title: Stabilization and prolonged reactivity of aqueous-phase ozone with cyclodextrin.
abstract: Recalcitrant organic groundwater contaminants, such as 1,4-dioxane, may require strong oxidants for complete mineralization. However, their efficacy for in-situ chemical oxidation (ISCO) is limited by oxidant decay and reactivity. Hydroxypropyl-β-cyclodextrin (HPβCD) was examined for its ability to stabilize aqueous-phase ozone (O3) and prolong oxidation potential through inclusion complex formation. Partial transformation of HPβCD by O3was observed. However, HPβCD proved to be sufficiently recalcitrant, because it was only partially degraded in the presence of O3. The formation of a HPβCD:O3clathrate complex was observed, which stabilized decay of O3. The presence of HPβCD increased the O3half-life linearly with increasing HPβCD:O3molar ratio. The O3half-life in solutions increased by as much as 40-fold relative to HPβCD-free O3solutions. Observed O3release from HPβCD and indigo oxidation confirmed that the formation of the inclusion complex is reversible. This proof-of-concept study demonstrates that HPβCD can complex O3while preserving its reactivity. These results suggest that the use of clathrate stabilizers, such as HPβCD, can support the development of a facilitated-transport enabled ISCO for the O3treatment of groundwater contaminated with recalcitrant compounds.
authors.affiliation: New Mexico State University, MSC 3Q, P.O. Box 30003, Las Cruces, NM 88003, USA.
authors.forename: Adam
authors.initials: A
authors.lastname: Dettmer
authors.affiliation: Enchem Engineering, Inc., 151 California Street, Newton, MA 02458, USA.
authors.forename: Raymond
authors.initials: R
authors.lastname: Ball
authors.affiliation: University of Rhode Island, Kingston, RI 02881, USA.
authors.forename: Thomas B
authors.initials: TB
authors.lastname: Boving
authors.affiliation: New Mexico State University, MSC 3Q, P.O. Box 30003, Las Cruces, NM 88003, USA.
authors.forename: Naima A
authors.initials: NA
authors.lastname: Khan
authors.affiliation: New Mexico State University, MSC 3Q, P.O. Box 30003, Las Cruces, NM 88003, USA.
authors.forename: Tanner
authors.initials: T
authors.lastname: Schaub
authors.affiliation: New Mexico State University, MSC 3Q, P.O. Box 30003, Las Cruces, NM 88003, USA.
authors.forename: Nilusha
authors.initials: N
authors.lastname: Sudasinghe
authors.affiliation: Pacific Northwest National Laboratory, Richland, WA 99354, USA.
authors.forename: Carlos A
authors.initials: CA
authors.lastname: Fernandez
authors.affiliation: New Mexico State University, MSC 3Q, P.O. Box 30003, Las Cruces, NM 88003, USA. Electronic address: kccarr@nmsu.edu.
authors.forename: Kenneth C
authors.initials: KC
authors.lastname: Carroll
mesh_terms: D000073738:2-Hydroxypropyl-beta-cyclodextrin; D004146:Dioxanes / Q000032:analysis* / Q000737:chemistry; D052918:Environmental Restoration and Remediation; D060587:Groundwater / Q000737:chemistry*; D006207:Half-Life; D008962:Models, Theoretical; D010084:Oxidation-Reduction; D010126:Ozone / Q000032:analysis / Q000737:chemistry*; D012996:Solutions; D021241:Spectrometry, Mass, Electrospray Ionization; D017550:Spectroscopy, Fourier Transform Infrared; D014874:Water Pollutants, Chemical / Q000032:analysis* / Q000737:chemistry; D047392:beta-Cyclodextrins / Q000032:analysis / Q000737:chemistry*
chemical_list: D004146:Dioxanes; D012996:Solutions; D014874:Water Pollutants, Chemical; D047392:beta-Cyclodextrins; D000073738:2-Hydroxypropyl-beta-cyclodextrin; D010126:Ozone; C025223:1,4-dioxane
keywords: Advanced oxidation; Cyclodextrin; Groundwater remediation, clathrate; ISCO; In-situ chemical oxidation; Ozone