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Chapter 2 1 Persistence of Persulfate in Uncontaminated Aquifer Materials Overview Batch and stop-flow column experiments were performed to estimate persulfate decomposition kinetic parameters in the presence of seven well-characterized aquifer materials. Push-pull tests were conducted in a sandy aquifer to represent persulfate decomposition under in situ conditions. The decomposition of persulfate followed a first- order rate law for all aquifer materials investigated. Reaction rate coefficients (kobs) increased by an order of magnitude when persulfate concentration was reduced from 20 g/L to 1 g/L, due to ionic strength effects. The column experiments yielded higher kobs than batch experiments due to the lower oxidant to solids mass ratio. The kinetic model developed from the batch test data was able to reproduce the observed persulfate temporal profiles from the push-pull tests. The estimated kobs indicate that unactivated persulfate is a persistent oxidant for the range of aquifer materials explored with half-lives ranging from 2 to 600 days. 1 Reproduced in part with permission from Sra, K.S., Thomson, N.R., Barker, J.F., 2010. Persistence of persulfate in uncontaminated aquifer materials. Environmental Science and Technology, 44 (8), 3098-3104. Copyright 2010 American Chemical Society. 11
Page 1: Persulfate Persistence and Treatabi
Page 5 and 6: Abstract Petroleum hydrocarbons (PH
Page 7 and 8: observed at 1 g/L as compared to 20
Page 9 and 10: Acknowledgements God, as some cynic
Page 11: simply conceded to, acknowledging t
Page 14 and 15: 3.3.1 Methods…………………
Page 17 and 18: List of Figures Figure 2.1. Persulf
Page 19: and (b) naphthalene……………
Page 23 and 24: Chapter 1 Introduction 1.1. GENERAL
Page 25 and 26: subsurface zones to minimize the or
Page 27 and 28: 2004; Dahmani et. al, 2006). Brown
Page 29 and 30: to activated persulfate utilization
Page 31: is presented here without change. C
Page 35 and 36: In the presence of aquifer material
Page 37 and 38: materials
Page 39 and 40: flow column experiments is that the
Page 41 and 42: Data from the control reactors indi
Page 43 and 44: Since the buffering capacity of car
Page 45 and 46: with 23 (2.6) where kcat is the min
Page 47 and 48: catalyzed reaction in the systems f
Page 49 and 50: COD test results illustrated loss o
Page 51 and 52: g/mL vs. 3.9±0.4 g/mL). This will
Page 53 and 54: flow mode of column operation was u
Page 55 and 56: Pilot-scale data are representative
Page 57 and 58: Ionic Strength (M) 0.5 0.4 0.3 0.2
Page 59 and 60: C/C o 0 0 10 20 30 40 50 Figure 2.6
Page 61: 39 Table 2.1. Selective chemical pr
Page 64 and 65: activation trials, lower stability
Page 66 and 67: solvents) (Anipsitakis and Dionysio
Page 68 and 69: catalyst drainage from the aqueous
Page 70 and 71: 2− − − 2− −• −• S2
Page 72 and 73: lined plastic cap and manually shak
Page 74 and 75: 3.4. RESULTS AND DISCUSSION 3.4.1.
Page 76 and 77: eaction with Fe(II) (Figure 3.1). C
Page 78 and 79: At a molar ratio of 10 for the 1 g/
Page 80 and 81: that persulfate degradation was inf
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persulfate treatability studies to
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C TOS /C o C TOS /C o C TOS /C o 10
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pH pH pH 14 12 10 8 6 4 2 0 14 12 1
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Table 3.2. Summary of activated per
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Chapter 4 Persulfate Oxidation of G
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minimize disturbance to above groun
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emediation of gasoline contaminated
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materials, ~29 g of the selected so
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Residual oxidant analysis was perfo
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The overall mass action law for oxi
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−• SO 4 and OH ● ). The kobs
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chelating agent (citric acid) and t
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indicates that at an extremely high
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extension, both the F1 fraction and
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natural activation and unactivated
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C/C o C/C o C/C o 1.2 1 0.8 0.6 0.4
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Table 4.1. Summary of experimental
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Chapter 5 In Situ Gasoline Source Z
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effectiveness in the treatment of t
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from 2.25 to 4.5 m. The injection w
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controller and connected to the tan
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To capture changes in the mass load
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Inorganic analysis consisted of per
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converted to SO . The estimate for
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inorganic species were flushed from
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observed for all MGCs. The mass loa
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end of the idealized injection slug
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monitoring fence-line was primarily
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Figure 5.2. Image of the persulfate
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Persulfate (mg/L) 2- SO4 (mg/L) Na
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M (g/day) ● M/M o ● ● 30 20 1
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Cumulative Mass (g) Cumulative Mass
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Chapter 6 Closure 6.1. CONCLUSIONS
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persulfate kinetic behavior. It hig
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persulfate implying that substantia
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conditions than bench-scale studies
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References CHAPTER 1 Appelo, C.A.J.
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Lundegard, P.D., Johnson, P.C., 200
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CHAPTER 2 Balazs, G.B., Cooper, J.F
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Langmuir, D., 1997. Aqueous Environ
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Kolthoff, I.M., Medalia, A.I., Raae
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CHAPTER 4 Agency for Toxic Substanc
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Lundegard, P.D., Johnson, P.C., 200
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CHAPTER 5 Agency for Toxic Substanc
Page 171:
Sudicky, E.A., 1986. A natural grad
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