Ascorbate-induced oxidation of formate by peroxodisulfate: product yields, kinetics and mechanism

Curtin, Maria; Taub, Irwin A.; Kustin, Kenneth; Sao, Narith; Duvall, Jeremy R.; Davies, Katharine I.; Doona, Christopher J.; Ross, Ernest

doi:10.1163/1568567041570384

Cited by 11 publications

(14 citation statements)

References 16 publications

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“…The oxidation power of persulphate is strongest when the production of sulphate free radicals (SO 4 •− ) with a standard redox potential of 2.6 V is activated by Fe 2+ [25,26], temperatures higher than 40 • C [26,27], reductants such as ascorbate [28] or ␥-irradiation [29]. Furthermore, electrolytic and photolytic generation of SO 4 •− from sulphates has been utilised in wastewater purification processes [26,[30][31][32] but not in soil remediation.…”

Section: Introductionmentioning

confidence: 99%

Integration of electrokinetics and chemical oxidation for the remediation of creosote-contaminated clay

Isosaari

Piskonen

Ojala

et al. 2007

Journal of Hazardous Materials

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Section: Introductionmentioning

confidence: 99%

Integration of electrokinetics and chemical oxidation for the remediation of creosote-contaminated clay

Isosaari

Piskonen

Ojala

et al. 2007

Journal of Hazardous Materials

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“…Ascorbic acid reacts with persulfate to initiate the production of the sulfate radical ion (·SO 4 – ) (Curtin et al 2004). Consequently, the oxidation of ascorbic acid can either occur by direct reaction with S 2 O 8 2– or by ·SO 4 – (rxns 5 to 8, Table 1).…”

Section: Discussionmentioning

confidence: 99%

“…The p K a values associated with these ascorbate species are AH 2 , p K a1 = 4.10; AH – , p K a2 = 11.79 (Lide 1993). The direct reaction between persulfate and ascorbic acid is relatively limited ( k 5 = 0.35 and k 6 = 0.02/M s) compared to oxidation of ascorbic acid by ·SO 4 – ( k 7 = 1 × 10 9 and k 8 = 1 × 10 8 /M s) (Curtin et al 2004). However, given the reaction rate equation (dAH 2 /d t = k 6 [S 2 O 8 2– ] [AH 2 ]) representative of the conditions in this experiment (pH < 4.1; [S 2 O 8 2– ] = 10.5 mmol/L, [AH 2 ] = 42 mmol/L), the initial rate of persulfate reaction was estimated to be high (30.2 mmol/h) and could account for significant consumption of persulfate.…”

Section: Discussionmentioning

confidence: 99%

“…The pK a values associated with these ascorbate species are AH 2 , pK a1 = 4.10; AH − , pK a2 = 11.79 (Lide 1993). The direct reaction between persulfate and ascorbic acid is relatively limited (k 5 = 0.35 and k 6 = 0.02/M s) compared to oxidation of ascorbic acid by ·SO 4 − (k 7 = 1 × 10 9 and k 8 = 1 × 10 8 /M s) (Curtin et al 2004). headspace analysis after 2 to 14 d storage (4 °C) indicated no loss of the initial persulfate concentration (2.5 g/L).…”

Section: Ascorbic Acidmentioning

confidence: 99%

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Groundwater Sampling at ISCO Sites: Binary Mixtures of Volatile Organic Compounds and Persulfate

Huling

Ko²,

Pivetz

2011

Groundwater Monitoring Rem

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In situ chemical oxidation involves the introduction of a chemical oxidant into the subsurface for the purpose of transforming groundwater contaminants into harmless by‐products. Owing to oxidant persistence, groundwater samples collected at hazardous waste sites may contain both the contaminant(s) and the oxidant in a “binary mixture.” Binary mixtures composed of sodium persulfate (2.5 g/L; 10.5 mM) and volatile organic compounds (VOCs) (benzene, toluene, m‐xylene, perchloroethylene, trichloroethylene) were analyzed to assess the impact on the quality of the sample. A significant decline (49 to 100%) in VOC concentrations was measured in binary mixtures using gas chromatography (GC) purge and trap, and GC mass spectroscopy headspace methods. Preservation of the binary mixture samples was achieved through the addition of ascorbic acid (99 to 100% VOC average recovery). High concentrations of ascorbic acid (42 to 420 mM) did not interfere in the measurement of the VOCs and did not negatively impact the analytical instruments. High concentrations of ascorbic acid favored the reaction between persulfate and ascorbic acid while limiting the reaction between persulfate and VOCs. If an oxidant is detected and the binary sample is not appropriately preserved, the quality of the sample is likely to be compromised.

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“…The PCS has also been adapted to operate with less stringent conditions to ensure Food Safety by inactivating the vegetative pathogens Listeria monocytogenes and Escherichia coli on fresh produce, such as whole tomatoes, and to extend the shelf-life of fresh-cut produce, for example, by inactivating the polyphenoloxidase browning enzyme in sliced apples 6,15 . To generate chlorine dioxide, the PCS uses novel effector chemistry that proceeds via oxidation-reduction reactions at near-neutral pH, thus eliminating the use of acids and the inherent difficulties of shipping, storing, handling, and disposing acidic wastes in far-forward military deployments 1,2,4,17 . In addition to the military, the PCS can also be used by Homeland Security/Defense; during natural disasters (Superstorm Sandy, tsunamis, hurricane Katrina) that incapacitate access to power, potable water, and waste removal; on-site by emergency first-responders; and in community hospitals or schools during power outages (blackouts and brown-outs).…”

Section: Introductionmentioning

confidence: 99%

The Portable Chemical Sterilizer (PCS), D-FENS, and D-FEND ALL: Novel Chlorine Dioxide Decontamination Technologies for the Military

Doona

Feeherry

Setlow

et al. 2014

JoVE

Self Cite

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There is a stated Army need for a field-portable, non-steam sterilizer technology that can be used by Forward Surgical Teams, Dental Companies, Veterinary Service Support Detachments, Combat Support Hospitals, and Area Medical Laboratories to sterilize surgical instruments and to sterilize pathological specimens prior to disposal in operating rooms, emergency treatment areas, and intensive care units. The following ensemble of novel, 'clean and green' chlorine dioxide technologies are versatile and flexible to adapt to meet a number of critical military needs for decontamination 6,15 . Specifically, the Portable Chemical Sterilizer (PCS) was invented to meet urgent battlefield needs and close critical capability gaps for energy-independence, lightweight portability, rapid mobility, and rugged durability in high intensity forward deployments 3 . As a revolutionary technological breakthrough in surgical sterilization technology, the PCS is a Modern Field Autoclave that relies on on-site, point-ofuse, at-will generation of chlorine dioxide instead of steam. Two (2) PCS units sterilize 4 surgical trays in 1 hr, which is the equivalent throughput of one large steam autoclave (nicknamed "Bertha" in deployments because of its cumbersome size, bulky dimensions, and weight). However, the PCS operates using 100% less electricity (0 vs. 9 kW) and 98% less water (10 vs. 640 oz.), significantly reduces weight by 95% (20 vs. 450 lbs, a 4-man lift) and cube by 96% (2.1 vs. 60.2 ft 3 ), and virtually eliminates the difficult challenges in forward deployments of repairs and maintaining reliable operation, lifting and transporting, and electrical power required for steam autoclaves. Video LinkThe video component of this article can be found at

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Ascorbate-induced oxidation of formate by peroxodisulfate: product yields, kinetics and mechanism

Cited by 11 publications

References 16 publications

Integration of electrokinetics and chemical oxidation for the remediation of creosote-contaminated clay

Integration of electrokinetics and chemical oxidation for the remediation of creosote-contaminated clay

Groundwater Sampling at ISCO Sites: Binary Mixtures of Volatile Organic Compounds and Persulfate

The Portable Chemical Sterilizer (PCS), D-FENS, and D-FEND ALL: Novel Chlorine Dioxide Decontamination Technologies for the Military

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