogen peroxide concentrations were maintained to minimize propagation reactions. These results indicate that using dilute concentrations of hydrogen peroxide for Fenton's ISCO may minimize potential metals mobility when treating contaminated soils and groundwater containing a mixture of organic and metal contaminants.

The reactive oxygen species responsible for the transformation of carbon tetrachloride (tetrachloromethane, CT) by modified Fenton's reagent using hydrogen peroxide (H2O2) concentrations >0.1 M was investigated. Addition of the hydroxyl radical scavenger 2-propanol to modified Fenton's reactions did not significantly lower CT transformation rates. Scavenging by 2-propanol not only confirmed that hydroxyl radicals are not responsible for CT destruction, but also suggested that a major product of an iron (III)-driven initiation reaction, superoxide radical anion (O2-), is the species responsible for CT transformation. To investigate this hypothesis, CT degradation was studied in aqueous KO2 reactions. Minimal CT degradation was found in CT-KO2 reactions; however, when H2O2 was added to the KO2 reactions at concentrations similar to those in the modified Fenton's reactions (0.1, 0.5, and 1 M), CT degradation increased significantly. Similar results were obtained when 1 M concentrations of other solvents were added to aqueous KO2 reactions, and the observed first-order rate constant for CT degradation correlated strongly (R2 = 0.986) with the empirical solvent polarity (E(T)N) of the added solvents. The results indicate that even dilute concentrations of solvents, including H202, can increase the reactivity of O2- in water, probably by changing its solvation sphere. The higher reactivity of O2- generated in modified Fenton's reagent, which has a less polar nature due to the presence of H2O2, may result in a wider range of contaminant degradation than previously thought possible.

A homologous series of n-alcohols was used as model contaminants to investigate the effect of hydrophobicity on the hydrogen peroxide concentration necessary in Fenton-like treatment for near-complete (>99%) destruction of compounds sorbed to soil. These probe compounds were selected because they exhibit equal reactivities with hydroxyl radicals, but have varied hydrophobicities. The standard Fenton reaction was first used to confirm equal hydroxyl radical reactivity for the n-alcohols. Central composite rotatable design experiments were then used to determine the conditions in an iron(III)-hydrogen peroxide system that resulted in 99% degradation of each of the probe compounds when sorbed to soil. The hydrogen peroxide concentrations required for 99% destruction of the sorbed compounds increased with probe compound hydrophobicity. Furthermore, hydrogen peroxide concentration requirements were directly proportional to the log octanol-water partition coefficients (logK(OW)) of each probe compound. This quantitative relationship may not be directly applicable to other organic contaminants, but a strong correlation between logK(OW) and hydrogen peroxide requirements for other contaminants will likely be found. These results confirm that hydrogen peroxide requirements for soil treatment increase as a function of contaminant hydrophobicity and provide a basis for the development of an algorithm for hydrogen peroxide requirements when modified Fenton's reagent is used for in situ chemical oxidation (ISCO).

The degradation of tetrachloromethane (carbon tetrachloride-CT) by modified Fenton's reagent (catalyzed hydrogen peroxide) was investigated using a range of hydrogen peroxide concentrations and 1 mM iron(III) catalyst. The documented reactive species in modified Fenton's reactions, hydroxyl radical (OH*), is not reactive with CT, yet CT degradation was observed in the Fenton's reactions and was confirmed by chloride generation. Because CT is not reactive with OH*, a reductive mechanism which may involve superoxide radical anion is proposed for CT degradation in modified Fenton's systems. Scavenging of reductants by excess chloroform prevented CT degradation, confirming a reductive mechanism. Similar to CT, three other oxidized aliphatic compounds, hexachloroethane, bromotrichloromethane, and tetranitromethane, were also degraded by modified Fenton's reagent. The results show that modified Fenton's reactions act through a reductive mechanism to degrade compounds that are not reactive with OH*, which broadens the scope of this process for hazardous waste treatment and remediation.

Hydrogen peroxide (H2O2) catalyzed by soluble iron or naturally occurring soil minerals, (i.e., modified Fenton's reagent) was investigated as a basis for mineralizing sorbed and NAPL-phase benzo[a]pyrene (BaP), a hydrophobic and toxic polycyclic aromatic hydrocarbon, in two soils of different complexity. 14C-Benzo[a]pyrene was added to silica sand and a silt loam soil, and mineralization was investigated using three-level central composite rotatable experimental designs. The effects of H2O2 concentration, slurry volume, and iron(II) amendment were investigated in the silica sand systems. In a Palouse loess silt loam soil, the variables included H2O2 concentration, slurry volume, and pH, with H2O2 catalyzed by naturally occurring iron oxyhydroxides. Regression equations generated from the data were used to develop three-dimensional response surfaces describing BaP mineralization. Based on the recovery of 14C-CO2, 70% BaP mineralization was achieved in the sand within 24 h using 15 M H2O2 and an iron(II) concentration of 6.6 mM with a slurry volume of 0.3 x the field capacity of the sand. For the silt loam soil, 85% mineralization of BaP was observed using 15 M H2O2, no iron amendment, and a slurry volume of 20 x the soil field capacity. The balance of the radiolabeled carbon remained as unreacted BaP in the soil fraction. Gas-purge measurements over 5 d confirmed negligible desorption under nontreatment conditions. However, oxidation reactions were complete within 24 h and promoted up to 85% BaP mineralization, documenting that the natural rate of desorption/dissolution did not control the rate of oxidation and mineralization of the BaP. The results show that catalyzed H2O2 has the ability to rapidly mineralize sorbed/NAPL-phase BaP and that partitioning, which is often the rate-limiting factor in soil remediation, does not appear to limit the rate of vigorous Fenton-like treatment.

The conditions that support the simultaneous activity of hydroxyl radicals (OH.) and heterotrophic aerobic bacterial metabolism were investigated using two probe compounds: (1) tetrachloroethene (PCE) for the detection of OH. generated by an iron-nitrilotriacetic acid (Fe-NTA) catalyzed Fenton-like reaction and (2) oxalate (OA) for the detection of heterotrophic metabolism of Xanthobacter flavus. In the absence of the bacterium in the quasi-steady-state Fenton's system, only PCE oxidation was observed; conversely, only OA assimilation was found in non-Fenton's systems containing X. flavus. In combined Fenton's-microbial systems, loss of both probes was observed. PCE oxidation increased and heterotrophic assimilation of OA declined as a function of an increase in the quasi-steady-state H2O2 concentration. Central composite rotatable experimental designs were used to determine the conditions that provide maximum simultaneous abiotic-biotic oxidations, which were achieved with a biomass level of 10(9) CFU/mL, 4.5 mM H2O2, and 2.5 mM Fe-NTA. These results demonstrate that heterotrophic bacterial metabolism can occur in the presence of hydroxyl radicals. Such simultaneous abiotic-biotic oxidations may exist when H2O2 is injected into the subsurface as a microbial oxygen source or as a source of chemical oxidants. In addition, hybrid abiotic-biotic systems could be used for the treatment of waters containing biorefractory organic contaminants present in recycle water, cooling water, or industrial waste streams.

Contaminant degradation, stoichiometry, and role of hydroxyl radicals (OH*) in four Fenton's systems were investigated using trichloroethylene (TCE) as a model contaminant. A standard Fenton's system, a modified soluble iron system with a pulse input of hydrogen peroxide, and two modified mineral-catalyzed systems (pH 3 and 7) were studied. In the standard Fenton's system, which had the most efficient reaction stoichiometry, 78% of the TCE was degraded; however, chloride analysis indicated that no more than two of the three chlorines were displaced per TCE molecule degraded. Although the modified soluble iron system was characterized by 91% TCE degradation, chloride analysis also indicated that no more than two of the chlorines were lost from the TCE. In the goethite system of pH 3, > 99% of the TCE was degraded. Near-complete release of chloride suggested that the TCE may have been mineralized. Only 22% degradation of TCE was achieved in the pH 7 goethite system. and there was minimal release of chloride. The mineral-catalyzed reactions exhibited the least efficient reaction stoichiometry of the four systems. Experiments using hydroxyl radical scavengers showed that the standard Fenton's system degraded TCE entirely by hydroxyl radical mechanisms, while approximately 10-15% of the degradation achieved in the modified soluble iron and goethite-catalyzed systems at pH 3 was mediated by non-hydroxyl radical mechanisms. In the goethite system at pH 7, only non-hydroxyl radical mechanisms were found. The goethite-catalyzed system at pH 3 effectively degraded the parent compound and may have the potential to mineralize contaminants when used for in situ soil and groundwater remediation and ex situ waste stream treatment in packed-bed reactors.

The relative oxidation of representative aromatic and aliphatic hydrocarbons found in gasoline was evaluated to provide the foundation for risk-based treatment of petroleum-contaminated soils and groundwater using modified Fenton's reagent (catalyzed hydrogen peroxide). Aromatic components of gasoline are considered more hazardous than the aliphatic fractions due to their higher mobility in the subsurface and their higher acute and chronic toxicities. Benzene, toluene, and mixed xylenes (BTX) were selected as aromatic compounds representative of unleaded gasoline, while nonane, decane, and dodecane (NDD) were used as model aliphatic compounds. The effects of hydrogen peroxide (H(2)O(2)) concentration, iron catalyst concentration, and pH on the degree of treatment of the model compounds were investigated using central composite rotatable experimental designs. Oxidation of the aromatic compounds required less iron and less H(2)O(2) than did oxidation of the aliphatic compounds, while proceeding more effectively at near-neutral pH. Greater than 95% of the BTX was treated at near-neutral pH using 2. 5% H(2)O(2) and 12.5 mM iron (III), while only 37% nonane, 7% decane, and 1% dodecane oxidation was achieved under the same conditions. The results show that the more toxic and mobile aromatic fraction was more effectively oxidized using less H(2)O(2) and more economical conditions, including near-neutral pH, compared to the aliphatic fraction. A process design based on treating only the aromatic fraction of petroleum may provide significantly lower costs when using modified Fenton's reagent for the treatment of contaminated soils and groundwater.

Rates of hydrogen peroxide decomposition, hydroxyl radical production, and oxygen evolution were investigated in silica sand-goethite slurries using unstabilized and stabilized hydrogen peroxide formulations. The goethite-catalyzed decomposition of unstabilized hydrogen peroxide formulations resulted in more rapid hydrogen peroxide loss and oxygen evolution relative to systems containing a highly stabilized hydrogen peroxide formulation. Systems at neutral pH and those containing higher goethite concentrations were characterized by higher rates of hydrogen peroxide decomposition and by more oxygen evolution. The stabilized hydrogen peroxide formulation showed greater hydroxyl radical production relative to the unstabilized formulations. Furthermore, hydroxyl radical production rates were greater at neutral pH than at the acidic pH regimes. The results suggest that when stabilized hydrogen peroxide is injected into the subsurface during in situ bioremediation, naturally occurring minerals such as goethite may initiate Fenton-like reactions. While these reactions may prove to be toxic to microorganisms, they have the potential to chemically oxidize contaminants in soils and groundwater.

Syndecans are a family of heparan sulfate proteoglycans implicated in cell-cell and cell-matrix interactions. To investigate the roles of syndecans in early development, we identified three syndecan family members in Xenopus laevis: Xsyn-1, Xsyn-2, and Xsyn-3. Xsyn-1 and Xsyn-2 are maternal mRNAs localized to the animal pole in blastulae, and are expressed in the ectoderm of gastrulae. In neurulae, Xsyn-1 is restricted to non-neural ectoderm and Xsyn-2 is restricted to neural ectoderm. In tailbud embryos, the three syndecans are expressed in adjacent, non-overlapping patterns. Xsyn-2 is expressed in the heart while Xsyn-1 is expressed in the underlying anterior endoderm. Xsyn-3 is expressed in the hindbrain, midbrain, and forebrain, while Xsyn-2 is expressed in the intervening regions. These results suggest that different members of the syndecan family have distinct developmental roles, perhaps acting as barriers to define tissue boundaries.

This study characterizes the mRNA expression of the retinoblastoma tumor suppressor gene in regenerating rat liver during 96 hr after 70% partial hepatectomy. A 960-bp BglII-OxaNI fragment of murine retinoblastoma cDNA was used to probe Northern blots of poly(A)(+)-enriched RNA isolated from regenerating liver. Two species of retinoblastoma mRNA, 2.8 kb and 4.7 kb long, were identified in control liver and exhibited an intensity ratio of 5:1, respectively. Expression of the 2.8-kb mRNA was reduced by 50% 1 hr after partial hepatectomy and was less than 10% of control values by 3 hr. The transcript began to reappear at 12 hr and returned to near-baseline levels by 24 hr. In contrast to the rapid disappearance of the 2.8-kb transcript, expression of the 4.7-kb mRNA increased 15-fold by 6 hr and returned to control levels by 18 hr after partial hepatectomy. Pretreatment of the animals with cycloheximide before partial hepatectomy completely stabilized steady-state levels of both mRNA transcripts through 6 hr. Nuclear run-on assays revealed a sixfold increase in transcription by 30 min and a return to near-baseline levels by 6 hr. The in vivo half-lives of the 2.8- and 4.7-kb transcripts in control livers were 39.5 and 41.2 min, respectively. The half-life of the 4.7-kb transcript 6 hr after partial hepatectomy was 39.1 min. Intravenous administration of transforming growth factor-beta 1, a known inhibitor of hepatocyte replication, just before partial hepatectomy caused no significant change in the modulation of the transcripts through 24 hr.(ABSTRACT TRUNCATED AT 250 WORDS)