1 s2.0 S2352186417300767 Main

Environmental Technology & Innovation 9 (2018) 303–322
Contents lists available at ScienceDirect
Environmental Technology & Innovation

journal homepage: www.elsevier.com/locate/eti
Recent advances in surfactant-enhanced In-Situ Chemical

Oxidation for the remediation of non-aqueous phase liquid
contaminated soils and aquifers
Abreham Tesfaye Besha a , Dawit N. Bekele b, *, Ravi Naidu b,c ,
Sreenivasulu Chadalavada b,c
a
Wollo University, College of Natural Science, P. O. Box, 1145, Dessie, Ethiopia
b
Global Centre for Environmental Remediation, ATC Building, University of Newcastle, University Dr, Callaghan NSW 2308, Australia
c
CRC for Contamination Assessment & Remediation of the Environment, Building X (Environmental Sciences Building), University of
South Australia, Mawson Lakes, SA 5095, Australia
highlights
• Understanding of S-ISCO chemical kinetics saves remediation time and resources.

• S-ISCO approached for NAPL and/or source zone remediation technology.
• S-ISCO is effective and provides near permanent solution for residual NAPLs.
• Versatile, cheap and non-food grade surfactants is highly needed.
article info a b s t r a c t
Article history: Protecting soils and groundwater from contaminants is a global challenge and remedi-
Received 11 March 2017 ating contaminated sites may require decades and many resources. Non-aqueous phase
Received in revised form 9 August 2017 liquids (NAPLs) resulting from oil and gas exploration or drilling, coal gas plants, leaking
Accepted 17 August 2017
storage tanks and wood treatment facilities are major contaminants of subsurface soil
Available online 26 August 2017
and groundwater. In-Situ Chemical Oxidation (ISCO) has certain limitations with respect
to cost, time, and rebound of contaminants when it is applied to remediation of NAPLs.
Keywords:
NAPLs The development of plant-based biodegradable and environmentally friendly surfactants
S-ISCO has opened the door to developing an innovative Surfactant Enhanced In-Situ Chemical
Surfactants Oxidation (S-ISCO) system for remediating hydrocarbon contaminated soils and aquifers.
Oxidant and activators This review highlights the state of the art of this technology and compares it to ISCO.
An overview on the three most important components of S-ISCO — surfactant/co-solvent
mixtures, the catalyst and/or the oxidant and the free radicals is presented. The major
factors affecting the application of S-ISCO for the remediation of contaminated sites are
highlighted. This review delivers a detailed explanation on the recent case studies and field
applications of S-ISCO and factors affecting its implementation.
© 2017 Elsevier B.V. All rights reserved.
Contents
1. Introduction............................................................................................................................................................................................. 304
2. State-of-the-art of In-situ Chemical Oxidation..................................................................................................................................... 305
* Corresponding author.
E-mail address: dawit.bekele@newcastle.edu.au (D.N. Bekele).
http://dx.doi.org/10.1016/j.eti.2017.08.004
2352-1864/© 2017 Elsevier B.V. All rights reserved.
304 A.T. Besha et al. / Environmental Technology & Innovation 9 (2018) 303–322
2.1. Advances of Surfactant Enhanced In-situ Chemical Oxidation .............................................................................................. 305

2.1.1. Surfactant Enhanced Product Recovery (SEPR) ........................................................................................................ 308
2.1.2. Advantages of S-ISCO.................................................................................................................................................. 308
2.2. Surfactants/co-solvents mixtures for NAPL removal ............................................................................................................... 309
2.2.1. Mechanism of surfactants for the removal of NAPL using S-ISCO........................................................................... 309
2.2.2. Evaluation of surfactants used for S-ISCO and their limitations ............................................................................ 311
2.3. Oxidants and catalyst/activators .............................................................................................................................................. 311
2.3.1. Activators/Catalyst chemicals and reagents ............................................................................................................. 312
2.3.2. Commonly used oxidants........................................................................................................................................... 312
2.4. S-ISCO treatability studies ........................................................................................................................................................ 315
3. Subsurface properties affecting the efficiency of S-ISCO ..................................................................................................................... 315
4. S-ISCO field demonstrations and performances ................................................................................................................................... 316
4.1. Former manufactured gas plant ................................................................................................................................................ 316
4.2. S-ISCO application for residential and other sites.................................................................................................................... 317
4.3. SEPR and S-ISCO sequential field application........................................................................................................................... 317
4.4. Ex-situ field application of S-ISCO ............................................................................................................................................ 320
5. Conclusion and future outlook............................................................................................................................................................... 320
References ............................................................................................................................................................................................... 320
1. Introduction
Volatile organic compounds (VOCs) are amongst the world’s most widely occurring environmental contaminants
of subsurface soil, groundwater and sediments because of the ubiquitous production and use of organic solvents and
hydrocarbon fuels (Rivett et al., 2005). Sources of VOCs contamination range from localized point sources (e.g. leaking
underground storage tanks and landfill sites) to non-point-source or diffuse pollution associated with industrial, agricultural
or defence sites (Siegrist et al., 2011; Stroo et al., 2012; USEPA, 2016). The sources include fuel stations, dry cleaners,
petroleum drilling, nuclear and military installations. A number of contaminated soils and groundwater sites and a range
of remediation technologies have been reported (Bekele and Naidu, 2015; Dugan et al., 2010; EthicalChem, 2016b,k; Hoag,
2009; Siegrist et al., 2011). To safeguard public health and the environment, there is a need for cost-effective and rapid
remedial action and an urgent need for further research and innovative technologies. Existing contaminated sites and recent
spills will remain on-going serious problems. For instance, in the USA an estimated 294,000 contaminated sites with clean-up
costs of $209 billion are required from 2004 to 2033 (Siegrist et al., 2011).
If high concentrations of VOCs are present in soil, they are toxic to bacteria and recalcitrant to biodegradation (Paria,
2008). Contaminants occur in the subsurface environment dissolved in water, sorbed to soil surfaces, as soil gas, and in
non-aqueous phase liquids (NAPLs). NAPLs are water immiscible and almost always embrace refractory compounds. NAPLs
generally fall into two groups based on their density: light non-aqueous phase liquids (LNAPLs); and dense non-aqueous
phase liquids (DNAPLs). LNAPLs are relatively soluble and volatile and tend to be relatively mobile, while DNAPLs typically
have the opposite properties and tend to adsorb onto soil, and have low solubility in water (CLU-IN, 2016; Müller and
Sedláčková, 2003; Mulligan et al., 2001; Siegrist et al., 2011). Common examples of DNAPLs include chlorinated solvents
such as trichloroethene (TCE), tetrachloroethylene (PCE or Perc); creosote, coal tar, TCA whereas LNAPLs are usually fuel
products, petroleum hydrocarbons (TPHs) and gasoline. Due to their water immiscibility and tendency to be sorbed to soil
materials, effective remedial technologies for NAPLs have been difficult to implement.
After being spilt on soil, migration of NAPL occurs by gravitational and capillary forces. It becomes a non-continuous
phase and forms residual mobile globules (Mulligan et al., 2001). Globules are entrapped in pores by capillary forces in soil
resulting in residual saturation. Permeation of NAPLs results in their retention in the unsaturated zone. Further infiltration
could trap NAPLs in the saturated zone. Consequently, the dissolution of NAPLs by residual saturation by water infiltrating
gradually through the unsaturated zone to the water table pollutes the groundwater (Müller and Sedláčková, 2003).
Recently, the remediation of NAPLs in groundwater using the pump-and-treat system has been improved to create
more effective and sustainable technologies of in-situ plume treatment. More recently source zone remediation has been
developed (EthicalChem, 2016b; Siegrist et al., 2011; Stroo et al., 2012). In-situ chemical oxidation (ISCO) (Bekele and
Naidu, 2015; Siegrist et al., 2011), in-situ surfactant/co-solvent flushing (Dugan et al., 2010; Mao et al., 2015; Strbak, 2000),
surfactant enhanced aquifer remediation (SEAR) (Abriola et al., 2005), in-situ thermal treatment (Kingston et al., 2010),
in-situ bioremediation (Kuppusamy et al., 2016) and in-situ chemical reduction (Stroo et al., 2012; Wit, 2013) were reported
to remediate source zone NAPLs contamination.
The application of ISCO to remediate NAPLs is limited to the dissolved phase in the subsurface, and is not suitable to
remediate sorbed or residual contaminants, ganglia of NAPLs in the unsaturated soils and source zone NAPLs (Brebbia, 2013;
Collins, 2012; Dugan et al., 2010; Hoag and Collins, 2011; Siegrist et al., 2011; Stroo et al., 2012; Wang et al., 2013). In
the last decade Surfactant Enhanced In-Situ Chemical Oxidation (S-ISCO) has been extensively used for in-situ remediation
technologies for removing NAPLs from soil and groundwater (Brebbia, 2013; EthicalChem, 2016d,e,f; Lanoue et al., 2011).
ISCO involves the injection or direct mixing of reactive chemical oxidants directly into the contaminated medium (soil or
groundwater) to destroy chemical contaminants in place. S-ISCO involves the reactive transport of surfactant and co-solvent
A.T. Besha et al. / Environmental Technology & Innovation 9 (2018) 303–322 305
that is the sequential combination of surfactant/co-solvent flushing followed by ISCO with which oxidant reaction is greatly
increased, leading to more efficient oxidant use. S-ISCO incorporates the following three key elements: surfactant and co-
solvent mixtures that emulsify NAPL-phase contaminants and desorb source zone contaminants; catalysts and oxidants that
generate powerful free-radical oxidant systems; and free radical oxidant systems that destroy solubilized contaminants.
Many reviews have been published regarding in-situ soil and groundwater remediation technologies (Dugan et al., 2010;
Kuppusamy et al., 2016; Mao et al., 2015; Mulligan et al., 2001; Siegrist et al., 2011; Stroo et al., 2012). In contrast, S-ISCO
is an emerging remediation technology for NAPL contaminated soil and groundwater and there is limited scientific peer-
reviewed literature covering its field applications. To date there has been no review article regarding S-ISCO and its field-
scale applications as a remedial technology for the destruction of NAPLs.
This paper reviews the state-of-the-art S-ISCO technology and the various factors that affect its applications. It presents
case studies of S-ISCO for field applications in various countries. To include the latest advances in S-ISCO selected information
from conference proceedings, non-reviewed and peer reviewed professional journals have been included.
2. State-of-the-art of In-situ Chemical Oxidation
The term ISCO is used to describe remediation technology that harnesses the power and speed of chemical reactions
to destroy contaminants within the subsurface (Siegrist et al., 2011; Stroo et al., 2012). It is a relatively mature and viable
technology for the remediation of contaminated groundwater, including sources and plumes in the aqueous phase (Siegrist
et al., 2011; Stroo et al., 2012; Tsitonaki et al., 2010). Site characterization, the type of contaminants and the design of the
oxidant delivery system affect the effectiveness of ISCO (Siegrist et al., 2011; Stroo et al., 2012; Tsitonaki et al., 2010).
The advantage of ISCO over other remedial technologies, if appropriately implemented, is the speed at which the process
proceeds (Dugan et al., 2010; Siegrist et al., 2011; Stroo et al., 2012). Contaminants can be destroyed upon initial contact with
the oxidant (Siegrist et al., 2011). However, the chemical oxidation reactions are short-lived, thus limiting the achievable
distribution from each injection point (Siegrist et al., 2011; Stroo et al., 2012). For this reason, ISCO requires multiple
injections and/or very close spacing injections. Besides being short-lived, the reactions may not be selective for the target
contaminants. ISCO may also affect building structures which raises concerns about the appropriateness of the application in
certain scenarios. Oxidants may also leave undesirable by-products or residues that can further compromise biodegradation
or interfere with future reactions in the soil (Siegrist et al., 2011; Stroo et al., 2012).
Sodium or potassium permanganate (NaMnO4 or KMnO4 ), sodium persulfate (Na2 S2 O8 ), catalyzed hydrogen peroxide,
(CHP, also known as modified Fenton’s reagent), and ozone are the major oxidants for the ISCO process (Dugan et al., 2010;
Siegrist et al., 2011; USEPA, 2016). The first three oxidants are injected as a liquid. Whereas ozone is injected as a gas and
it is used less often. Peroxone, percarbonate and calcium peroxide are less commonly used oxidants. A detailed explanation
of the oxidants’ properties, reaction chemistry, interaction in the subsurface and treatability of different COC was reviewed
by Siegrist et al. (2011). The exact chemical reactions vary with the oxidant type, the subsurface geochemistry and type of
contaminant (Siegrist et al., 2011). The oxidant generates highly reactive free radicals which in turn quickly oxidize the target
contaminants. Activation of the oxidant depends on temperature, pH, and salinity and these factors vary with the oxidant
type and contaminants (Siegrist et al., 2011).
Although ISCO is cost-effective for in-situ destruction of many organic contaminants, it has limited applications in source
zone destruction for large masses of DNAPLs contaminants (Siegrist et al., 2011; Stroo et al., 2012). As ISCO fails to remediate
source zone contamination the possibility of rebound is expected since the sorbed and free phase contaminants re-dissolve
into the aqueous phase (Siegrist et al., 2011; Stroo et al., 2012). Following rebound, second or third injections may be needed
and this increases the overall cost of the project (Stroo et al., 2012; USEPA, 2016). Fig. 1 illustrates the remediation of PCE from
groundwater. Due to the rebound of the PCE from unaddressed soil and free phase plume, the groundwater concentrations
of the PCE soon recovered (EthicalChem, 2016a). The contaminants dissolve again into the groundwater and return with a
concentration that can approach pre-treatment levels.
ISCO takes place primarily as aqueous phase reactions in the groundwater; highly hydrophobic contaminants sorbed
to soil particles and NAPLs are not freely available for oxidation. Additionally, contaminants are difficult to remove from
low-permeability fractured-rock by ISCO. For this reason, S-ISCO was specifically developed to overcome the limitations
associated with inability of ISCO to oxidize sorbed NAPLs contaminants (See Table 1.).
2.1. Advances of Surfactant Enhanced In-situ Chemical Oxidation
S-ISCO is a verified co-elution technology that removes tightly sorbed hydrophobic contaminants such as NAPLs, thereby
reducing the flux of groundwater constituents at contaminated sites (Brebbia, 2013; Collins, 2012; Dahal et al., 2016; Hoag,
2009; Hoag and Collins, 2011; Lanoue et al., 2011). The process consists of S-ISCO chemistry – surfactant/co-solvent, oxidants
and activators for the remediation process. It was first developed by the then VeruTEK Technologies Inc and patented under
US number 7976241 in July 2011 (Hoag and Collins, 2011). All of VeruTEK’s intellectual property and other assets were
acquired by EthicalChem LLC, which specializes in plant-based, ‘‘green’’ chemistry for the environmental and oil production
industries. VeruSOL is generally recognized as a safe plant oil-based co-solvent and surfactant system, derived from citrus
fruit, coconut and castor oils. VeruSOL desorbs contaminants from soils and emulsifies them into the aqueous phase and in
this way greatly increases the contaminants’ surface area for oxidation (EthicalChem, 2016a).
306
A.T. Besha et al. / Environmental Technology & Innovation 9 (2018) 303–322
Table 1
Comparison of S-ISCO and ISCO.
S-ISCO ISCO References

Enables greater contaminant/oxidant contact with hydrophobic Inadequate contact between the oxidant and the chemicals of concern (Wanget al., 2013)
contaminants (COC)
Suitable for the remediation of tightly sorbed contaminants such as Suitable for dissolved phase and lightly sorbed contaminants (Dugan et al., 2010; EthicalChem, 2016a,c)
chlorinated solvents and NAPLs
Addresses source zone and reduces the total oxidant needed over Source zone remediation is very difficult because of residual saturation (EthicalChem, 2016d)
project lifetime
Provides permanent solution for groundwater treatment for NAPLs and Complete removal is possible for dissolved phase groundwater plumes (Siegrist et al., 2011)
plumes
Mostly removes NAPLs solely and avoids follow up treatments Coupling with other remedial technologies is necessary to remove (Dugan et al., 2010; USEPA, 2016)
NAPLs
No rebound due to source zone/residual contaminant treatment Rebound is a common phenomenon (Siegrist et al., 2011)
It is environmentally friendly because of the VeruSOL Residues from the process may inhibit biodegradation (EthicalChem, 2016c,d)
Non-aqueous and aqueous phase systems reactions are possible Only limited to aqueous phase system (EthicalChem, 2016c,d)
Fast and energy efficient for NAPLs’ destruction Slow NAPLs destruction process (Lanoue et al., 2011)
Treatment length varies from 1 week to 6 months Clean up may take a few months to years (USEPA, 2016)
Cost-effective at sites for source zone destruction of NAPLs Very costly to remove source zone contamination of NAPLs (EthicalChem, 2016a,c)
It uses 4%–8% peroxide Typically uses 12%–16% peroxide (EthicalChem, 2016b,e)
VeruSOL reduces H2 O2 consumption Multiple injections are required (Siegrist et al., 2011; USEPA, 2016)
VeruSOL with H2 O2 decreases exothermic reactions and results in safe Highly exothermic and the temperature of aquifer material and (Siegrist et al., 2011; USEPA, 2016)
implementation groundwater may rise
3.0
2.5
2.0
1.5
1.0
0.5
0.0
01/01/01
11/01/02
11/01/03
11/01/04
11/01/05
11/01/06
11/01/07
11/01/08
11/01/09
Fig. 1. Groundwater PCE (mg/L) in the source area, relative to ISCO (EthicalChem, 2016a).
Fig. 2. Comparison of ISCO and S-ISCO of TCE column experiment after 14 days using alkaline persulfate as an oxidant (Hoag, 2010).
S-ISCO addresses NAPL source zone remediation including the elimination of the rebound of contaminants. It utilizes an
oxidant with the plant-based biodegradable surfactant/co-solvent mixture to desorb and emulsify NAPLs and larger fractions
of hydrocarbons (Brebbia, 2013; Collins, 2012; Dahal et al., 2016; Hoag, 2009; Lanoue et al., 2011). The injected S-ISCO
chemicals travel through the subsurface with the groundwater providing timely and permanent solutions to soil, water, and
residual free-phase contamination (contamination which refers to LNAPL floating on a layer of water or visible at surfaces)
(Brebbia, 2013; Naidu, 2013).
The overall rate of S-ISCO reactions is determined by the rate at which the contaminants partition into the aqueous phase.
As the concentration of VeruSOL increases, the rate and extent of emulsification the subsequent rate of chemical oxidation
increases. As a result the aqueous phase transfer of contaminants increases and this leads to faster and more complete NAPL
destruction (EthicalChem, 2016m). S-ISCO reactions are more efficient than those of ISCO, thereby decreasing the project
length and energy consumption (Lanoue et al., 2011). Fig. 2 shows soil column tests on highly DNAPL contaminated soils,
and it is evident that there is a visual difference between the amounts of DNAPLs remaining (left hand side of Fig. 2) after
14 days of ISCO treatment. There were no DNAPLs observed with the naked eye after the NAPLs were treated with S-ISCO.
Continued control of immobilization of NAPL in the soil pore space by S-ISCO treatment is crucial to this process.
Fig. 3. The differences between SEPR and S-ISCO.
S-ISCO is a proven technology for both bench and field scale studies, and has been implemented in countries in the
United States and Australia to remediate sorbed and free NAPLs (Brebbia, 2013; Collins, 2012; Hoag, 2009). The reaction
by-products from S-ISCO reactions are environmentally benign and furthermore, VOCs are not released into the ambient air
during application.
2.1.1. Surfactant Enhanced Product Recovery (SEPR)

For a significant NAPL concentration in the subsurface EthicalChem’s patented Surfactant Enhanced Product Recovery
(SEPR) can be implemented followed by S-ISCO. SEPR/S-ISCO has been implemented at field scale to remediate soil and
groundwater contaminants such as creosote DNAPLs (EthicalChem, 2016d), polycyclic aromatic hydrocarbons (PAHs) and
TPHs (EthicalChem, 2016e). SEPR involves the simultaneous injection of surfactants/co-solvents in line with low doses of
hydrogen peroxide to mobilize free phase products through recovery wells (EthicalChem, 2016c). Following SEPR recovery,
S-ISCO chemicals (usually VeruSOL with activated persulfate) are injected to destroy residual NAPLs. SEPR technology is
designed to reduce the viscosity of NAPLs, lower the interfacial tension (IFT) between NAPLs and water, remove bulk free-
phase NAPL from the subsurface, and thereby significantly reduce the contaminant mass and optimize subsequent S-ISCO
implementation. The surfactant used during the SEPR process forms a weak emulsion that separates readily once the NAPLs
are recovered, but the surfactant used during the S-ISCO process forms a strong emulsion with contaminants for aqueous
phase oxidation (EthicalChem, 2016e,l). When the VeruSOL and the hydrogen peroxide are injected together for the SEPR
process, the oxygen gas released during peroxide decomposition causes the surfactant to foam up. This creates bubbles
that accelerate the transport of NAPL to the recovery wells (EthicalChem, 2016l,n). The surfactant can be recovered by
temperature cycling method (Prukop, 1995) or by treating the emulsion with brine and partitioning agent (Newcombe,
1980). Fig. 3 illustrates the SEPR and S-ISCO technology. The advantage of SEPR is recovery of the products that they have
potential applications for other uses, or they can be disposed off-site (EthicalChem, 2016e). SEPR technology does not require
the addition of activators as natural minerals and inorganic compounds in the subsurface provide sufficient activation. The
disadvantage, however, is that SEPR uses larger amounts of VeruSOL than S-ISCO.
At some point after the SEPR process, S-ISCO implementation occurs in two phases. Phase I with VeruSOL and with
sodium persulfate serves to remove residual soil contamination, while phase II can be done with VeruSOL injection and low
concentrations of H2 O2 to destroy residual emulsified groundwater. Overall, the SEPR and S-ISCO processes were effective in
significantly reducing the amount of free phase and residual contamination present in the subsurface (EthicalChem, 2016e).
2.1.2. Advantages of S-ISCO

S-ISCO can also be employed ex-situ with a less expensive and more environmentally friendly alternative to soil
excavation and off-site disposal, followed by pump-and-treat activities (Hoag, 2010; Lanoue et al., 2011). In comparison
to excavation, thermal or stabilization processes, S-ISCO does not generate any wastes on-site (Lanoue et al., 2011). This
leads to a much reduced carbon greenhouse gas footprint. S-ISCO also has an advantage over surfactant flush methods; in
the latter, the surfactant can travel alone through the subsurface without an oxidant which is not the case in S-ISCO. In
S-ISCO, the simultaneous injections of the oxidants and surfactants together with the activators are designed to eliminate
or minimize the risk of the surfactant being consumed more rapidly than the oxidant. In addition, S-ISCO technology does
not require recirculating or extraction pumps as for heavy machinery used in excavations.
2.2. Surfactants/co-solvents mixtures for NAPL removal
Remediation of NAPLs or other sorbed hydrophobic contaminants using oxidant alone is very difficult since the slow
rate of dissolution of sorbed phase/NAPLs limits the rate of oxidation of the oxidants. Surfactants are surface active agents
that reduce the surface tension of a liquid and decrease the interfacial tension between two liquids (Dugan et al., 2010;
Mulligan et al., 2001). They play between the interfaces, for example, an oil and water. Surfactants are amphiphilic molecules
possessing both polar head (hydrophilic or water loving) and a non-polar tail (hydrophobic, lipophilic, fat or oil loving). The
hydrophilic part is composed of an anion or cation and the hydrophobic end is composed of long chain hydrocarbon. In a
solution containing organic compounds, surfactants form a spherical structure in such a way that the polar head aggregates
towards the water and the nonpolar tail attract the organic compound (Mao et al., 2015). The threshold concentration at
which this process occur is known as the critical micelle concentration (Dugan et al., 2010; Mao et al., 2015; Mulligan et
al., 2001; Naidu, 2013). For the successful application of S-ISCO, determining the micelle concentration is crucial (Hoag and
Collins, 2011).
Micelles can readily disperse NAPLs and dramatically enhance their solubility in the aqueous phase. Dissolved contami-
nants in the aqueous phase are available for either biotic (Bezza and Chirwa, 2016; Yan-Zheng et al., 2007) or abiotic (Wang
et al., 2013; Zheng et al., 2016) reaction mechanisms. As stated previously, water solubility is the controlling removal
mechanism for most organic contaminants in soil and groundwater; therefore, surfactants can accelerate desorption of
NAPLs from soil and simultaneously promote oxidation of organic pollutants by increasing their solubility. The mobility
of NAPLs and sorbed contaminants is restricted by capillary forces; however, surfactants are able to emulsify NAPLs and
subsequently increase their mobility by reducing the interfacial tension (Bezza and Chirwa, 2016; Dugan et al., 2010; Hoag
and Collins, 2011; Mao et al., 2015; Wang et al., 2013; Zheng et al., 2016).
Previous studies have reported high surfactant concentration hinders both the oxidation of surfactant as well as the
micelles as the formation of micelles act as a protective layer sterically hindering oxidation phenomena (Trellu et al., 2017).
These authors mentioned that the use of high concentration of surfactant is the solution to get extra free micellar compound
to achieve oxidation of organic compounds. For this type of oxidation, it may be better to use SEPR followed by S-ISCO in order
to increase oxidation of the contaminants and to recover some of the surfactant and thereby reducing the cost of remediation
process. Also to get selective oxidation and to reduce the protective layer formed by the surfactant during oxidation process,
it might be useful to use strong oxidant like persulfate.
2.2.1. Mechanism of surfactants for the removal of NAPL using S-ISCO

Various complementary mechanisms could trigger the destruction of NAPLs using surfactant or surfactant co-solvent
mixtures. These include: reductions of IFT between the aqueous and NAPL phases, enhanced solubility of NAPLs components
in the aqueous phase, swelling of the NAPL phase relative to the aqueous phase, and, under certain conditions, complete
miscibility of the aqueous and NAPL phases (Hoag and Collins, 2011). Reduction of IFT between the aqueous and NAPLs
phases to a level where the NAPL is mobile in the subsurface increases mobilization of the NAPL phase and follows the Winsor
type II system (Mehta and Kaur, 2011). Winsor type II system is the water in oil phase where the oil is the mobile phase and
water lies inside the micelle (Mehta and Kaur, 2011); which is typical of the SEAR flushing product recovery process. In
this process, NAPLs are the mobile phase and require pumping wells for their recovery (Hoag and Collins, 2011; Mao et al.,
2015). Complete recovery of contaminants and the injected chemicals utilizing the SEAR process is difficult and the injection
wells are expensive. The ultimate goal of SEAR is mobilization and recovery of NAPLs through extraction wells without
involving chemical methods (Hoag and Collins, 2011). If the dissolved and mobilized phases of NAPLs are not collected from
the subsurface by extraction wells, the movement of the contaminants increases and can contaminate more of the subsurface
than prior to the treatment.
Matching the fate, transport and reaction of the co-solvents and surfactants with the activity of the free radical-based
chemical oxidant is the outstanding technical advantage of this process. To simultaneously transport the surfactant and
oxidants through the subsurface and to the target NAPL contaminated zones, the immediate resistance of the plant oil-based
surfactant to chemical oxidation is critical. S-ISCO uses Winsor Type I micelles in which the hydrophilic part is the exterior
and the hydrophobic part is the interior; water is the continuous phase and the NAPL is inside the micelle (EthicalChem,
2016i; Hoag, 2009; Hoag and Collins, 2011). Together with the mixture of oil and water, the surfactant creates a nano-
and micro-emulsion where the NAPL is solubilized as a single phase and dissolution of constituents occurs without NAPL
mobilization (Hoag, 2009; Hoag and Collins, 2011). Once the target contaminants are dissolved and enter the aqueous
phase they become available for concurrent oxidation. As observed in Fig. 4, the formation of smaller diameter nano- and
micro-emulsion increases the exposure of NAPL to the aqueous phase by increasing its surface area, thereby increasing the
oxidants’ efficiency in contacting and oxidizing the contaminants (EthicalChem, 2016a,m). For the S-ISCO process, selecting
the VeruSOL mixture depends on the nature of the DNAPL components. In particular, the mole fraction and the octanol–water
partition coefficients (Kow) of the individual organic compounds are important (Hoag and Collins, 2011; Yalkowsky et al.,
1983).
Fig. 4. Effect of surfactant on NAPL when emulsified. (a) volume: 50 cubic feet; surface area 200 square feet (b) volume 50 cubic feet; emulsion diameter
1 mm; surface area 91,440 square feet and (c) volume 50 cubic feet; emulsion diameter 91,493,000 mm; surface area 220 square feet. The interface area
between the oxidant and the contaminants increased due to the formation of emulsion (EthicalChem, 2016a).
70000
60000
TPH Concentration (mg/L)
50000
40000
30000
20000
10000
0
0 10 20 30 40 50 60
VeruSOL 3 Concentration (g/L)
Fig. 5. Enhanced solubilization of the former manufactured gas plants (MGP) DNAPL with VeruSOL (Hoag, 2009).
A surfactant by itself cannot oxidize contaminants and the use of oxidants together with surfactants/co-solvents
mixtures has long been sought by researchers to remediate chlorinated solvents (Li, 2004; Li and Hanlie, 2008; Zhai
et al., 2006). Mobilization and oxidation of chlorinated solvent with co-solvent/surfactant and permanganate has been
demonstrated. Permanganate is a strong oxidizing agent and suitable for oxidizing organic compounds comprising carbon–
carbon double bonds, aldehyde or hydroxyl groups. However, permanganate is not suitable for non-chlorinated hydrocarbon
NAPLs or some chlorinated solvents such as chloroethane and chloromethane (Dugan et al., 2010; Hoag and Collins,
2011; Siegrist et al., 2011). Additionally, permanganate reduction results in insoluble MnO2 and CO2 which clog the
pores of fine-grained soils (Dugan et al., 2010; Hoag and Collins, 2011; Siegrist et al., 2011; Stroo et al., 2012). The
discovery of persulfate as an oxidant for organic contaminants in the soil avoids the problems associated with the use of
permanganate.
New technologies that combine the advantages of surfactant and chemical oxidation using persulfate have been proposed
to remediate DNAPLs (Stroo et al., 2012; Tsai et al., 2009; Zheng et al., 2016). A study by Tsai et al. (Tsai et al., 2009) reported
that Tween⃝ R
80 (a biodegradable surfactant) with ratios of persulfate: Tween⃝ R
80: PCE of 30:2:1, and with the persulfate
activated by basic oxygen furnace slag, achieved PCE contaminated groundwater degradation of 92%. The reaction rate
increased as the concentration of Tween⃝ R
80 increased, possibly due to the enhanced dissolution of TCE by Tween⃝ R
80.
In a batch experiment, with an optimal ratio of persulfate: citrate: Fe2+ : PCE of 15:15:5:1 coupled with Tween⃝ R
80,
approximately 80%–84% removal was achieved for homogeneous and heterogeneous porous media, respectively (Zheng
et al., 2016). Tween⃝ R
80 alone removed about 52% and 67% of PCE DNAPL from the two porous media, respectively. These
results indicated that enhanced removal of PCE was achieved by combining persulfate and Tween⃝ R
80. Based on a feasibility
⃝
R
study by Tsai et al. (Tsai et al., 2009), Tween 80 combined with an oxidant could be highly efficient and cost-effective for
in-situ remediation of PCE. Using the synergistic effects of the oxidants together with the activators, Tween⃝ R
80 can be used
for S-ISCO application to remediate source zone DANPLs.
S-ISCO technology uses a patented biodegradable, U.S. Food and Drug Administration (USFDA) Generally Recognized as
Safe (GRAS) food-grade co-solvent and VeruSOL to solubilize immiscible phase DNAPL organic compounds in groundwater
(EthicalChem, 2016i; Hoag, 2009; Hoag and Collins, 2011; Lanoue et al., 2011). The products (CO2 , H2 O, and O2 ) of S-ISCO
reactions are not hazardous. As shown in Fig. 5, when the VeruSOL addition increases, DNAPL and adsorbed contaminants’
solubility increases in the aqueous phase without the NAPL being physically mobilized (Hoag, 2009; Hoag and Collins, 2011;
Lanoue et al., 2011; Wang et al., 2013).
Fig. 6. The relationship between IFT and two surfactants - VeruSOL-3 and VeruSOL-200 - at different concentrations (Wang et al., 2013).
Wang et al. (2013) examined the capacity of surfactants to desorb or solubilize TPH from soil. The solubilization
enhancement factor (SEF), which is the ratio of the TPH concentration in the presence of a surfactant to the TPH concentration
without surfactant, was 7 for VeruSOL-3. In addition, the IFT of VeroSOL-3 was lower than that of VeruSOL-200, indicating
that VeruSOL-3 solubilizes more contaminants at a given concentration, which is consistent with the Chun-Huh (Eq. (1)). As
the VeruSOL-3 dose increases, the IFT between two liquids decreases (Fig. 6).
σ = C /(Vo /Vs )2 (1)
Where σ is the IFT, (Vo /Vs ) is the ratio of solubilized oil volume to the total surfactant volume and C is a constant (Huh, 1979).
2.2.2. Evaluation of surfactants used for S-ISCO and their limitations

VeruSOL has the advantage of being ‘‘green’’ in that it is biodegradable, non-toxic and stable in the presence of
contaminants. It is synthesized from coconut oil, citrus fruits and ethylated castor oil (a mixture of ethylene oxide with
castor oil). Coconut oil and citrus fruits are food grade additives used in large-scale food industries. Likewise, castor oil is
used as a food additive, flavouring agent, skin care product and in cosmetics. It may be preferable to use safe, biodegradable,
and environmentally friendly substances for contaminant remediation that are not competitive with food or other industries.
The application of available surfactants is limited to certain geochemical compositions. Large doses of surfactant or
oxidant and long application times are required to effectively remediate soil from contaminants (USEPA, 2016). Therefore,
optimizing the amount of surfactant and oxidant, subject to various geochemical constraints will not only increase the rate of
desorption and dissolution of contaminants but also decrease the time required for the total oxidation process. A versatile and
inexpensive chemical surfactant that saves time and resources is in high demand by environmental remediation industries.
However, if the oxidant is overly reactive with the surfactant or cosolvent, the overall oxidant demand will increase, which
may counteract any benefit achieved by the higher contaminant concentration. Consequently, a key success for S-ISCO is
finding a compatible surfactant–oxidant combination that allows for effective oxidation of the contaminant with minimal
reaction of the oxidant with the surfactant (Siegrist et al., 2014).
2.3. Oxidants and catalyst/activators
The use of surfactant alone during S-ISCO treatment is not enough because it increases groundwater contaminant
concentrations especially hydrophobic ones. In the absence of oxidant, surfactant leads to unwanted contaminant mobi-
lization in the subsurface and off-site migration (Gryzenia et al., 2009; Makkar and Rockne, 2003). Consequently, oxidants
that are simultaneously injected together with surfactants are important to successfully remediate contaminated soil or
groundwater. Catalysts and oxidants generate powerful free radical oxidant systems for the destruction of contaminants in
the soil and groundwater. Non-productive oxidant consumption may occur due to oxidation of incidental organic matter
and free radical scavengers (Fallis et al., 2009; Siegrist et al., 2011). For this reason, a balance between selection of oxidants
and novel activators, and site-specific conditions (its contaminations, hydrological and geological characteristics and nearby
sensitive receptors) should be considered for the aqueous phase S-ISCO system.
Fig. 7. Destruction of contaminants with 5 g/L sodium persulfate VeruTek’s G-nZVI vs Fe-EDTA; Experimental conditions (Control: reaction time 360 min;
G-nZVI: reaction time 60 min; Fe-EDTA: reaction time 360 min) and (Non-detected: ND <12) (McAvoy, 2011).
2.3.1. Activators/Catalyst chemicals and reagents

Different activation methods have been used for persulfate (S2 O28− ) and CHP. These include alkaline conditions, iron
chelates, such as Fe(II) ethylenedinitrilotetraacetic acid (Fe-EDTA); Fe (III) ethylenediamine-N,N’- disuccinic acid (Fe-EDDS);
and a designer catalyst for peroxide, Fe(III) complexes of tetraamido macro/cyclic (Fe-TAML). Additionally, H2 O2 can be used
to activate persulfate (EthicalChem, 2016e). Sodium hydroxide (pH 10–12) is frequently utilized for alkaline activation of
S2 O28− so that free radicals are generated.
Chelated iron such as Fe-EDTA can be employed for both peroxide and persulfate, which are both cheap and easy to use.
It does not require pH adjustment since the injected oxidants typically create a similar pH (4) range in which the Fe-EDTA
functions optimally. The disadvantages of iron chelate are that soil organic matter reacts with the iron chelate (Dahmani
et al., 2006; Peng et al., 2015) and there is competition between soil organic matter and Fe (III)-EDTA for the contaminants’
reactive radicals (Peng et al., 2015), therefore decreasing its power to activate persulfate. Synthesized nano-scale zero-valent
iron (G-nZVI) is one of the most widely used activators for S-ISCO applications (Patil et al., 2016; Wang et al., 2013). G-nZVI
enables oxidants to destroy contaminants more rapidly than Fe-EDTA or Fe-EDDS, with a lower mass of oxidant consumed
per mass of contaminant destroyed (Fig. 7). G-nZVI has high specific surface area, low standard reduction potential and can
move further into the subsurface (Kuppusamy et al., 2016; Patil et al., 2016), and with both H2 O2 and persulfate, it is able to
destroy organic contaminants and reduce the amount of oxidant needed (Hoag, 2009).
Different activation methods such as surfactant activation of persulfate at acidic and basic pH could save costs and be
used for S-ISCO applications as an alternative to other activation techniques (Elloy et al., 2014). Additionally, soil organic
matter containing phenolic moieties at basic pH activate persulfate and can play its part in S-ISCO applications; however,
the mechanism of its activation is not well understood (Ahmad et al., 2013). Activation of persulfate with carbon nanotubes
(CNT) has shown promise as a novel treatment technology for the oxidation of organic matter in water (Lee et al., 2015).
These activators have potential to be used as an alternative for S-ISCO applications after feasibility studies.
2.3.2. Commonly used oxidants

Persulfate (S2 O28− ). Persulfate usually occurs in the form of sodium, potassium or ammonium salts but sodium persulfate
is the most widely used form for ISCO applications. It has the highest solubility and the residual products formed after its
applications are not harmful (Tsitonaki et al., 2010). The persulfate ion is a strong oxidant with a large potential of (E 0 = 2.1
V Vs SHE). In the subsurface with iron, including chelating agents, it generates a free sulphate radical (SO.−
4 ) with an oxidizing
potential of (E 0 = 2.6 V Vs SHE) and this radical is important for the remediation of a wide range of soil and groundwater
contaminants (Crimi and Taylor, 2007; EthicalChem, 2016a; Liang et al., 2004). Sodium persulfate reacts less with natural
organic matter (NOM) and it is appropriate for remediating contaminated aquifers containing high NOM (Stroo et al., 2012;
Tsitonaki et al., 2010). Fig. 8, illustrates the mechanism of sulphate activation and various scavenging reactions. In fact,
other scavenging reactions need to be recognized and quantified in order to better understand and optimize the capacity
of the system for contaminants’ destruction. Organic chelating agents (e.g., citric acid, sodium citrate) can inhibit undesired
SO.−4 consumption in the Fe
2+
persulfate activation system (Ko et al., 2012; Liang et al., 2004; Zhao et al., 2013). Chelating
agents control the availability of free Fe2+ ion present in the system in order to slow down the generation of SO.−4 and increase
degradation efficiency.
(a) Iron activation.
(b) Alkaline activation.
Fig. 8. The mechanism of sulphate radical activation (a) with iron and (b) with alkaline in soil subsurface.
More complex contaminants usually found in silt, clay or bedrocks at depth can be treated by persulfate (EthicalChem,
2016a, c; Siegrist et al., 2011; Stroo et al., 2012; Tsitonaki et al., 2010). It is stable and lasts from weeks to months in the
soil after its application (Chen et al., 2015; Crimi and Taylor, 2007; Ko et al., 2012). For example, with reference to S-
ISCO implementation at a Brownfield coal tar contaminated site in New York, persulfate remained active for five months
after VeruSOL and alkaline activated persulfate injection was stopped (Fig. 10) (Collins, 2012). After the oxidative reaction
of S-ISCO ceased, sulphate reducing bacteria also degraded contaminants in the soil and thereby increased the efficiency
of persulfate injection (Cassidy et al., 2015). However, persulfate reduces the biodegradation potential of other types of
microbes in the subsurface (Richardson et al., 2009). In places where the generation of soil vapours is a concern, persulfate
is preferred to peroxide because it does not generate gas during decomposition. It accelerates both the radius of influence
of injections and the contact time with recalcitrant compounds (Chen et al., 2015; Dugan et al., 2010; Hoag, 2009; Lanoue et
al., 2011). With different activation methods laboratory results of ISCO applications of persulfate have been documented for
the destruction of contaminants in soils and groundwater (Crimi and Taylor, 2007; Dahmani et al., 2006; Deng et al., 2015;
Peluffo et al., 2015; Peng et al., 2015, 2016).
Together with surfactant and different activators the persulfate radical is able to destroy a wide range of contaminants
in the soil subsurface, including TPH and PAHs, in 14 days using S-ISCO applications (Wang et al., 2013). Sodium persulfate
activation with G-nZVI in the emulsion successfully reduced the concentration of TPHs and PAHs by more than 96% (Wang
et al., 2013). Other activators (Fe-EDTA with sodium persulfate, Fe-TMAL with H2 O2 at a pH = 9 and sodium persulfate with
alkaline condition with pH >12) mineralized TPHs and PAHs very well but, G-nZVI performed better than all other activation
Fig. 9. Mechanism for activating hydroxyl radical using iron as a catalyst in the well-known Fenton’s reagent in the soil subsurface.
methods. There are two implications here: first, dissolved phase contaminants in emulsion were oxidized at a very fast rate
indicating S-ISCO are very fast processes; and second, G-nZVI had better oxidative performance than the others. Furthermore
the presence of amorphous iron nanoparticles (50 nm in diameter) increased the rate of sulphate radical activation (Peluffo
et al., 2015; Tsitonaki et al., 2010; Wang et al., 2013). However, the possible ecotoxicological effect of G-nZVI is yet to be
clarified. G-nZVI has success in USA, but not in Europe because of societal acceptance and regulatory barriers (Mueller et al.,
2012).
Hydrogen peroxide (H2 O2 ). Hydrogen peroxide is effective for oxidizing straight forward hydrocarbons (low to medium)
contaminants such as BTEX, free phase NAPLs, PAHs and fuel oils in groundwater and vadose soils (Dugan et al., 2010;
EthicalChem, 2016a). When activated with an appropriate catalyst, H2 O2 produces a powerful hydroxyl radical (OH·) that
rapidly reacts with and destroys aqueous phase contaminants. It is a very reactive species with an oxidizing potential of
(E 0 = 2.7 V Vs SHE). It converts contaminants into a less toxic forms and mineralizes them to CO2 , H2 O and O2 , and does not
yield by-products that affect water quality, through an advanced oxidation process, for example, the operative destruction
method (Fig. 9).
Different radicals are formed during H2 O2 activation and these radicals dominate the reaction at different concentration
of oxidant, catalyst, organic or inorganic solutes and pH (Pereira et al., 2012; Siegrist et al., 2011). Also some contaminants
may only degrade under specific chemistry conditions. The hydroxyl radical is one of the most important in hydrogen
peroxide oxidation system. It is a strong non-specific oxidant. Different organic compounds will react with hydroxyl radicals
at different kinetic rates, depending on their affinity for the oxidant. As a result, hydroxyl radical can selectively destruct the
target contaminants.
Hydrogen peroxide is shorter lived than persulfate and it decomposes easily in soil matrices, which limits its transport and
effectiveness (Chen et al., 2015; Crimi and Taylor, 2007; Dugan et al., 2010; Ko et al., 2012; Siegrist et al., 2011). The addition
of an organic acid such as phytate was tested to stabilize hydrogen peroxide so that it persisted longer and moved further
down gradient (Smith et al., 2015). H2 O2 can be used without an activator but in most cases it is catalyzed with an activator
to produce the hydroxyl radical and the term catalyzed hydrogen peroxide (CHP). For a small radius of influence such as near
sensitive receptors, H2 O2 is effective and preferable to persulfate. For metal-encased subsurface it is also an ideal oxidant
since it reacts quickly and is not corrosive to metals as could be the case with sodium persulfate (EthicalChem, 2016a). In
addition, peroxide can be used with persulfate as a first treatment stage. Peroxide quickly addresses the shallower, more
reactive, contamination before persulfate provides a longer-lasting treatment for deeper, more recalcitrant contaminants
(EthicalChem, 2016a, n). CHP with iron activation is the most commonly used oxidant for contaminants in the soil subsurface
in ISCO applications. One of the disadvantages of H2 O2 is that it lowers the pH of the soil in the subsurface and inhibits
biodegradation (Kastner et al., 2000). To couple oxidation with bioremediation Fenton’s reagent could be designed to operate
at a pH higher than 4.5. The removal of hydrocarbons in the soil and groundwater using CHP has been documented elsewhere
recently (Crimi and Taylor, 2007; Pardo et al., 2015a, b; Smith et al., 2015).
Fig. 10. Results of groundwater monitoring conducted during S-ISCO treatment. This shallow well screened from 3.35 to 6.71 m below ground surface
(bgs), was down-gradient to four injection wells into which the proprietary chemicals and alkaline-activated sodium persulfate were injected during the
period from October 2010 to the end of February 2011 (Collins, 2012). (For interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
H2 O2 and persulfate are the two most widely used S-ISCO oxidants and permanganate was found to be ineffective for
removing NAPL because of the precipitation of MnO2 . The addition of a water-soluble polymer stabilizing agent that controls
MnO2 particle formation improves its delivery to lower permeability zones (West et al., 2008) and it may be worth trying
permanganate as an oxidizing agent for S-ISCO applications.
2.4. S-ISCO treatability studies
Laboratory treatability testing using contaminated site soil and groundwater, pilot and field scale trails, are crucial before
implementing full-scale S-ISCO treatment at contaminated sites (EthicalChem, 2016a, b, f; Hoag, 2009; Hoag and Collins,
2011). In particular, the pilot test is very informative and important for optimizing the concentration and injections of the
S-ISCO chemistry and determining the flow patterns. For successful implementation, and to truly evaluate how well S-ISCO
performs, both online and offline monitoring are critical (EthicalChem, 2016a; Hoag, 2009). Monitoring can be conducted
before, during and after S-ISCO injections. Monitoring water quality parameters (pH, conductivity, oxidation reduction
potential (ORP), IFT, oxidant concentrations and dissolved oxygen), of groundwater collected for onsite analysis, offsite
observation and sampling of wells for NAPLs, and contaminant analysis after collection of soil and groundwater are included
(Fig. 10).
3. Subsurface properties affecting the efficiency of S-ISCO
Factors including the adsorption behaviour of the surfactant to the soil, its interaction with the oxidant, its ability to
desorb contaminants from the soil, its toxicity and biodegradability, are crucial for its successful implementation on the
field (Mao et al., 2015). These authors also noted some non-scientific factors such as the cost of surfactants and the extent
of the contaminated site. It is evident that soil types, particularly their pH, cation exchange capacity, (CEC), particle size, and
permeability all affect S-ISCO’s removal efficiency. For instance, a decline in pH below the favourable range for persulfate
oxidation during S-ISCO at a former MGP site decreased the rate of contaminant oxidation (EPRI, 2013).
Selection and effective delivery of the oxidant and surfactant into the subsurface is determined by hydrogeological
and geochemical conditions of the land to be remediated. These in turn determine the subsequently injected oxidant’s
ability to travel to the desired treatment depth in the subsurface for successful decomposition of NAPLs. A detailed study
and understanding of the hydrogeological and geochemical characteristics of a given site is required. For instance, an
underground storm sewer line which ran directly through the treatment area resulted in a reduction in S-ISCO efficiency at
a former MGP site (EthicalChem, 2016e). Also the reaction between the oxidant and the contaminants of concern (COC), and
natural subsurface materials like NOM and minerals, influence the effectiveness of S-ISCO. Strategically installed monitoring
wells on-site and off-site will make it possible to control the movement of the S-ISCO chemistry and the status of the sensitive
receptors around the site. The issue of soil pore clogging and resultant build-up of pressure during the injection may change
the flow of the S-ISCO chemicals preferentially through high permeability zones. This will result in reduced S-ISCO contact
in zones of low permeability (EPRI, 2013).
For the treatment of contaminants in silty and clayey soils, and other soils with low permeability, the uniformity of
the dispersion of chemicals, and the treatment radius of influence, can be enhanced by using Primwave pressure pulsing
injection. This method uses a sidewinder tool to generate subsurface pressure waves (EthicalChem, 2016a, 2016c,2016g).
Based on site-specific conditions and the results of laboratory treatability and pilot tests, the correct ratio and dosage
of surfactant, oxidant and activator need to be determined for full-scale S-ISCO application in the field. This is because
the effectiveness of S-ISCO is based on the optimized parameters and the overall adjustment of the treatment plan is
determined by laboratory and pilot scale tests. Controlling the movement of the oxidant, activators and the surfactant to
the desired treatment depth interval in the subsurface is also crucial. It is important because successful transportation of the
surfactant–oxidant mixture through the subsurface will generate the maximum contact between the oxidant system and
the contaminants.
The interactions between the surfactant and the oxidant are also important. In the presence of contaminants the
surfactant persists and the oxidant is able to react with the contaminants; however, in the absence of contaminants the
surfactant is susceptible to oxidation (EthicalChem, 2016m). The movement of the S-ISCO oxidants and surfactant also affects
the technology’s effectiveness (Fig. 10). Fig. 10 illustrates the changes in persulfate and VeruSOL in the subsurface along with
TPH, versus the time it takes to oxidize the emulsified contaminants. The analysis of site groundwater monitoring revealed
the presence of S-ISCO chemicals in various wells at a site, throughout and after implementation.
Initial increased conductivity (shown as the red brown line in Fig. 10) in wells water samples indicates oxidation
and successful activation of the oxidant and its reaction with dissolved contaminants. The reduction in IFT concentration
followed by the rise in TPH concentration indicates that the active solution desorbed and solubilized the contaminants in the
aqueous phase. Over time the concentration of TPH with elevated conductivity indicated that the desorbing contaminants
were oxidized. When the injection ended the persulfate remained in the subsurface; however, reaction with solubilized
contaminants slowed down as the alkaline conditions that were used for its activations became more acidic. However, the
continued increase in conductivity and decrease in TPH concentration indicated the reactions continued.
Other factors affecting the efficiency of S-ISCO include:
• Potential adverse effects such as those from geochemical properties, and any other environmental media (residence,
water bodies) potentially affected by the treatment, should also be monitored.
• Weather conditions during the S-ISCO’s implementation also affect the process, for example rain, snow and wind in
winter (EPRI, 2013).
• An urban setting with building structures and sewer lines in the subsurface; NAPLs source ‘‘architecture’’, that is to
say, the spatial distributions of NAPLs in the subsurface may affect the oxidant’s movement. The site stratigraphy
(layering and stratification) affects the distribution of the DNAPL in the subsurface, and therefore the contaminant
architecture plays a critical role.
4. S-ISCO field demonstrations and performances
The selection of treatment technology options for in-situ remediation is constrained by regulations, cost, the extent of
contamination, presence of other contaminants and other important site-specific variables (CLU-IN, 2016). Similarly, site
conditions also influence other off-site treatment options. The physical properties of NAPLs, especially their relatively low
solubility and high specific gravity, can impact the effectiveness of pump-and-treat methods (CLU-IN, 2016). The presence
of DNAPLs also make it more difficult to reach regulatory closure and that is one of the main driving forces for using source
reduction technologies like S-ISCO to remediate DNAPLs in the subsurface.
Field studies and full-scale remediation using S-ISCO technology are still limited but, the known cases of S-ISCO suggest
good prospects. Several industrial and residential sites such as MGP (EthicalChem, 2016c, 2016e, 2016f, 2016h), a wood
treatment facility (EthicalChem, 2016d), an underground storage tank site (EthicalChem, 2016b), a textile manufacturing
company (EthicalChem, 2016g), a pipeline pumping station (EthicalChem, 2016i), a trucking facility (EthicalChem, 2016j),
home heating oil at a private residence (EthicalChem, 2016k), and various other contaminated sites have been remediated by
S-ISCO. This section provides a comprehensive overview of relevant S-ISCO case studies being applied to the remediation of
NAPLs in source zones and dissolved plumes. S-ISCO delivers the best results for sorbed NAPL, saturated zone contamination,
in permeable soil, around structures, deep contamination (>6.1 m) and with soluble hydrocarbons and chlorinated solvents
4.1. Former manufactured gas plant
S-ISCO was implemented to remediate a MGP at a Brownfield coal tar contaminated site in New York state using injections
of VeruSOL (5 g/L), Na2 S2 O8 (25–50 g/L) and NaOH (20 g/L), and with a 5-month S-ISCO period and more than 90% of the
coal tar was removed (EthicalChem, 2016c). The coal tar was mainly present as NAPL within the pore spaces of the sandy
and silty soil. The contaminant amount which was 11,969 kg of naphthalene and 18,425 kg of VOCs and SVOCs exceeded
the New York State Department of Environmental Conservation (NYSDEC) regulatory limit. NAPLs present in fine soils, silts
and clays are challenges for in-situ remediation and for this case study, Primawave Pressure-Pulsing and the RemMetrik
Process was used. A laboratory treatability test was conducted to select and optimize the S-ISCO chemistry while the pilot
test set out to incorporate a Primawave pressure-pulsing technology. Five months after the injections were completed;
S-ISCO destroyed 90.3% of total VOCs and SVOCs and 95% of naphthalene. Eleven months after the injection of S-ISCO the
analysis also revealed that groundwater monitoring wells screened across the treatment interval (3.0–6.7 m bgs) had met
the ambient water quality standards (AWQS). Moreover, there was no rebound and the contaminants’ concentrations were
likely to decrease as a result of biological activity. At another MGP site in New York, that used Na2 S2 O8 (72,674 kg), VeruSOL
(3314 kg) and Fe-EDTA (475 kg), S-ISCO treatment lasting 70 days resulted in total reductions of 843 kg of total VOCs and
SVOCs, and 3600 kg of medium range petroleum hydrocarbons from the soil (EthicalChem, 2016h). Soil and gas samples
collected at 6.1 m bgs showed approximate reductions of 92% in BTEX and 91% in total VOCs.
Contaminants found in clay and silt soils are difficult to remediate because the distribution of the oxidant along the
subsurface results in minimum contact between the oxidant and contaminants. To reduce this problem, a tool such as
RemMetrik methodology which uses Primawave Pressure-Pulsing Process Technology generates pressure waves and opens
the soil pore spaces (EthicalChem, 2016c, 2016g). Augmented with this technology, S-ISCO remediates soil and groundwater
contaminated with 1, 1, 1 -trichloroethane (1, 1, 1-TCA) with injection at a depth of 3.0–4.6 m bgs (EthicalChem, 2016g).
With approximately 46,182 L of total fluids consisting of Na2 S2 O8 , 15–50 g/L; NaOH, 12–50 g/L; VeruSOL, 5–15 g/L, the
commercial soil clean-up objectives were met (EthicalChem, 2016g). In addition, 90% of post-treatment samples met the
more stringent residential use of soil clean-up objectives (EthicalChem, 2016g). It is worth mentioning that adsorption of
organic contaminants to NOM with very slow desorption rate, high reactivity of oxidant towards soil constituents and low
permeability of matrix limits ISCO application.
4.2. S-ISCO application for residential and other sites
With a low persulfate to contaminants ratio (4.2:1), S-ISCO achieved site clean-up objectives for the destruction of soil
extractable petroleum hydrocarbon (EPH) at a former truck service facility site in New Jersey within 7 days (EthicalChem,
2016b). Samples taken 5 months after injection of the oxidant showed that the average concentration of the EPH in the soil
was reduced from 5075 mg/kg to 3098 mg/kg (EthicalChem, 2016b). For specific site criteria within the specified period of
implementation it is apparent that a reduction of oxidant consumption is possible with S-ISCO. S-ISCO was implemented to
remediate soil and groundwater LNAPLs in pipeline pumping station (EthicalChem, 2016i) and for TPH in home heating oil
at a residence in New Jersey in three days (EthicalChem, 2016k). Soil sampled from the lower vadose zone (7.62–7.77 m bgs)
treated with S-ISCO resulted in a reduction to 432 mg/kg of C6-C35 TPH from 60,000 mg/kg, and 0.54 mg/kg of BTEX from
1271 mg/kg (EthicalChem, 2016i). For the groundwater, TPH was reduced by more than 99.93% and that of BTEX by 99.72%.
With this result, each regulatory closure goal was exceeded the limit and fulfilled the objective of the site specific conditions
(EthicalChem, 2016i). In the New Jersey site TPH concentration the soil averaged 16,763 mg/kg and the impact was observed
in both the vadose and the saturated zones from 4.3 to 6.7 m bgs. The system used a pressurized system for injection of about
68,137 L of chemicals (5–10 g/L VeruSOL with 3% H2 O2 ) and the solution was injected across 14 locations at 0.61 m depth
intervals. Samples taken one month after S-ISCO injection showed that TPH concentration were reduced by more than 80%,
and regulatory Residential Direct Contact Soil Remediation Standards (RDCSR) clean-up criteria were achieved (EthicalChem,
2016k). Site regulatory closure was achieved and both the residence and the home were not impacted negatively.
4.3. SEPR and S-ISCO sequential field application
A sequential treatment approach consisting of SEPR and S-ISCO was implemented at full scale at sites heavily contami-
nated with DNAPL (EthicalChem, 2016d, 2016e). At a former wood treatment facility at Bridgeville, Delaware, USA, 52,617 L
of SEPR chemicals (1–10% VeruSOL and 4–8% of H2 O2 ) and 113,562 L of S-ISCO chemicals (5–10 g/L VeruSOL with 50– 100 g/L
of persulfate) at a 1.8–4.6 m depth interval removed 81% of the DNAPL (EthicalChem, 2016d). Increasing the volume of SEPR
chemicals increased the DNAPL from the subsurface. Post-treatment groundwater samples showed the elimination of visual
DNAPLs and there were no free by-products (EthicalChem, 2016d). The sequential use of SEPR and S-ISCO was also used to
treat a former MGP site located in Sydney, Australia (EthicalChem, 2016e). A total of 21,000 L of SEPR chemicals (20–40 g/L
surfactant and 0.5–1.0% H2 O2 ) was injected through wells for over 2.5 weeks. The S-ISCO treatment took place in two phases
for 4.5 weeks. Phase one consisted of 5–15 g/L VeruSOL and 50–100 g/L Na2 S2 O8 and was designed to destroy residual and
emulsified contaminant remaining in soil after the SEPR process. In phase two, 0.5–4% of H2 O2 for sulphate activation and
5–10 g/L VeruSOL was used to destroy residual emulsified groundwater contaminants. The SEPR process was successful and
a total of 950 L of bulk free-phase DNAPL was removed. The S-ISCO phase revealed that site criteria were achieved for TPH
in 30 of 31 soil samples and total PAHs were below tar-containing material criteria in 24 of 33 soil samples (EthicalChem,
2016e). (See Table 2.)
Though the sequential approach successfully removed free bulk DNAPL, complete removal was not achieved at both sites
within the timeframe of the site works. For complete DNAPL removal within a specified period of time increasing the dosage
of the S-ISCO chemicals and having a sound and detailed understanding of the preferred pathways of the oxidant system in
the subsurface may help.
318
Table 2
S-ISCO remediation of soils contaminated with petroleum hydrocarbons.
Site name COC Area (m2 ) and Type and/or amount of Duration S-ISCO reduction References
depth (m bgs) S-ISCO chemistry used
of remediated
sites

Former Defence, TCE – VeruSOL - 7.7g/L – >99% (EthicalChem,
Department Australia Persulfate - 185 g/L, 2016a)
NaOH - 22 g/L
Brownfield, Queens New PAHs & BTEX Area-2954.2 VeruSOL-329,545 kg 5 months Benzene (85%), toluene (81%), (EthicalChem,
York, USA Depth – Na2 S2 O8 - 152,000 kg ethylbenzene (75%), total xylenes (60%) 2016c)
3.048–6.7056 NaOH-61,950 kg BTEX (67%) & naphthalene (95%), total
SVOCs & VOCs (90.3%)
Brownfield, Queens New PAHs & BTEX Area - 2954.2 VeruSOL-329,545 kg 5 months Benzene (100%), ethylbenzene (100%), (EthicalChem,
York, USA Depth – Na2 S2 O8 - 152,000 kg toluene (98%), total xylenes (96%) 2016c)*
3.048–6.7056 NaOH-61,950 kg naphthalene (100%)
Brownfield, Queens New PAHs & BTEX Area - 2954.2 VeruSOL-329,545 kg 5 months Xylenes (92%), benzene (87%), (EthicalChem,
York, USA Depth – Na2 S2 O8 - 152,000 kg ethylbenzene (90%), BTEX (91%) 2016c)**
3.048–6.7056 NaOH - 61,950 kg
Seaboard Lumber, Creosote & DNAPL Depth – VeruSOL/iron activated – DNAPL removal > 85% (EthicalChem,
Delaware, USA 1.8288–4.572 -Na2 S2 O8 /NaOH Post-treatment groundwater analysis 2016d)** &***
showed no free products
MGP Gasworks, Sydney, PAHs, TPH & BTEX – VeruSOL/iron 6.5 weeks TPH (C10-C14)-(100%), TPH (C15-C28)- (EthicalChem,
Australia activated-Na2 S2 O8 , H2 O2 (97%), TPH (C29-C36)-(97%) and total 2016e)***
PAHs-(73%) and 950 L DNAPL was
removed
Former Truck Service EPH – VeruSOL, alkaline 7 days Reduction of an average of 3100 mg/kg (EthicalChem,
Facility in New Jersey, activated - Na2 S2 O8 post-S-ISCO injection 2016b)
USA
Manufactured Gas Plant TPHs, VOCs & SVOCs Depth VeruSOL-1724 kg 2 weeks The necessary clean-up criteria had been (EthicalChem,
(MGP) site in Hartford, –3.3528–4.8768 Na2 S2 O8 –3402 kg achieved and the client’s remediation 2016f)
Connecticut, USA NaOH-360 kg objective was achieved
Manufactured Gas Plant TPHs, VOCs & SVOCs 1 088 622 kg of VeruSOL - 2021 L 5 days TPH reduced by an average value of 92%, (EthicalChem,
(MGP) site in Hartford, contaminated Na2 S2 O8 –17 413 L VOCs and sVOCs exceeded the clean-up 2016f)****
Connecticut, USA soil H2 O2 - 17 034 L criteria
Textile Manufacturing TCA Depth –3.048 - VeruSOL, alkaline (NaOH), – Cis-1, 2 DCE (89%), 112-TCA (97%), PCE (EthicalChem,
Company, New York, USA 4. 572 activated Na2 S2 O8 (70%) and Benzene (98%) 2016g)
(continued on next page)
Table 2 (continued)
Site name COC Area (m2 ) and Type and/or amount of Duration S-ISCO reduction References

depth (m bgs) S-ISCO chemistry used
of remediated
sites
Textile Manufacturing TCA Depth –3.048 - VeruSOL, alkaline (NaOH), – Total VOCs (86%), TCA (82%), 112-TCA (EthicalChem,
Company, New York, USA 4. 572 activated Na2 S2 O8 (93%), 1, 1-DCA (93%), chloroethane (74%) 2016g)**
Former MGP, New York, PAHs & BTEX Area - 24,281 VeruSOL, Na2 S2 O8 and Fe 70 days 3600 kg medium range petroleum (EthicalChem,
USA Depth 9.144 - EDTA hydrocarbons and 843 kg total VOCs were 2016h)
–10.668 removed
Former MGP, New York, PAHs & BTEX Area - 24,281 VeruSOL, Na2 S2 O8 and Fe- 70 days BTEX (92%) and VOCs (91%) (EthicalChem,
USA Depth 9.144 EDTA 2016h)*
–10.668
Pipeline pumping station Diesel & Gasoline LNAPL Depth VeruSOL, H2 O2 – All detectable NAPLs were removed from (EthicalChem,
Texas, USA –7.62–7.7724 interstitial pores TPH (C6 –C35) (99.33%), 2016i)
BTEX (99.96%)
Pipeline pumping station Diesel & Gasoline LNAPL Depth VeruSOL, H2 O2 – LNAPL removed (EthicalChem,
Texas, USA –7.62–7.7724 TPH (>99.72%) 2016i)**
BTEX (>99.72%)
Trucking Facility, Georgia, Diesel Depth VeruSOL, Na2 S2 O8 – Visual NAPL was destroyed to below the (EthicalChem,
USA –3.3528–6.7056 state threshold 2016j)****
Private Residence, New Fuel oil (heating oil) Depth - 3.048 VeruSOL, H2 O2 3 days An average TPH removal >86% (EthicalChem,
Jersey, USA 2016k)
*
S-ISCO application for the reduction of soil vapours in the ground.
**
S-ISCO remediation of groundwater contaminated with petroleum hydrocarbons.
***
S-ISCO implemented after SEPR treatment.
****
The remediation method is known as Surfactant enhanced ex-situ chemical oxidation (S-ESCO), but S-ISCO chemistry was applied to soils above ground; bgs-below ground surface.
319
4.4. Ex-situ field application of S-ISCO
With S-ISCO chemistry soil contaminants can be remediated using an ex-situ method at sites (EthicalChem, 2016f).
At a former MGP site in Hartford, Connecticut, 1,088,622 kg of TPH, VOCs and SVOCs from 3 m bgs-unsaturated zone
contaminated soil was excavated and treated ex-situ. With 17,034 L of H2 O2 , 17,413 L of persulfate and 242 kg of VeruSOL,
the site criteria for VOCs and SVOCs were met and TPH was reduced by an overall average of 92% (EthicalChem, 2016f).
3429 kg of persulfate, 172 kg of VeruSOL and 363 kg of NaOH were injected into the subsurface at approximately 3.3 to 4.9
m bgs as per the S-ISCO treatment. Following the injection of S-ISCO chemicals the target clean-up criteria were achieved for
the site. With both methods (S-ISCO and S-ESCO) a total of 4,218,409 kg of contaminated soil was treated at a cost of about
$US 55/metric ton (EthicalChem, 2016f).
S-ESCO was also used to treat diesel NAPL at a trucking facility in Georgia, USA (EthicalChem, 2016j). Soil excavated from
3.3 to 3.7 m bgs was blended with H2 O2 and VeruSOL in above-ground mixers for one week. Further, a total of 302,832 L
of contaminated water and NAPL was pumped into a storage tanks and pulled off-site. The result showed that 75% of the
NAPL was removed. The diesel range organic (DRO) level was below 1000 ppm which is the threshold required by the State
of Georgia (EthicalChem, 2016j). Moreover, post-treatment monitoring revealed no visual NAPL remained at the site. The
advantages of S-ESCO compared to the conventional pump-and-treat technology are: firstly, it is implemented at the site;
secondly, it is relatively inexpensive and does not require the soil being transported and disposed of off-site; and thirdly, the
S-ESCO can be completed within a short period of time, whereas conventional pump-and-treat technology may take several
weeks to years.
5. Conclusion and future outlook
S-ISCO is a relatively environmentally benign chemical solution based on biodegradable plant oil-based surfactants that
enable effective dissolution and emulsification. S-ISCO represents a profound improvement over previous ISCO for the
remediation of source zone NAPL contaminated sites and dissolved plumes with less injections of oxidant to contaminant
ratio. Moreover, it is possible to reduce the use of chemicals and increase cost-effectiveness. S-ISCO is effective in treating
residual NAPLs from sources and is a relatively fast process. The chances of rebound occurring are very low and the technol-
ogy provides a near permanent solution for groundwater contaminant removal from plumes. S-ISCO has been successfully
implemented internationally near various sensitive receptors and water bodies. S-ISCO does not create additional risks to
the public or the environment as with many ex-situ-based remedial technologies.
According to the S-ISCO field scale implementation, reductions of up to 100% for some VOCs and more than 90% of
TPHs and BTEX were achieved. For some of the NAPLs, source zone regulatory closure did exceed the regulatory limit. The
sequential technology consisting of SEPR and S-ISCO could provide a much faster and more cost-effective solution to remove
bulk NAPLs than S-ISCO alone. Emerging trends and promising products from nanotechnology have also benefited S-ISCO
technology. G-nZVI makes moving nanoparticles over long distances in the subsurface much easier. The development and
use of nanomaterial for remediation technologies should be recognized, however, their full impacts on the environment
have yet to be assessed.
The application of available surfactants is limited to certain geochemical compositions based on costly materials.
Currently, surfactants are mostly prepared from coconut oil, citrus fruit, and castor oil. A versatile and less expensive
chemical surfactant that saves time and resources, and that does not compete with food supplies, is in high demand by
environmental remediation industries. In connection with this, other issues that should be considered involve: the range of
concentrations that can be treated; effects of soil type; potential latent effects (including concentration rebound, the fate of
oxidant and surfactant, soil property changes, microbial changes and time required to establish re-equilibrium. To continue
as a promising technology that contributes to a healthy environment and future sustainability, S-ISCO technology need to
resolve all issues pertaining to its application.
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Environmental Technology & Innovation 9 (2018) 303–322

Contents lists available at ScienceDirect

Environmental Technology & Innovation

Recent advances in surfactant-enhanced In-Situ Chemical

• Understanding of S-ISCO chemical kinetics saves remediation time and resources.

2.1. Advances of Surfactant Enhanced In-situ Chemical Oxidation .............................................................................................. 305

2. State-of-the-art of In-situ Chemical Oxidation

2.1. Advances of Surfactant Enhanced In-situ Chemical Oxidation

S-ISCO ISCO References

Fig. 3. The differences between SEPR and S-ISCO.

2.1.1. Surfactant Enhanced Product Recovery (SEPR)

2.1.2. Advantages of S-ISCO

2.2. Surfactants/co-solvents mixtures for NAPL removal

2.2.1. Mechanism of surfactants for the removal of NAPL using S-ISCO

σ = C /(Vo /Vs )2 (1)

2.2.2. Evaluation of surfactants used for S-ISCO and their limitations

2.3. Oxidants and catalyst/activators

2.3.1. Activators/Catalyst chemicals and reagents

2.3.2. Commonly used oxidants

(a) Iron activation.

(b) Alkaline activation.

2.4. S-ISCO treatability studies

3. Subsurface properties affecting the efficiency of S-ISCO

4. S-ISCO field demonstrations and performances

4.1. Former manufactured gas plant

4.2. S-ISCO application for residential and other sites

4.3. SEPR and S-ISCO sequential field application

A.T. Besha et al. / Environmental Technology & Innovation 9 (2018) 303–322

A.T. Besha et al. / Environmental Technology & Innovation 9 (2018) 303–322

4.4. Ex-situ field application of S-ISCO

5. Conclusion and future outlook

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