FMC Environmental Solutions

Peroxygen Talk
October 2010
Activated Persulfate Chemistry: Combined Oxidation and Reduction Mechanisms
Klozur activated persulfate is a very robust technology that is capable of destroying a wide range of
organic contaminants and is equally effective on highly reduced contaminants such as BTEX and
polyaromatic hydrocarbons and highly oxidized species such as 1,1,1-TCA, carbon tetrachloride,
methylene chloride and chloroform. Such versatility demonstrates a very rich and robust chemistry for
persulfate in which well-known oxidative pathways and recently elucidated reductive mechanisms both
play important roles. This edition of Peroxygen Talk explores the dual nature of activated persulfate
systems, which can act as a strong, reactive oxidant and be a source of unique, reductive species. In
addition, combinations of zero valent iron (ZVI) and persulfate will be explored in term of providing
oxidizing and reducing conditions to a chlorinated solvent site.
Persulfate Oxidation Chemistry
The persulfate anion is a strong oxidant, with an oxidation potential of 2.12 V:
S2O8-2 + 2 H+ + 2 e- 2 HSO4However, the persulfate anion typically has slow oxidative kinetics at ordinary temperatures for most
contaminant species and really can only be applied to a limited number of contaminants, such as TCE or
xylene, to be effective. As a result, persulfate is typically activated 1-3 for use to oxidize most
contaminants or concern. In the presence of certain activators, persulfate anion can be converted to
the sulfate radical, an even stronger oxidant with an oxidation potential of 2.6 V:
S2O8-2 + activator SO4- + (SO4- or SO4-2)
Under acidic conditions, persulfate anion can hydrolyze to form hydrogen peroxide:
S2O8-2 + 2 H2O H2O2 + 2 HSO4Hydrogen peroxide itself has an oxidation potential of 1.77 V, and in the presence of various activators,
can for the hydroxyl radical, with a potential of 2.8 V, making it the strongest oxidant available for
remediation applications. In addition, sulfate radicals can react with water also to form hydroxyl
radicals. Under stronger acidic conditions, persulfate can form peroxymonopersulfate anions, with an
oxidation potential of 1.44V
S2O8-2 + H2O HSO5- + HSO4As a result, persulfate solutions may contain several different oxidant and radical species. One
consequence of this mixture of oxidizing species is that multiple pathways for contaminant oxidation
may exist, increasing the probability of reducing the target compound concentrations. However, such
diversity of oxidant species makes the assessment of the stoichiometric amount of persulfate needed
to destroy a given concentration of contaminant problematic, and thus it is common practice to revert
back to the basic, two electron transfer associated with the persulfate anion (seen in first equation
above) to determine the stoichiometric persulfate demand.

Formation of Superoxide: Reduction Chemistry Via Persulfate

In addition to reactive oxidizing species, it has recently been shown that persulfate can also generate the
reductive specie, super oxide (O2-), under certain activation conditions. Watts, et al4 demonstrated that
under alkaline activation conditions through the addition of OH- , persulfate generates both sulfate
radicals and superoxide by the following combined reaction:
2 S2O8-2 + 2 H2O 3SO4-2 + SO4- + O2- + 4 H+
Watts explains this reaction as proceeding through an intermediate reaction between hydroperoxide
(HOO-) and persulfate anion. Furthermore, under these highly alkaline conditions, sulfate radical can
react with hydroxide to form hydroxyl radicals
SO4- + OH- SO4-2 + OH
In this paper, Watts then demonstrates that the alkaline activated persulfate system can degrade
contaminants such as hexachloroethane (HCA), a highly oxidized species which is used as a probe for
reactions with superoxide. Alkaline activated persulfate has also been shown to react effectively with
carbon tetrachloride5, which contains fully oxidized carbon thought to only degrade through reductive
pathways.
Watts also recently6 proposed that hydrogen peroxide- activated persulfate can lead to the generation
of superoxide radicals as well. This is mediated via the generation of hydroperoxide by iron - activated
hydrogen peroxide, and then as in the high pH activation scenario, the hydroperoxide reacts with
persulfate anion to form sulfate radical and superoxide species. Evidence of this has been observed
with the activated persulfate destruction of carbon tetrachloride5. Watts, et al, also demonstrated the
formation of superoxide in mineral-activated persulfate systems7, particularly in systems containing
goethite (FeOOH).
The following table lists the potential reactive species potentially present in activated persulfate
systems.
Potential Reactive Species in an Activated Persulfate System
Species
Potential (V)
-2
Persulfate anion
S2O8
+2.1
Sulfate radical
SO4+2.6
Hydrogen peroxide
H2O2
+1.8
Hydroxyl radical
OH
+2.8
Monopersulfate
HSO5
+1.4
HOOHydroperoxide
O2-
Superoxide
-0.2

Combinations of Persulfate and Zero Valent Iron (ZVI)

Zero valent iron is a reductive technology that has been used over the years to treat chlorinated solvent
contaminated sites. Recently, it has been demonstrated that persulfate can be activated using zero
valent iron (ZVI), a well recognized reducing agent for chlorinated solvents8-13, making for a combined
oxidant reductant remediation tool. While the use of hydrogen peroxide or permanganate with ZVI is
detrimental to both the oxidant and the ZVI9, ZVI persulfate combinations have been shown to be
effective on TCA8,9, carbon tetrachloride8,9, TCE8,10, 12 and dinitrotoluene13. It has been suggested11 that
the mechanism of persulfate activation is by a two step process, whereas the ZVI is the source of
divalent iron, which can be used to generate sulfate radicals from persulfate.
Fe0 + O2 + H2O 2 Fe+2 + 4 OHS2O8-2 + Fe+2 Fe+3 + SO4- + SO4-2
Of course, persulfate can react directly with the ZVI to form divalent iron and sulfate, a non-productive
reaction. However, unlike permanganate and hydrogen peroxide, sulfate radical production appears to
be significant as compared to the non-productive rusting of the ZVI or decomposition of persulfate.9 As
a result, ZVI persulfate combinations can provide a source of both oxidative and reductive destruction
of chlorinated contaminants.
Application of ZVI and persulfate combinations has been demonstrated at the field scale.14, 15 In both of
these cases, ZVI, persulfate and hydrogen peroxide were applied to sites contaminated with BTEX and
naphthalene, resulting in significant reductions of the contaminants. Application of persulfate and ZVI
can occur through co-injection (sequentially or simultaneously). But it can also be imagined that a
permeable reactive barrier (PRB) be emplaced with the ZVI, then the persulfate injected up-gradient of
the barrier and allowed to flow through the ZVI in concert with the contaminants, activating as it passes
through the PRB.
Conclusion
Activated persulfate provides a unique technology that can provide both oxidative and reductive
processes to treat a wide range of contaminants that can be applied to soils and groundwater. As a
result, persulfate is effective in destroying a wide range of organic contaminants and can address mixed
contaminant plumes of petroleum products and chlorinated solvents. Persulfate can also be combined
with zero valent iron, not only to provide activation for the persulfate, but as a source of combined
oxidative and reductive chemistries.
1. Peroxygen Talk #1, Choosing the Right Activator for Klozur Persulfate, January, 2006.
2. Block, P.A., R.A. Brown and D. Robinson. Novel Activation Technologies for Sodium Persulfate
In Situ Chemical Oxidiation, 4th International Conference on the Remediation of Chlorinated
and Recalcitrant Compounds, Monterey, CA, 2004.
3. Klozur Technical Bulletin #1 Activator Selection Guide (see Klozur Resource Center,
www.klozur.com)
4. Furman, O., A. Teel, and R.J. Watts. Mechanism of Base Activation of Persulfate. Environ . Sci.
Technol. 44, p 6423 6428, 2010.

5. Root, D.R. and P.A. Block. Investigation of Chlorinated Methanes Treatability Using Activated
Sodium Persulfate, First International Conference On Environmental Science and Technology,
2005.
6. R.J. Watts presentations at the 2nd Southeastern In Situ Soil and Groundwater Remediation
Conference (2010, Raleigh, NC) and on the 2010 FMC Environmental Webinar Series
7. Ahmad, M., A.L. Teel and R.J. Watts. Persulfate activation by subsurface minerals. J.
Contaminant Hydrology 115, p 34 45, 2010.
8. FMC Patent: US 7,785,038
9. Brown, R.A., D. Robinson and P.A. Block. Simultaneous Reduction and Oxidation: Combining
Sodium Persulfate and Zero Valent Iron. 3rd Oxidative Reductive Technology (ORT)
Conference, 2004.
10. Padmanabhan, A.R. Novel Simulataneous Reduction / Oxidation Process for Destroying Organic
Solvents. Masters Thesis: Worcester Polytechnic Institute, 2008.
11. Liang, C. and M.C. Lai. Trichloroethylene Degradation by Zero Valent Iron Activated Persulfate
Oxidation, Env. Eng. Sci. 25, p 1071 1077, 2008.
12. Oh, S.Y., H.W. Kim, J.M. Park, H.S. Park and C. Yoon. oxidation of polyvinyl alcohol by
persulfate activated with heat, Fe (II) and zero valent iron. J. Haz Mat 168, p 346 351, 2009.
13. Oh, S.Y., S.G. Kang and P.C. Chiu. Degradation of 2,4-dinitrololuene by persulfate activated with
zero valent iron. Science of the Total Environment 408, p 3464 3468, 2010.
14. Scalzi, M. Synergistic Treatment of BTEX Compounds Using Oxidation and Free Radical
Chemistries. Battelle Bioremediation Conference, Baltimore, 2009.
15. Scalzi, M. Implementation and Evaluation of an Innovative Treatment of Xylenes and
Naphthalene Using Oxidation and Biological Mechanisms. Battelle Bioremediation Conference,
Baltimore, 2009.