Scott G. Huling

Effect and mechanism of persulfate activated by different methods for PAHs removal in soil

The influence of persulfate activation methods on polycyclic aromatic hydrocarbons (PAHs) degradation was investigated and included thermal, citrate chelated iron, and alkaline, and a hydrogen peroxide (H₂O₂)-persulfate binary mixture. Thermal activation (60 °C) resulted in the highest removal of PAHs (99.1%) and persulfate consumption during thermal activation varied (0.45-1.38 g/kg soil). Persulfate consumption (0.91-1.22 g/kg soil) and PAHs removal (73.3-82.9%) varied using citrate chelated iron. No significant differences in oxidant consumption and PAH removal was measured in the H₂O₂-persulfate binary mixture and alkaline activated treatment systems, relative to the unactivated control. Greater removal of high molecular weight PAHs was measured with persulfate activation. Electron spin resonance spectra indicated the presence of hydroxyl radicals in thermally activated systems; weak hydroxyl radical activity in the H₂O₂-persulfate system; and superoxide radicals were predominant in alkaline activated systems. Differences in oxidative ability of the activated persulfate were related to different radicals generated during activation.

Polycyclic Aromatic Hydrocarbon Biodegradation as a Function of Oxygen Tension in Contaminated Soil

Abstract Laboratory tests were conducted to determine the effect of soil gas oxygen concentration on the degradation and mineralization of spiked 14C-pyrene and nonspiked 16 priority pollutant polycyclic aromatic hydrocarbons (PAH) present in the soil. The soil used for the evaluation was taken from a prepared-bed land treatment unit at the Champion International Superfund Site in Libby, Montana. This soil was contaminated with wood preserving wastes including creosote (composed primarily of polycyclic aromatic hydrocarbons and pentachlorophenol). Degradation rates of 14C-pyrene and PAH compounds were found to be enhanced under soil gas oxygen concentrations between 2% and 21% in the contaminated soil. Between 45% and 55% of 14C-pyrene spiked onto the soil was mineralized after 70 days at soil gas oxygen levels between 2% and 21%. No statistically significant mineralization was found to occur at 0% oxygen concentrations. Mineralization of 14C-pyrene in contaminated soil poisoned with mercuric chloride was determined to be less than 0.5%. Degradation of indigenous nonradiolabeled PAH in non-poisoned soil was statistically significantly greater than in poisoned soil. These results indicated that the degradation of 14C-pyrene and PAH compounds was biological and would occur under low oxygen concentrations. For example, the use of soil aeration technology in order to achieve continued treatment for buried lifts of soil while new lifts are added will decrease the total time for soil remediation of the prepared-bed.

Persulfate oxidation of MTBE- and chloroform-spent granular activated carbon.

Activated persulfate (Na(2)S(2)O(8)) regeneration of methyl tert-butyl ether (MTBE) and chloroform-spent GAC was evaluated in this study. Thermal-activation of persulfate was effective and resulted in greater MTBE removal than either alkaline-activation or H(2)O(2)-persulfate binary mixtures. H(2)O(2) may serve multiple roles in oxidation mechanisms including Fenton-driven oxidation, and indirect activation of persulfate through thermal or ferrous iron activation mechanisms. More frequent, lower volume applications of persulfate solution (i.e., the persulfate loading rate), higher solid/solution ratio (g GAC mL(-1) solution), and higher persulfate concentration (mass loading) resulted in greater MTBE oxidation and removal. Chloroform oxidation was more effective in URV GAC compared to F400 GAC. This study provides baseline conditions that can be used to optimize pilot-scale persulfate-driven regeneration of contaminant-spent GAC.

Influence of peat on Fenton oxidation

A diagnostic probe was used to estimate the activity of Fenton-derived hydroxyl radicals (.OH), reaction kinetics, and oxidation efficiency in batch suspensions comprised of silica sand, crushed goethite (alpha-FeOOH) ore, peat, and H2O2 (0.13 mM). A simple method of kinetic analysis is presented and used to estimate the rate of .OH production (POH) and scavenging term (ks), which were used to establish the influence of organic matter (Pahokee peat) in Fenton systems. POH was greater in the peat-amended systems than in the unamended control, and ks was approximately the same. Any increase in scavenging of .OH that resulted from the addition of peat was insignificant in comparison to radical scavenging by reaction with H2O2. Also, treatment efficiency, defined as the ratio of probe conversion to H2O2 consumption over the same period was greater in the peat-amended system. Results suggest that .OH production is enhanced in the presence of peat by one or more peat-dependent mechanisms. Fe concentration and availability in the peat, reduction of Fe(III) to Fe(II) by the organic matter, and reduction of organic-complexed Fe(III) to Fe(II) are discussed in the context of the Fenton mechanism.

Fundamentals of ISCO Using Hydrogen Peroxide

Radicals known to play significant roles in hydrogen peroxide chemistry include the hydroxyl radical (OH ), superoxide radical (O2 ), and perhydroxyl radical (HO2 ). Different radicals dominate the reaction under different chemistry conditions, and are controlled by parameters such as concentration of the oxidant, catalyst, organic or inorganic solutes, and pH. This can affect performance as some contaminants may only degrade under specific chemistry conditions.

Fenton-like degradation of MTBE: Effects of iron counter anion and radical scavengers.

Fenton-driven oxidation of methyl tert-butyl ether (MTBE) (0.11-0.16mM) in batch reactors containing ferric iron (5mM) and hydrogen peroxide (H(2)O(2)) (6mM) (pH=3) was performed to investigate MTBE transformation mechanisms. Independent variables included the forms of iron (Fe) (Fe(2)(SO(4))(3).9H(2)O and Fe(NO(3))(3).9H(2)O), H(2)O(2) (6, 60mM), chloroform (CF) (0.2-2.4mM), isopropyl alcohol (IPA) (25, 50mM), and sulfate (7.5mM). MTBE, tert-butyl alcohol and acetone transformation were significantly greater when oxidation was carried out with Fe(NO(3))(3).9H(2)O than with Fe(2)(SO(4))(3).9H(2)O. Sulfate interfered in the formation of the ferro-peroxy intermediate species, inhibited H(2)O(2) reaction, hydroxyl radical (()OH) formation, and MTBE transformation. Transformation was faster and more complete at a higher [H(2)O(2)] (60mM), but resulted in lower oxidation efficiency which was attributed to ()OH scavenging by H(2)O(2). CF scavenging of the superoxide radical (()O(2)(-)) in the ferric nitrate system resulted in lower rates of ()O(2)(-) reduction of Fe(III) to Fe(II), ()OH production, and consequently lower rates of MTBE transformation. IPA, an excellent scavenger of ()OH, completely inhibited MTBE transformation in the ferric nitrate system indicating oxidation was predominantly by ()OH. ()OH scavenging by HSO(4)(-), formation of the sulfate radical (()SO(4)(-)), and oxidation of MTBE by ()SO(4)(-) was estimated to be negligible. The form of Fe (i.e., counter anion) selected for use in Fenton treatment systems impacts oxidative mechanisms, treatment efficiency, and post-oxidation treatment of residuals which may require additional handling and cost.

Comparative study on oxidative treatments of NAPL containing chlorinated ethanes and ethenes using hydrogen peroxide and persulfate in soils

The goal of this study was to assess the oxidation of NAPL in soil, 30% of which were composed of chlorinated ethanes and ethenes, using catalyzed hydrogen peroxide (CHP), activated persulfate (AP), and H(2)O(2)-persulfate (HP) co-amendment systems. Citrate, a buffer and iron ligand, was amended to the treatment system to enhance oxidative treatment. Four activation/catalysis methods were employed: (1) oxidant only, (2) oxidant-citrate, (3) oxidant-iron(II), and (4) oxidant-citrate-iron(II). The NAPL treatment effectiveness was the greatest in the CHP reactions, the second in HP, and the third in AP. The effective activation and catalysis methods depended on the oxidant types; oxidant only for CHP and HP and oxidant-citrate-iron for AP. The treatability trend of chlorinated ethanes and ethenes in the soil mixture was as follows: trichloroethene > tetrachloroethene > dichloroethane > trichloroethane > tetrachloroethane. A significant fraction of persulfate remained in the oxidation systems after the 2-day reaction period, especially in the citrate-iron(II) AP. In general, oxidation systems that included citrate maintained a post-treatment pH in the range of 7-9. A final pH of AP oxidation systems was acidic (pH 2-3), where a molar ratio of citrate-iron(II) was less than 1.8 and where no citrate was amended.

NDMA treatment by sequential GAC adsorption and fenton-driven destruction

N-nitrosodimethylamine (NDMA) is a highly toxic environmental contaminant that was first detected in groundwater tainted by rocket fuel manufacturing wastes. NDMA is also a by-product of certain industrial processes including the chlorination of treated water and wastewater. Water treatment by carbon adsorption is costly because NDMA partitions only sparingly to carbon and frequent carbon replacement or regeneration is required. If activated carbon could be regenerated cheaply and quickly in place, NDMA adsorption on carbon, an easily implemented technology, could become attractive. In this study, the feasibility of adsorbing NDMA onto carbon followed by in-place carbon regeneration using Fentons reagent was assessed. Batch and column tests indicated that the concentration of sorbed NDMA can be lowered to nondetectable levels in hours using reasonable hydrogen peroxide and iron concentrations. Three-log destruction of sorbed NDMA loaded to 1.04 mg NDMA/g carbon was achieved in approximately 12 h. Results...

Identification of persulfate oxidation products of polycyclic aromatic hydrocarbon during remediation of contaminated soil

The extent of PAH transformation, the formation and transformation of reaction byproducts during persulfate oxidation of polycyclic aromatic hydrocarbons (PAHs) in coking plant soil was investigated. Pre-oxidation analyses indicated that oxygen-containing PAHs (oxy-PAHs) existed in the soil. Oxy-PAHs including 1H-phenalen-1-one, 9H-fluoren-9-one, and 1,8-naphthalic anhydride were also produced during persulfate oxidation of PAHs. Concentration of 1,8-naphthalic anhydride at 4h in thermally activated (50°C) persulfate oxidation (TAPO) treatment increased 12.7 times relative to the oxidant-free control. Additionally, the oxy-PAHs originally present and those generated during oxidation can be oxidized by unactivated or thermally activated persulfate oxidation. For example, 9H-fluoren-9-one concentration decreased 99% at 4h in TAPO treatment relative to the control. Thermally activated persulfate resulted in greater oxy-PAHs removal than unactivated persulfate. Overall, both unactivated and thermally activated persulfate oxidation of PAH-contaminated soil reduced PAH mass, and oxidized most of the reaction byproducts. Consequently, this treatment process could limit environmental risk related to the parent compound and associated reaction byproducts.

In-situ regeneration of saturated granular activated carbon by an iron oxide nanocatalyst

Granular activated carbon (GAC) can remove trace organic pollutants and natural organic matter (NOM) from industrial and municipal waters. This paper evaluates an iron nanocatalyst approach, based on Fenton-like oxidation reactions, to regenerate spent GAC within a packed bed configuration after saturation by organic compounds. Specifically, we focus on regenerating GAC packed beds equilibrated with varying influent concentrations of phenol, a model organic compound. Iron nanocatalysts were synthesized using ferric chloride, a chemical already used as a coagulant at municipal WTPs, and reacted with hydrogen peroxide (H(2)O(2)) for the purpose of in-situ regeneration. Up to 95% of phenol adsorption capacity was regenerated for GAC equilibrated with 1000 mg/L of phenol. Using this technique, at least four adsorption-regeneration cycles can be performed sequentially for the same batch of GAC with fresh iron nanocatalysts while achieving a regeneration efficiency of 90 ± 5% between each loading. Moreover, the iron nanocatalyst can be recovered and reused multiple times. Lower initial adsorbate concentrations (10-500 mg/L) resulted in a slightly lower saturated adsorbent-phase concentration of phenol and lower regeneration efficiencies (72 ± 5%). Additionally, this catalytic in-situ regeneration was applied to GAC saturated by NOM. A slightly lower regeneration efficiency (60%) was observed for the Suwannee River NOM adsorption capacity of GAC. The next step is validation in a pilot-scale test that applies this regeneration technique to a GAC adsorber employed in NOM removal.