Peroxygen Talk

Measurement of Persulfate in Solution

The determination of persulfate concentration in groundwater post in situ application is critical in
determining parameters such as the persulfate radius of influence (ROI) achieved and the residence time of the
persulfate in the contaminated zone. In general, measurement of persulfate concentration in the field is
problematic. Metals, either native to the soil or added for persulfate activation, may interfere with various persulfate
analytical methods, yielding variable, inaccurate or misleading results. In addition, some methods, which may be
suitable for the laboratory, may not be suitable for field application due to the need of sensitive or expensive
detection equipment. In this edition of Peroxygen Talk, the measurement of persulfate in ground water is explored.
A more detailed review, including comparisons between various persulfate analytical methods, can be found in
Reference 1.

Analytical Methods Involving Persulfate – Iron Reactions

Persulfate anion will oxidize divalent iron [Fe(II) ] to form trivalent iron [ Fe(III) ] in the reaction:

S2O8-2 + 2 Fe+2  2 Fe+3 + 2 SO4-2 Equation 1

Quantitative determination of persulfate concentration can be achieved by first adding in excess a known amount of
Fe (II) to the persulfate solution. A portion of the Fe(II) is then converted to Fe(III) via Equation 1. The remaining
Fe (II) is then titrated with either a known concentration of potassium permanganate [ KMnO 4 ]to a pink end-point or
ceric sulfate [ Ce(SO4)2 ] to a Ferroin indicator end-point (a color change from orange to clear or light blue). As an
example, for permanganate:

MnO4- + 5 Fe+2 + 8 H+  Mn+2 + 5 Fe+3 + 4 H2O Equation 2

Using the volume of permanganate or ceric sulfate needed to reach the endpoint (which occurs when all of the
remaining Fe (II) is oxidized), allows for the determination of how much persulfate was originally present :

Fe (II) reacted with persulfate = Fe (II) total – Fe (II) reacted with permanganate Equation 3

then:

Moles of persulfate = moles of Fe (II) reacted with persulfate / 2 Equation 4

As this method is dependent upon a known quantity of Fe (II) in the test solution, naturally occurring iron
and other reduced metals and residual contaminant that may react with the permanganate or cerric sulfate, in the
groundwater can significantly impact the quantification of the persulfate concentration. Also, additives such as
chelates, as when using chelated metal activation for persulfate, may cause interference with the titration. For
example, Fe(III)-EDTA will interfere with the permanganate titration, but not so with the ceric sulfate titration.
Addition of other oxidants, such as hydrogen peroxide likewise will impact the accuracy of the method, as additional
oxidant will also oxidize the Fe(II), making it difficult to determine the persulfate contribution. For hydrogen
peroxide – persulfate combinations, it is possible to react the peroxide with ceric sulfate first, to a Ferroin end-point,
as the ceric sulfate will preferentially react with hydrogen peroxide over persulfate. When the end-point is reached,
the hydrogen peroxide will have been consumed (which will also give a quantifiable measurement of the peroxide in
solution). Then the permanganate or ceric sulfate back-titration of Fe (II) can be utilized to quantify the remaining

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 Peroxygen Talk

persulfate. The above titration method can provide a very accurate measurement of persulfate in solution. But
typically it is only applicable in a laboratory, due to the instrumentation and chemicals required.

Application in the field

We have developed an easy-to-use, onsite titration kit for the measurement of persulfate in groundwater that
addresses the limitations mentioned above, the new Klozur® Persulfate Field Test Kits. Two kits are currently
available, one for use when activating Klozur persulfate with either high pH or with iron sulfate, and a second kit for
use when activating Klozur persulfate with chelated iron. If hydrogen peroxide is being used as the activator,
please contact us for additional support.

Iodiometric Methods

Persulfate anion will react with potassium iodide as:

S2O8-2 + 2 I-  2 SO4-2 + I2 Equation 5

I2 forms a brown color. In the laboratory, this method can be made quantitative by titrating the resulting solution with
thiosulfate, reducing the I2 back to I-, the end-point identified by the disappearance of the brown color. This can be
enhanced by the addition of starch, which will form an intense blue complex with I2 in the presence of I-.
Disappearance of the blue color indicates the end-point when I- has been consumed. This method will have less
interference from native metals as compared to the persulfate - iron method described above. However, accuracy
will be affected by the instability of I2 and the sensitivity of the reaction to the timing of the addition of the starch
indicator.

Application in the field

The presence of persulfate can be qualitatively assessed by looking for a color change when starch is
added to a solution of the groundwater and potassium iodide. If persulfate is present, a blue color will appear.
However, instability of thiosulfate solutions, oxidation of I - by air and sunlight and the sensitivity of the end-point on
the addition timing of the starch limit the use of this method as a quantitative assessment tool in the field for
persulfate concentration.

Spectroscopic Methods

Huang, et al2 developed a laboratory spectroscopic method for the quantification of persulfate. The method
is based on the oxidation of Fe(II) by persulfate to Fe(III). The Fe (III) is then complexed with thiocyanate (SCN -),
which forms an intense red color. A spectrophotometer is then used to determine the concentration of the iron -
thiocyanate complex as a function of absorbance at a wavelength of 450 nm. As this method is dependent upon
Equation 1, it is subject to the same interferences from background iron concentrations and chelating agents as
described for the persulfate – iron methods.
Several other spectroscopic methods have been developed for persulfate as well. These have been
reported in reference 1 and by Williams3. In general, spectroscopic methods can obtain a high degree of
quantification in a laboratory setting. However, the applicability to use in the field is somewhat limited due to the
need of spectrophotometers. These methods may be suitable to mobile field labs equipped with the appropriate
devices.

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 Peroxygen Talk

Novel Techniques for Future Development

Gillian1, in work supported by Arcadis, developed a couple of new spectroscopic methods for the analytical
determination of persulfate concentration. One of these includes the use of indole as a reactant with persulfate,
forming a distinctive blue-colored compound. A second method utilizes the reaction of persulfate with
promethazine-HCL, which forms a red-colored compound. Gillian1 reports that in particular, the promethazine-
HCL procedure has potential to be developed into a field test method, provided that iron concentrations in the
groundwater are not high. Rossabi4 et al described a novel approach to using ion chromatography to measure
aqueous persulfate concentrations, and reported a measurement range of 0 – 500 mg persulfate / liter.

Other Field Measurement Methods

There are commercially available persulfate test kits on the market. These are predominately based on the
permanganate back-titration of Fe (II), Equation 1, which relies on matching a shade of purple to a subsequent
persulfate concentration. Such kits can have significant interference from native groundwater iron or residual
contaminant. In addition, these kits can be too sensitive in that they may indicate the presence of persulfate into
the mg / L range, far below the effective persulfate dosing for most contaminated sites.
Secondary parameters, such as conductivity and sulfate concentration can be used to monitor the effective
movement of persulfate in the subsurface. Persulfate injection will significantly increase the conductance of
groundwater due to the increase in ion concentrations. Down-well conductivity probes and direct-push rod probes
have been used successfully to determine the presence of persulfate in groundwater. Commercially available
sulfate concentration kits have also been used to determine the presence of persulfate in down-gradient monitoring
wells, as persulfate is consumed through reaction, it generates sulfate. Dissolved oxygen, ORP and pH
measurement can also be used to track persulfate in the subsurface through its impact on groundwater parameters.

1. Lai, Gillian. “Development of Analytical Methods for Estimation of Oxidants Concentrations”. Master’s thesis, Imperial
College, London, September, 2007.

2. Huang, K.C., Couttenye, R.A. and Hoag, G.E. “Kinetics of heat-assisted persulfate oxidation of methyl terty-butyl ether
(MTEBE)”. Chemosphere 49, p 413-420, 2002.

3. Williams, W. J. Handbook of Anion Determination. 1979, London, Butterworths.

4. Rossabi, J. and B. Fassolt. “Ion Chromotography for Persulfate and Total Oxidant Demand Analysis”. 1st Annual
Southeastern In Situ Soil and Groundwater Remediation Conference, Raleigh, NC 2007.

The content in this document was originally published in Peroxygen Talk dated August 2010.

Klozur is a trademark of PeroxyChem. Copyright  2016 PeroxyChem. All rights reserved. The information contained herein is presented to the best of our
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