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N sodium thiosulfate (Kolthoff and Belcher, 1957). Solution pH was measured using with aFisher Accumet 900 pH meter.AnalysisExtracts containing anisole, nitrobenzene and 1, 3, 5-trinitrobenzene were analyzed on aHewlett-Packard 5890 gas chromatograph fitted with a 15 m x 0.53 mm (i.d.) SPB-5 capillarycolumn and a flame ionization detector (FID). The injector port and detector port temperaturesfor anisole and nitrobenzene were 200˚C and 250˚C, respectively. The initial oven temperaturewas 70˚C. The program rate was 20˚C min -1 , and the final temperature was 210˚C. Gaschromatographic conditions for the analysis of 1,3,5-trinitrobenzene included an initial oventemperature of 160˚C and a final temperature of 190˚C. The program rate was 10˚C min -1 , theinjector temperature was 200˚C, and the detector temperature was 250˚C. Extracts containingcarbon tetrachloride were analyzed on a Hewlett-Packard 5890A gas chromatograph fitted with a15 m x 0.53 mm (i.d.) Equity-5 capillary column and an electron capture detector (ECD). Theinjector port and detector port temperatures were 100˚C and 250˚C, respectively. A split flowwas used with the initial oven temperature at 50˚C; the program rate was 30˚C min -1 , and thefinal temperature was 170˚C.16
6.1.3. Base-Activated Persulfate Treatment of Contaminated Soils with pH Drift fromAlkaline to CircumneutralMaterialsSodium persulfate (>98%) and hexachloroethane (99%) were purchased from Sigma-Aldrich. Mixed hexanes, nitrobenzene (99%), sodium hydroxide, sodium bicarbonate, andsodium carbonate were obtained from J.T. Baker. Sodium thiosulfate (99%) and n-hexane werepurchased from Fisher Chemical. Potassium iodide (99%) was purchased from Alfa Aesar.Deionized water was purified to >18.0 MΩ•cm with a Barnstead Nanopure II deionizing system.SoilsTwo horizons of a surface soil, collected from an open slope near Kamiak Butte, WA,were used in base-activated persulfate reactions. The two horizons (KB1 and KB2) were chosenbecause of their varying soil organic carbon contents but similar mineralogy (Table 6.1.3.1). Thesoils were crushed using a soil grinder and sieved through a 1.65 mm sieve. Organic carboncontent was determined by the Walkley-Black method (Walkley and Black, 1934). Particle sizedistribution was analyzed using the pipette method (Gee and Bauder, 1986). The citratebicarbonate-dithioniteextraction method was used to determine amorphous and crystalline ironand manganese oxyhydroxides content (Jackson et al., 1986). Cation exchange capacity wasanalyzed by saturation with sodium acetate at pH 8.2 (U.S. Soil Conservation Service, 1972).Physical and chemical properties for the KB1 and KB2 soils are listed in Tables 6.1.3.1 and6.1.3.2.Soil organic matter (SOM) was removed from the two soils by addition of 20% hydrogenperoxide (H 2 O 2 ) (Robinson, 1927). Soil slurries received periodic additions of H 2 O 2 and wereheated to 60° C until a visible color change of dark to light in the soil occurred indicating that theSOM was removed. Soils were dried at 55° C, pulverized, and sieved with a 1.65 mm sieve.Probe CompoundsThe probe compounds were selected based on their relative reactivities with each of thereactive oxygen species. Nitrobenzene (NB) was used to detect hydroxyl radicals (k OH• = 3.9 ×10 9 M -1 s -1 ) but not sulfate radicals (k SO4• - ≤ 10 6 M -1 s -1 ) (Buxton et al., 1988; Neta et al., 1977).Hexachloroethane (HCA) was selected as a probe for superoxide and other reductants (k O2 .- =400 M -1 s -1 ) because it has negligible reactivity with oxidants; e.g., hydroxyl radicals arenonreactive with perchlorinated aliphatic compounds (k OH . ≤ 1 x 10 6 M -1 s -1 ) (Haag and Yao,1992; Afanas’ev, 1989).Experimental ProceduresVOA vials were prepared with 10 g of the KB1, KB2, KB1-No SOM, or KB2-No SOMsoils. Each vial received 18 mL of the sodium hydroxide:sodium persulfate solution; the vialswere mixed, and then incubated in a water bath at 25˚C (±2˚C).Once the pH in the reactors declined to 12, a series of vials received 2 mL of one of theconcentrated probe compounds (10 mM NB or 0.005 mM HCA) which yielded final solutionconcentrations of 1 mM NB or 0.0005 mM HCA, respectively. Probe degradation was thenmonitored by periodically extracting the entire vial contents with 5 mL of hexane and analyzing17
Page 1 and 2: FINAL REPORTEnhanced Reactant-Conta
Page 3 and 4: 2. FRONT MATTERTable of Contents1.
Page 5 and 6: 7.1.1. Persulfate Activation by Maj
Page 7 and 8: List of TablesTable 5.1. Second ord
Page 9 and 10: Figure 7.1.2.7. Degradation of the
Page 11 and 12: Base:persulfate ratio of 2:1; c) Ba
Page 13 and 14: nitrobenzene; 15 mL total volume. E
Page 15 and 16: Figure 7.2.7.5. CB degradation in b
Page 17 and 18: Figure 7.3.1.31. Persulfate concent
Page 19 and 20: List of AcronymsBETBTEXCBCECCHPCTDC
Page 21 and 22: KeywordsIn situ chemical oxidation,
Page 23 and 24: 4. OBJECTIVEThe goal of research co
Page 25 and 26: strong (E 0 = 2.1 V), water-soluble
Page 27 and 28: Persulfate also has the unique prop
Page 29 and 30: enzenes react with sulfate radicals
Page 31 and 32: tomography (XRCT) is a non-destruct
Page 33 and 34: The diffusion of a remedial agent t
Page 35 and 36: SoilsA surface soil and two fractio
Page 37: 6.1.2. Persulfate Activation by Sub
Page 41 and 42: 6.2. Persulfate Reactivity Under Di
Page 43 and 44: temperatures were 220˚C and 270˚C
Page 45 and 46: time point and were capped to minim
Page 47 and 48: form of hydroperoxide. Control reac
Page 49 and 50: 6.2.4. Persulfate Activation By Phe
Page 51 and 52: °C, detector temperature of 270 °
Page 53 and 54: Analytical ProceduresHexane extract
Page 55 and 56: Soil organic matter (SOM) was remov
Page 57 and 58: 6.2.8. Effect of Sorption on Contam
Page 59 and 60: 6.3. Effect of Persulfate on Subsur
Page 61 and 62: Table 6.3.2.2. Chemical properties
Page 63 and 64: Figure 6.3.2.1. Falling head permea
Page 65 and 66: StartPrepareilImage generationandre
Page 67 and 68: cure for 24 hr. The Palouse loess w
Page 69 and 70: 7. RESULTS AND ACCOMPLISHMENTS7.1.
Page 71 and 72: Table 7.1.1.1. Persulfate decomposi
Page 73 and 74: aControlPositive controlFerrihydrit
Page 75 and 76: aControlPositive controlFerrihydrit
Page 77 and 78: a1Nitrobenzene, C/C 00.80.60.40.20C
Page 79 and 80: a1Hexachloroethane, C/C 00.80.60.40
Page 81 and 82: Table 7.1.1.4. Persulfate decomposi
Page 83 and 84: Table 7.1.1.5. Nitrobenzene decompo
Page 85 and 86: Table 7.1.1.6. HCA decomposition ra
Page 87 and 88: aControlPositive control0.03 g Goet
Page 89 and 90:
7.1.2. Persulfate Activation by Sub
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a1b1Nitrobenzene remaining after 48
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a1Anisole (mM)0.80.60.40.2Unactivat
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aNitrobenzene (mM)10.80.60.40.20Una
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a1, 3, 5-Trinitrobenzene (mM)10.80.
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All of the mineral persulfate syste
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7.1.3. Base-Activated Persulfate Tr
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1412KB1KB2108pH64200 1 2 3 4 5 6Tim
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a0.5Persulfate Concentration (M)0.4
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aPersulfate Concentration (M)0.50.4
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pH Drift in Soil SlurriespH was mon
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a1412108pH6420pH 12pH 10pH 80 3 6 9
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a141210pH8642pH 12pH 10pH 800 1 2 3
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aNitrobenzene Concentration (C/C o)
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Superoxide Radical and Reductant Ge
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aHexachloroethane Concentration (C/
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7.1.4. Summary of Factors Controlli
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Figure 7.2.1.1. Persulfate decompos
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Figure 7.2.1.2. Degradation of the
Page 127 and 128:
adical and hydroxyl radical. A simi
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Detection of Reactive Oxygen Specie
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Figure 7.2.1.7. Degradation of the
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7.2.2. Effect of Basicity on Persul
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The mechanism of base-activated per
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Effect of Persulfate Concentration
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Relative rates of reactive oxygen s
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Relative rates of reductant generat
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ConclusionThe reactive species gene
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abFigure 7.2.3.1. a) First order de
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Figure 7.2.3.3. Effect of ionic str
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persulfate. Persulfate decomposes r
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Figure 7.2.3.6. Stoichiometry for t
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Figure 7.2.3.8. Effect of copper (I
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2 S 2 O 82-→ O 2 (7.2.3.9)To inve
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7.2.4. Persulfate Activation By Phe
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hexachloroethane, with pentachlorop
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1Anisole (C/C 0)0.80.60.4ControlPos
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a.Nitrobenzene (C/C o)10.80.60.4Con
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Mechanism of Persulfate ActivationT
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Degradation of pentachlorophenoxide
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Hydroxyl radical generation in the
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CompoundSuccinicAcidMolecularFormul
Page 173 and 174:
The generation of hydroxyl radicals
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Table 7.2.5.2. Isomers of the alcoh
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a. b.Control, w/o alcoholn-Pentanol
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The results of Figures 7.2.5.5 and
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Control, w/o aldehydeFormaldehydeAc
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a. b.11Nitrobenzene (C/C 0)0.80.60.
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Control (Deionized water)Positive C
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Page 189 and 190:
1Nitrobenzene (C/C o)0.80.60.40.2Co
Page 191 and 192:
1Nitrobenzene (C/C o)0.80.60.40.2Co
Page 193 and 194:
Page 195 and 196:
Page 197 and 198:
1Hexachloroethane (C/C o)0.80.60.40
Page 199 and 200:
1Hexachloroethane (C/C o)0.80.60.40
Page 201 and 202:
ConclusionThe results of this resea
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1PCE (C/C 0)0.80.60.40.2Control1:12
Page 205 and 206:
Aromatic ContaminantsThe degradatio
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ConclusionThe results of this resea
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Activated Persulfate Treatment of S
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Figure 7.2.8.4. CHP treatment of HC
Page 213 and 214:
Figure 7.2.8.6. Base-activated pers
Page 215 and 216:
7.2.9. Summary of Persulfate Activa
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hematite, and goethite. However, pH
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Figure 7.3.1.2. XRD spectra for goe
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Figure 7.3.1.4. XRD spectra for goe
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Figure 7.3.1.6. XRD spectra for hem
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Figure 7.3.1.8. XRD spectra for hem
Page 227 and 228:
Figure 7.3.1.10. XRD spectra for fe
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Figure 7.3.1.12. XRD spectra for fe
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Figure 7.3.1.14. XRD spectra for bi
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Figure 7.3.1.16. XRD spectra for bi
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Figure 7.3.1.18. XRD spectra for ka
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Figure 7.3.1.20. XRD spectra for ka
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Figure 7.3.1.22. XRD spectra for mo
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Figure 7.3.1.24. XRD spectra for mo
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1Persulfate (C/C 0)0.80.60.40.2Unac
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Page 247 and 248:
Page 249 and 250:
141210pH86Unactivated persulfateIro
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Page 253 and 254:
Page 255 and 256:
Page 257 and 258:
7.3.2. Effect of Persulfate Formula
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Persulfate AlonePersulfate + Iron (
Page 261 and 262:
Persulfate AlonePersulfate + Iron (
Page 263 and 264:
with deionized water was 0.16. Thes
Page 265 and 266:
hydraulic conductivity. These chang
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7.4. Transport of Persulfate into L
Page 269 and 270:
0.1 M Persulfate Diffusion in Palou
Page 271 and 272:
Persulfate concentration (M)0 0.2 0
Page 273 and 274:
However, the concentration of base-
Page 275 and 276:
Numerous phenoxides, including chlo
Page 277 and 278:
9. LITERATURE CITEDAfanas’ev, A.M
Page 279 and 280:
Crooks, V.E., Quigley, R.M. 1984. S
Page 281 and 282:
Huang, K.C., Zhao, Z., Hoag, G.E.,
Page 283 and 284:
Lunenok-Burmakina, V.A., Aleeva, G.
Page 285 and 286:
Peyton, G.P. 1993. The free-radical
Page 287 and 288:
Todres, Z.V. 2003. Organic ion radi
Page 289 and 290:
10. APPENDICESList of Technical Pub
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