Final Report - Strategic Environmental Research and Development ...

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This report was prepared under contract to the Department of Defense StrategicEnvironmental Research and Development Program (SERDP). The publication of thisreport does not indicate endorsement by the Department of Defense, nor should thecontents be construed as reflecting the official policy or position of the Department ofDefense. Reference herein to any specific commercial product, process, or service bytrade name, trademark, manufacturer, or otherwise, does not necessarily constitute orimply its endorsement, recommendation, or favoring by the Department of Defense.
2. FRONT MATTERTable of Contents1. COVER PAGE .............................................................................................................................. i2. FRONT MATTER ........................................................................................................................ iiTable of Contents ...................................................................................................................... iiList of Tables ............................................................................................................................ viList of Figures .......................................................................................................................... viiList of Acronyms .................................................................................................................. xviiiKeywords ................................................................................................................................. xxAcknowledgements ................................................................................................................. xx3. ABSTRACT .................................................................................................................................. 04. OBJECTIVE ................................................................................................................................. 15. BACKGROUND ............................................................................................................................ 26. MATERIALS AND METHODS ..................................................................................................... 126.1. Factors Controlling the Decomposition of Persulfate in the Subsurface ................... 12ii
Page 1: FINAL REPORTEnhanced Reactant-Conta
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 and 38: 6.1.2. Persulfate Activation by Sub
Page 39 and 40: 6.1.3. Base-Activated Persulfate Tr
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
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Soil organic matter (SOM) was remov
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6.2.8. Effect of Sorption on Contam
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6.3. Effect of Persulfate on Subsur
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Table 6.3.2.2. Chemical properties
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Figure 6.3.2.1. Falling head permea
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StartPrepareilImage generationandre
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cure for 24 hr. The Palouse loess w
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7. RESULTS AND ACCOMPLISHMENTS7.1.
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Table 7.1.1.1. Persulfate decomposi
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aControlPositive controlFerrihydrit
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aControlPositive controlFerrihydrit
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a1Nitrobenzene, C/C 00.80.60.40.20C
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a1Hexachloroethane, C/C 00.80.60.40
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Table 7.1.1.4. Persulfate decomposi
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Table 7.1.1.5. Nitrobenzene decompo
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Table 7.1.1.6. HCA decomposition ra
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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
Page 133 and 134:
7.2.2. Effect of Basicity on Persul
Page 135 and 136:
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
Page 151 and 152:
Figure 7.2.3.6. Stoichiometry for t
Page 153 and 154:
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
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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
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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
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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
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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
Page 219 and 220:
Figure 7.3.1.2. XRD spectra for goe
Page 221 and 222:
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
Page 231 and 232:
Figure 7.3.1.14. XRD spectra for bi
Page 233 and 234:
Figure 7.3.1.16. XRD spectra for bi
Page 235 and 236:
Figure 7.3.1.18. XRD spectra for ka
Page 237 and 238:
Figure 7.3.1.20. XRD spectra for ka
Page 239 and 240:
Figure 7.3.1.22. XRD spectra for mo
Page 241 and 242:
Figure 7.3.1.24. XRD spectra for mo
Page 243 and 244:
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 (
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Persulfate AlonePersulfate + Iron (
Page 263 and 264:
with deionized water was 0.16. Thes
Page 265 and 266:
hydraulic conductivity. These chang
Page 267 and 268:
7.4. Transport of Persulfate into L
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0.1 M Persulfate Diffusion in Palou
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Persulfate concentration (M)0 0.2 0
Page 273 and 274:
However, the concentration of base-
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Numerous phenoxides, including chlo
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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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