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REVIEW ARTICLE OPEN

Fenton and Fenton-like wet oxidation for degradation and

destruction of organic radioactive wastes
1✉ 2,3,4 1 1
Sam A. Walling , Wooyong Um , Claire L. Corkhill and Neil C. Hyatt

Fenton or Fenton-like oxidation for treatment of organic radioactive wastes is a promising technology with applications to a range
of organic wastes. This review details this process; exploring potential challenges, pitfalls and opportunities for industrial usage with
radioactive wastes. The application of this process to real radioactive wastes within pilot-plant settings has been documented, with
key findings critically assessed in the context of future waste production. Although this oxidation process has not found
mainstream success in treatment of radioactive wastes, a lower temperature oxidation system bring certain benefits, specifically for
higher volume or problematic organic wastestreams.
npj Materials Degradation (2021)5:50 ; https://doi.org/10.1038/s41529-021-00192-3

INTRODUCTION from alkaline conditions (such as cements). This may compromise

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The safe and economical treatment of wastes arising throughout wasteform integrity, result in chelating organic species or non-
the nuclear fuel cycle is a complex problem due to not only aqueous phase liquids, which may enhance radionuclide transport
different material characteristics (liquid effluents, organic/inor- post-disposal, result in a fire risk, or simply be not compatible with
ganic solids, gaseous discharges, etc.) but also the radiological existing waste treatment routes designed for inorganic waste-
considerations. Routine operation of nuclear power plants, fuel streams8. Some organic wastes are more easily categorised and
manufacturing, reprocessing, research and decommissioning treated than others. Higher volume plastic materials: PVC gloves,
closed facilities are but some of the few operations liable to wrapping, sample bags, PPE, etc., from known sources, and known
generate radioactive wastes. These exist as a wide array of solids, chemistries can be routed via nuclearised existing technologies
liquids, sludges, ion-exchange resins, etc., which are processed (such as supercompaction or incineration)4,9. More challenging
and disposed of according to international and national regula- organic wastes, such as organic sludges, animal matter, algae,
tions1–3. These aspects, combined with varying regulatory frame- contaminated oils, etc., may have a more hetereogeneous nature,
works across the world do, however, give rise to circumstances in no dedicated waste treatment route, or uncertain provenance.
which non-standard treatment technologies can play a key role, The wide variety and composition of organic nuclear wastes has
especially for small volume or orphan wastes for which construc- led to challenges in materials treatment, and opportunities for
tion or utilisation of large-scale conventional processing plants alternative treatment processes. One such treatment family is that
may be economically or technically unjustifiable. of advanced wet oxidation, which has at various times found a
Inorganic wastestreams, although not without their inherent receptive audience (although not often full commercialisation).
challenges, are often able to be conditioned via existing The attraction of wet-oxidation processes are typically the promise
technologies. This may be vitrification within a glass matrix, of a lower temperature decomposition system, which utilises
solidification via cementation/bituminisation, immobilisation relatively non-toxic materials (metal catalysts, hydrogen peroxide,
within a ceramic matrix or simply securely encased within a oxygen), with the output of treated effluents/slurries which can
sturdy container if activity levels and chemistry of the waste easily integrate into existing waste treatment processes (e.g. on-
permit3–5. As such these wastes (and radioactive elements) are site liquid effluent decontamination or cementation plants)10–12. A
typically either chemically incorporated within a durable matrix, or lower temperature aqueous system holds the potential for more
are physically encapsulated by a matrix for which the chemistry simple off-gas requirements, reduced risk of corrosion from high-
and durability is understood. Processing conditions for these temperature acids, and a much lower risk of radioelement
materials can be readily tailored to waste compositions. Glasses volatilisation. Coupling this to the potential for large reductions
can be formulated with lower melting temperatures, to avoid in volume of treated wastes, wet oxidation has drawn continued
volatilisation of certain radionuclides during processing (e.g. attention as a technology of interest. Such a system is capable of
caesium or iodine). Different classes of cements can be used to full operation within a mobile setup, much like a mobile
reduce heat output, or vary the internal pH to avoid corrosion/ cementation plant or supercompaction system—further adding
interaction with wastes, and ceramic formulations can be adjusted potential flexibility to this technology13,14.
to incorporate various host elements or impurities6,7. This review aims to provide a brief overview of current Fenton
Organic wastes pose a different challenge to safe waste and Fenton-like wet-oxidation technology, the current scientific
disposal. Although not typically as highly active as spent fuel or understanding, and a deeper look into historical and current
many other higher activity wastes, their organic nature may make applications of this wet-oxidation process to nuclear wastes
them susceptible to degradation over time from heat, radiolysis or around the world. Although not currently a technology which has

1
Immobilisation Science Laboratory, Department of Materials Science and Engineering, The University of Sheffield, Sheffield, UK. 2Division of Advanced Nuclear Engineering
(DANE), Pohang University of Science and Technology (POSTECH) 77 Cheongam- ro, Nam-GU, Pohang, Gyeongbuk, Republic of Korea. 3Division of Environmental Science and
Engineering (DESE), Pohang University of Science and Technology (POSTECH), Pohang, Gyeongbuk, Republic of Korea. 4Nuclear Environmental Technology Institute (NETI),
Pohang, Gyeongbuk, Republic of Korea. ✉email: s.walling@sheffield.ac.uk

Published in partnership with CSCP and USTB

 S.A. Walling et al.
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found widespread usage within the nuclear industry, this has Eq. 2 is slower than Eq. 1, and iron can also be lost due to Fe3+
found niche applications, the lessons from which need to be ions forming insoluble ferric hydroxide precipitates at circumneu-
understood for this technology to have a place within nuclear tral pH. Consequently, the pH within Fenton reaction process
waste treatment in the future. needs careful control, with an optimum pH of ~2.8–3.0 where
both Fe3+ and Fe2+ both exist in solution. Unfortunately, at lower
pH levels, hydroxyl radicals are increasingly scavenged by protons,
FENTON OXIDATION and Fe2+ decreases—again decreasing the reaction efficiency10,19.
Principles Although Fenton reactions produce strongly oxidising radicals,
Fenton oxidation can be classed as an advanced oxidation their high reactivity and low selectivity requires continuous in situ
process, in which H2O2 and a source of Fe2+ ions are utilised to production for organic material degradation16. This requires a
produce hydroxyl radicals in situ, which go on to decompose careful balancing of pH, H2O2 concentration and supply of Fe2+ to
organic materials. This reaction was first reported by Fenton in maximise the production of hydroxyl radicals, while minimising
1894, showing tartaric acid oxidation by ferrous sulphate and any terminal reactions which remove these radicals from
H2O215. Since this time, Fe catalysed oxidation has proved to solution20. Additionally, optimal efficiency of input chemicals is
degrade many organic materials, and is the subject of innumer- required to reduce costs and minimise secondary effluent streams
able papers and reviews detailing specific mechanisms. (e.g. iron hydroxide precipitates).
The Fenton reaction utilises Fe2+/Fe3+ redox with H2O2 to
produce hydroxyl and hydroperoxyl radicals. The hydroxyl radical Modified Fenton-like systems
possesses an extremely strong oxidation potential, with estimates Improvements and modifications to the traditional Fenton process
varying between ~2.0–2.8 Eo (V), putting the hydroxyl radical have been realised with the aim of increasing reaction kinetics,
between fluorine and ozone among common oxidants16–18. This maintaining catalyst reactivity and/or further reduction of
strong oxidation potential can be exploited to degrade con- remaining organics in treated solutions. Routes to achieving these
ventionally refractory bio-recalcitrant organic pollutants, such as include usage of alternative homogeneous catalysts, utilising
phenols, pesticides, pharmaceuticals and organic solvents10,19. heterogeneous catalysts and using more complex setups such as
The Fenton process is furthermore of great interest due to rapid
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photo- and electro-Fenton.

Fe/H2O2 reactions, relatively cheap input chemicals, and the ability Fe catalysts are the most commonly used homogeneous
to progress these reactions at ambient pressure/temperature. catalyst, being geologically ubiquitous and much less of a
Such a system is able to be used as a pre-treatment within existing pollutant concern than other metals, as well as being the best
wastewater treatment plants, and enables the oxidation of organic understood system. Other catalyst elements are available how-
materials or pollutants to intermediate species, which can be ever, with potential for usage of essentially any other element for
further fully mineralised to non-toxic CO2, H2O and inorganic salts which multiple oxidation states exist within an aqueous state. This
(if inorganic elements are present)10,17,20. opens up opportunities for oxidation at different pH ranges,
A multitude of studies have been published concerning specific potentially affecting wastes in different ways. Catalysts do require
mechanisms within a Fenton reaction, with debate ongoing. The careful selection, as problems of toxicity with discharged treated
generally agreed upon mechanism of reactions are Eqs. 1–2, in effluents are a risk, if usage of certain elements such as Cu or Cr is
which Fe2+ and Fe3+ both react with peroxide, cycling to produce encouraged.
radicals, which promote organic degradation. Fe2+ acts as the Cu is a choice for non-Fe Fenton-like oxidation processes,
primary catalyst, with regeneration of Fe3+ by peroxide. However, although acting in a potentially different mechanism to Fe.
regeneration of Fe2+ from Fe3+ is very slow compared to the main Alongside a traditional redox system in Eqs. 8 and 910,23, Walling
Fe2+ reaction, by at least three orders of magnitude10,16,17,19,21,22. and Kato proposed that the Cu–H2O2 system likely involved
Fe2þ þ H2 O2 ! Fe3þ þ OH þ OH (1) organocopper intermediates or ligand transfer, and with potential
redox coupling with Fe3+ (Eq. 10)24, more recently a wide range of
Fe3þ þ H2 O2 ! Fe2þ þ O2 H þ Hþ (2) Cu-organic and Cu-inorganic mechanisms have been reviewed25.
Cu alone, or in combination with Fe can achieve improved
2+
In principle, with an excess of Fe and H2O2 most organics oxidation of materials24,26–28, with the potential for utilisation of
should be mineralised to CO2 and H2O; however, competitive copper bearing wastes23, avoiding further metal additions. One
processes occur which hinder this. While there are many other advantage of copper is the apparent wider pH range over which
side reactions, including interactions with organic material which Cu is an active Fenton-like reagent, with particular efficiency closer
can affect the products and kinetics, some of the most important to neutral pH26,29.
are Eqs. 3–7, in which the hydroxyl and hydroperoxyl radicals are
removed through various mechanisms10,16,19,21: Cu2þ þ H2 O2 ! Cuþ þ HO2 þ Hþ (8)

Fe3þ þ O2 H ! Fe2þ þ O2 þ Hþ (3) Cuþ þ H2 O2 ! Cu2þ þ HO þ HO (9)

Fe2þ þ O2 H ! Fe3þ þ O2 H (4) Cuþ þ Fe3þ Ð Cu2þ þ Fe2þ (10)

Fe2þ þ OH ! Fe3þ þ OH (5) Mn has found some usage as an effective catalyst, particularly
when combined with Fe or Cu as a multi-element catalyst29–31. Co
H2 O2 þ OH ! O2 H þ H2 O (6) (often activated with persulfate) and Ru have also been
successfully studied as catalysts10. The lure of multiple oxidation

OH þ OH ! H2 O2 (7) states over a very wide pH range has drawn researchers to the use
of Cr as a Fenton catalyst, finding effective degradation of organic
In these reactions the hydroxyl radical can be scavenged by pollutants32–34. Bokare and Choi reported an extensive study of
H2O2, Fe2+ and by additional *OH, all of which reduce the the usage of a Cr(VI)/H2O2 and combined Cr(III)-Cr(VI)/H2O2 system
efficiency of degradation. Additionally, wastage of peroxide itself for 4-chlorophenol degradation, finding the dual role of H2O2 as
can occur due to self-decomposition (especially at higher both an oxidant and reductant for Cr can establish a redox cycle
temperatures)19. The process is typically rate limited by the with effective degradation properties35,36—with the option to
presence of Fe2+ ions in solution. Regeneration of Fe3+ to Fe2+ via reduce back to a less toxic Cr(III) after destruction has completed.

npj Materials Degradation (2021) 50 Published in partnership with CSCP and USTB
 S.A. Walling et al.
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Modification of the catalyst physical properties is a variation on various combinations of the above have been researched, such as
the traditional Fenton system, which is increasingly popular. sono-photo-Fenton, hetereogeneous electro-Fenton, etc51.
Specifically, instead of a traditional system in which both H2O2 and
Fe2+/Fe3+ both exist within solution, a heterogeneous catalyst can
be utilised where the catalysing element is solely, or part of a solid NUCLEAR APPLICATIONS OF WET OXIDATION
matrix, with Fenton reactions largely occurring at the solid–liquid Although there are a large body of potential radioactive and toxic
surface interface. Claimed benefits include enabling Fenton wastes, which could be suitable for treatment using a Fenton-like
reactions to occur at the catalyst surface over a wider pH range, process, open scientific literature studying these wastes is
with a lower risk of forming ferric hydroxide sludges, and somewhat limited. The bulk of available literature details
potentially avoiding the requirement for neutralisation of treated treatment of ion-exchange resins, with pilot-plant trials under-
waters16,17,37. The usage of a solid catalyst also enables potential taken by national institutions, and detailed later per country. As
recovery, regeneration (if required) and re-use after (especially such this section will largely focus on wet oxidation of ion-
with magnetic catalysts), greatly reducing by-products which exchange resins, although available literature for other wastes will
require disposal. be discussed, including that for decontamination liquids and
Fe-based hetereogeneous catalysts have been widely explored, contaminated organic solvents.
with their efficiency governed by many variables, including pH,
temperature, Fe oxidation state, surface area and Fe substitution Ion-exchange resins
with other cations17. Iron oxides are among the most well
researched, low cost options for hetereogeneous catalysis, but Ion-exchange materials find extensive usage throughout the
research also encompasses iron containing soils, pyrite, goethite, nuclear fuel cycle, both inorganic materials (e.g. zeolites) and
hematite, zerovalent iron, magnetite and engineered iron- organic resins. Organic ion-exchange resins (IERs) are utilised for
silicalites17,19,21,38,39. Of these, magnetite (Fe3O4) is among the controlling radioactivity within nuclear power plants, particularly
most promising, featuring a spinel structure (AB2X4), containing steam condensate polishing, primary coolant purification, cooling
both Fe2+ and Fe3+ sites. The flexible spinel structure opens up pond activity control and (coupled with organic acids) corrosion/
the option of co-doping20. Iron oxides with Co2+, Cu2+, Cr2+ and activation product removal. Their specific usage governs the
Mn2+ in place of Fe2+ can increase reactivity17,38. Doping onto the radioactivity within the spent resins, though common radio-
Fe3+ site with Cr3+, V3+ or elements with a higher charge and nuclides within spent resins include 137Cs, 90Sr, 60Co, 59Fe, 54Mn,
14
similar ionic radii like Ti4+ and Nb5+ have also shown improve- C and 3H52,53. Typically, these resins are granular (or sometimes
ments. These improvements have been proposed to be due to powdered), highly dispersible material which often require
thermodynamically favourable redox pairs (Fe3 /Fe2+ and Mn+/Mn immobilisation per national guidelines prior to disposal.
+1
), and the generation of oxygen vacancies, which at the catalyst Many modern routine usage ion-exchange resins for the nuclear
surface aid in radical production20,38,40. industry consist of either strong cation or strong anion resins, with
Other hetereogeneous catalysts include clays (often pillared to sulfonated (as H+, Fig. 1) or quaternary ammonium (as OH−)
make them reactive), hydrotalcites intercalated with transition functional groups, respectively. These functional groups are
metals (e.g. Cu/Al-LDH), zeolites (e.g. Fe exchanged ZSM-5), usually on a backbone of a crosslinked styrene-divinylbenzene
transition elements embedded on silica/alumina supports, among polymer (DVB), with specific crosslinkage and chemistry varying
others16,19,21,41–44. Cu, Mn, Co and Cr oxide minerals all find usage, between manufacturers. Although sometimes used separately,
although the toxicity of the latter two limits usage other than as many applications of these resins are as a mixed bed of anion/
minor dopants10,25. Although typically a transition element, a few cation resins combined, though targeted applications (such as Cs
other elements can find usage as catalysts. Cerium has come to abatement in cooling pond water) may favour cation selective
attention due to Ce3+ /Ce4+ cycling45. With CeO2 this forms a resins. The quantity of these materials produced, and the
peroxide-like species on the surface, limiting reactivity; however,
pre-treating with sulphuric acid has shown to create a reactive
surface10,46. Aluminium (especially as zerovalent Al) can be
utilised, although typically requires a pH lower than 4 or Al2O3
can form on the surface, limiting reactivity10.
Other than varying the catalyst chemistry or physical properties,
coupling a Fenton reaction with an external source of UV light
(photo-Fenton) has proven to be a popular method for enhancing
degradation of various wastes. Typically, either a UV lamp or solar
light is utilised to photo-reduce Fe3+ to Fe2+, assisting the
removal of a bottleneck within the traditional Fenton process. This
appears to be particularly effective if degradation products (such
as carboxylic acids) form Fe3+ complexes47–49. UV radiation can
also directly cause photodegradation of organic contaminants,
and at wavelengths less than 260 nm can also cause photolysis of
H2O210,16,19. Although successful, limitations of this method
include the extra equipment required to operate, issues with
efficiency in heavily polluted waters or due to particulate matter
blocking light.
Other less well developed Fenton-like systems exist, typically
relying on an additional external source of energy to enhance
degradation. Electro-Fenton utilises a potential passed between
an anode and cathode, resulting in continuous in situ generation
of H2O2 and anodic oxidation of organic matter10,19,50. Sono-
Fenton harnesses ultrasonic waves to enhance HO* generation,
and creating cavitation bubbles which can assist degradation of Fig. 1 Structure of a crosslinked polystyrene divinylbenzene ion-
pollutants (especially hydrophobic chemicals)10,19. Furthermore exchange resin. Structure shown as sulfonated in H+ form.

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 S.A. Walling et al.
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opportunities for substantial volume reduction if treatment is the ratio of catalysts (if using more than one catalyst), and
successful has in part driven research into Fenton-like oxidation of whether any pre-equilibration was undertaken between the resin
spent organic ion-exchange resins. and catalysts. This presents a multi-dimensional and interdepen-
Overall, the Fenton-like oxidation of organic IERs can be very dent set of reaction variables, with difficulty in recommending an
effective, with reported reductions in organic carbon of >98%, ‘ideal’ concentration, but certain trends are evident for the
with the capability to just use a source of Fe, H2O2 and some pH multitude of data.
control. Resulting liquids are normally neutralised, resulting in a First, pre-equilibration of resins with at least some part of the
sulfate rich product, along with the precipitation of many catalyst solution often results in faster degradation times
radionuclides. Shorter treatment times typically result in a higher (especially for cationic resins) and a reduction in foaming
residual organic content, and a higher presence of lightweight observed (notably for anionic samples). Recommended pre-
organic species, which appear relatively resistant to Fenton soaking times vary from 15–30 min12,58 to 20–24 h13,55. For anionic
oxidation. The mass balance for wet oxidation of a typical cation resins, the addition of citric acid during pre-soaking has been
styrene-divinylbenzene ion-exchange resin can be split into the utilised to firstly acidify, and secondly claimed to result in chelated
oxidation of a styrene monomer (Eq. 11) and a divinylbenzene catalyst ions binding to anion-resin functional sites due to anionic
monomer (Eq. 12), with the degree of crosslinkage formed via metal citrate species56,58–60. These methods are likely to increase
additions of DVB within the resin directly affecting H2O2 Fenton-like reactions occurring at the resin surface, rather than in
requirements the bulk liquid, and increase the efficiency of initial resin
breakdown. However, due to a risk of catalyst chelation by
C8 H8 þ 20H2 O2 ! 8CO2 þ 24H2 O (11)
degradation products, it is sometimes favoured to pre-equilibrate
with some catalyst, then continuously feed remaining catalyst
C10 H10 þ 25H2 O2 ! 10CO2 þ 30H2 O (12)
throughout the reaction12,55
Functionalisation of resins to form strong cation and strong Strong evidence exists for an optimal concentration of catalyst,
anionic resins will affect this degradation, Eqs 13 and 14 detail with numerous studies finding enhanced dissolution with
idealised oxidation of a styrene monomer with function sulfate increasing catalyst concentrations, which hits a maximum before
and quaternary ammonium groups, respectively. dissolution declines with further increases in catalyst concentra-
tion. This could be due to wasteful H2O2 decomposition within
C8 H8 SO3 þ 20H2 O2 ! 8CO2 þ H2 SO4 þ 23H2 O (13)
bulk liquid, rather than at the resin surface with increased catalyst
concentrations. For example, Xu et al found a 0.3 M Fe2+ catalyst
C12 H19 NO þ 31H2 O2 ! 12CO2 þ NH4 OH þ 38H2 O (14)
performed better than either 0.1 or 0.5 M catalyst for cationic
Degradation of cationic resins can result in a drop in pH due to resins (Fig. 2a)57, resulting in earlier resin breakdown and lower
release of sulfuric acid (but also due to acidic short chain organic final COD values, whereas de Arujano found 50 mM FeSO4
species). Degradation of anionic resins, detailed in Eq. 14, releases resulted in more effective degradation than 25 or 100 mM for
alkali species into solution (i.e. NH4OH), though in the boiling mixed resins12. Precise catalyst strength varies greatly, dependant
solution this is likely to result in outgassing of ammonia and on the amount of catalyst added, specific molarity, quantity of
overall result less effect on pH. resin, amount of other liquids present, temperature of decom-
A typical Fenton oxidation setup for wet oxidation of resins position and the time of decomposition. The latter of these—time
consists of a reactor vessel (often glass) into which ion-exchange —appears to have a great effect when determining an ‘optimum’
resins are added. To this both a catalyst and H2O2 are added, catalyst concentration. An optimum level of catalyst is often
either initially or slowly over several hours, with the mixture determined by varying molar concentrations of catalyst, running
agitated (often magnetically or with forced air bubbling) and the an experiment for a set time, and comparing COD/TOC values of
whole vessel heated. A distillation head is typically present in resultant liquors. Often these results show a continued downward
larger studies (and pilot-plant applications), either refluxing trend in COD/TOC values with time—indicating even a suboptimal
condensed liquids back into the reactor, or distilling these into a level of catalyst might result in similar COD/TOC values if
separate collection vessel. On pilot plants an off-gas system is experiments were undertaken for slightly longer12,58,61, although
connected to the system to scrub ammonia and any radionuclides with an obvious increase in peroxide usage and time taken to
evolved, whereas in laboratory scale these typically exist solely to degrade resins. An optimum catalyst also needs to take into
capture evolved carbon within alkaline traps for quantification. account any risks of aggressive reactions, as higher levels of
Resins are usually fully solubilised (if not fully mineralised), with catalyst additions to anion resins in particular have been shown to
inorganic residues precipitating at the bottom of the reactor risk excessive foaming62. Further problems occur when trialling
vessel. Within pilot plants these residues and any supernatant are ‘real’ active resins, due to the concentration and variety of metal
typically neutralised, with the resultant slurry to be encapsulated ions accumulated during operation. Co substituted resins have
(often within a cement). resulted in lower final COD values than raw resins57, while during
In general, Fe is utilised with H2O2 as an effective catalyst for larger pilot-plant trials the presence of V appears to reduce
ion-exchange resin oxidation reactions, particularly for cationic efficiency, and overall real resins display an increased tendency to
resins11,54–57, with input often as FeSO4·7H2O dissolved into a foam compared to inactive simulants63,64.
solution to a specific molarity. For anionic or mixed anionic/ The tendency to froth or foam is not just restricted to active
cationic resins the usage of either Cu or a combined Cu:Fe catalyst samples. Raw cationic resins degrade relatively easily; however,
has widely been found to be the most effective13,54–56,58—with anionic and mixed cation:anion resins show a marked tendency to
the usage of Fe alone not producing the lowest chemical oxygen froth and foam during degradation56,62,65. The reason for this is
demand (COD) values. Other catalysts have found some usage, not fully understood, although release of ammonia during
with mixed Mn:Cu and Ni:Cu catalysts also effective for anion-resin degradation has been postulated to cause foaming62,65. The
degradation55. A table of key reference papers which tackle IER dosing of small volumes of organic anti-foaming agents (silicon
degradation are listed in Table 1. based, or tri-butyl phosphate) has been successful in reducing
The optimum amount of catalyst to add within these reactions foaming56,58,62, as has pre-soaking resins with citric or acetic
is a complicated issue, as results vary by molar strength of catalyst acid58,65.
solution, amount of catalyst added to weight of resin, whether the The optimum amount of H2O2 to add into these reactions is a
catalyst is added at the start of reaction or continuously particularly difficult assessment. Resins are shown to degrade
throughout (and if added continuously, at what feeding rate), more quickly with faster additions of H2O2, with an overall lowest

npj Materials Degradation (2021) 50 Published in partnership with CSCP and USTB
 S.A. Walling et al.
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Table 1. Ion-exchange resin papers (homogeneous).

Ref Catalyst Oxidant Notes (all dark Fenton unless Waste

specified)

Zaharodna et al.67 FeSO4·7H2O H2O2 (15%) No reflux/condensation Cation resin:

(Fe) Continuous 40–60 °C Amberjet 1500H
additions
Zaharodna et al.68 FeSO4·7H2O H2O2 (15%) Dark and UV photo-Fenton Cation resin:
(Fe) Continuous No reflux/condensation Amberjet 1500H
additions 50 °C
Gunale et al.73 CuSO4, FeSO4 H2O2 (30%) Pre-processing for O2 wet oxidation Cation resin:
(Fe, Cu) Batchwise second step INDION-223H
additions 95 °C
Wan et al.58 CuSO4·5H2O, FeSO4·7H2O H2O2 (30%) No reflux/condensation Anion resin:
(Fe, Fe + Cu) Bulk at start 95 °C Amberlite IRN 78
Xu et al.61 CuSO4·5H2O H2O2 (30%) No reflux/condensation Cation resin:
(Cu) Continuous 95 °C Amberlite IRN 77
additions
Xu et al.57 CuSO4·5H2O, FeSO4·7H2O H2O2 (30%) Vapour condensation outside Cation resin:
(Fe, Cu) Bulk at start reactor ZG C NR 500
60–90 °C
de Araujo and FeSO4·7H2O H2O2 (25%) No reflux/condensation Cation + anion resins:
Marumo12 (Fe) Continuous 40–60 °C Amberlite IR 120 + Amberlite IRA 410
additions
Feng et al.54 CuSO4·5H2O, FeSO4·7H2O, H2O2 (30%) No reflux/condensation Mix of cation and anionic resins:
FeCl3, Fe2(SO4)3, iron powder Continuous Amberlite IRN 77 + Amberlite IRN 78
(Fe, Cu, Fe + Cu) additions
Kubota11 Fe3+ H2O2 (9–18%) No reflux/condensation in main Cation:
(Fe) Bulk at start degradation system Dowex 50 W X8
Wan et al.66 CuSO4·5H2O, FeSO4·7H2O H2O2 (30%) Condensation apparatus on CO2 Cation:
(Fe, Cu, Fe + Cu) Continuous collection system Amberlite IRN 77
additions 60–97 °C
Wu and Wu65 CuSO4, FeSO4 H2O2 (60%) Influence of varying acids Cation: Purolite NRW-100
(Fe—cation only, Cu— Continuous Reflux Anion: Purolite NRW-400
anion only) additions 97–102 °C
Anti-foaming agent
Feng et al.69 FeSO4·7H2O H2O2 UV photo-Fenton Cation: Amberlite IRN 77
(Fe) (30%) 100 °C
Continuous
additions
Kim et al.189 CuCl, FeSO4 H2O2 (28%) Electro-Fenton Cation: Amberlite IRN 77
(Fe, Cu, Fe + Cu) Continuous Reflux
additions 80–100 °C
Huang et al.190 FeSO4·7H2O H2O2 (50%) Fluidised bed reactor Cation: Purolite NRW−100
(Fe) Continuous 75 °C
additions

resulting COD when higher total quantities of H2O2 are added (e.g. consistently found near-boiling temperatures to produce the most
as shown in Fig. 2b)11,57,65. The more quickly H2O2 is added, rapid and efficient degradation of resins. Temperatures lower than
however, the more likelihood of parasitic side-reactions and for 90 °C have consistently resulted in higher final COD values, and
H2O2 wastage, both not only increasing overall cost but also sometimes incomplete resin degradation54,56–58,66. Helpfully, once
increasing the volume of resultant liquid effluents. The final initiated, the degradation of IERs is heat-generating, sometimes
acceptable TOC/COD values for a liquid effluent also plays an resulting in self-sustained heating during much of the reaction
important role, as driving these values down lower will require time57—especially for larger industrial-scale setups13. Though
more H2O2 even after complete resin degradation—with dimin- concerns have been raised that higher temperatures will
ishing returns and higher H2O2 wastage as TOC/COD values are encourage thermal breakdown and wastage of H2O212, studies
lowered, especially if the resultant effluent contains a high have shown a higher release of O2 at 83–93 °C compared to
proportion of difficult to mineralise organic material. This is 90–99 °C, and a lower CO2 release at the lower tempera-
clearly illustrated in Fig. 3, where continued degradation of resins tures55,56—emphasising the benefits of higher temperature
and associated CO2 release reaches a crossover point with O2 reactions.
release from H2O2 breakdown, indicating the increasing wastage The effect of pH on degradation of IERs is not clear cut. Due to
of H2O2 the longer reactions proceed. the high organic loading during decomposition of these materials,
Degradation temperatures play a pivotal role in the efficient and the interplay between acidic organic products, sulphuric acid/
degradation of IERs, with utilised temperatures often much higher ammonia generated during decomposition, the pH can alter
than many Fenton oxidation studies for conventional wastewaters significantly during degradation. Without altering pH before or
or pollutants. Degradation of IERs using Fenton-like reactions has during reaction, Jian found cationic resin degradation to result in a

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 S.A. Walling et al.
6

Fig. 2 Varying experimental parameters to enhance degradation. Effect of catalyst (Fe2+) dosage (a), and H2O2 additions (b) on IER
degradation at 75 °C, adapted from data in Xu et al.57. Variables fixed at 75 °C, pH 0.01, 200 mL H2O2 addition and 0.3 M Fe2+ unless the
variable is under investigation.

Fig. 3 Variation in gas evolution over time during ion-exchange resin degradation. Release of CO2 and O2 measured by Geng. et al.56 (a)
and Jian et al.55 (b). Results adapted from sources for comparison.

final liquor pH of 1.0–1.5, anionic resins pH 4.0 and mixed resins control has not been definitely decided—it seems likely that
pH 2.055 (although Srinivas found cation residual liquids to be pH decomposition of resins impose their own pH regime, although
2–3, anion resins pH 6–7, and mixed resins pH 262). Due to the many researchers promote the addition of citric acid to resins
issues with recording accurate pH levels (and constant adjusting) (especially anionic resins, but also cationic), which is likely to result
during reactions (near boiling, high turbidity, etc.), many in a pH of 2–356,58.
researchers adjust the pH before reactions commence. Some The destruction of ion-exchange resins is a multi-stage process,
adjust, and find best results at pH 2–354,56,58,67, others much lower likely consisting of varied reactions at ion-exchange sites,
(down to 0.01)57,61, some at circumneutral pH12,62. Feng found destruction of the linear polymer backbone, and oxidation of
initial pH of 2 resulted in highest COD removal, but pH of up to aromatic components. Once reactions have started, resins are
6 still resulted in >90% COD removal over the same time for fairly rapidly degraded into soluble products, often with a solution
cationic resins—with pH of 1, 2 and 3 all performing similarly for colour change56,57. Degradation of cation resins has been the
anionic resins at 180 min reaction time54. Overall the issue of pH most studied, with desulfonation of these resins the first step in

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 S.A. Walling et al.
7
oxidative decomposition. A degradation plateau can occur after organic calcium salts can equally enhance cement setting, such as
desulfonation, suggesting complexation of Fe by organic acids calcium formate88,89—these could become issues if high levels of
inhibiting Fe3+–Fe2+ reduction, and thereby limiting further organics remain after oxidation.
reactions if Fe content is low. Analysis of liquids reveals a wide
array of lower molecular weight organics are detected during Decontamination liquid wastes
decomposition, including succinic, maleic, acetic, oxalic and formic
Chemical decontamination of nuclear facilities (either routine, or
acids—along with terephthalic acid from crosslinking68. Formic
post-operational) typically utilises organic chelating agents within
and oxalic acid were the two most abundant degradation
an aqueous medium to remove activation products from nuclear
products identified, with formic acid predominating at lower
facilities (such as those arising from activation of stainless steel/
catalyst concentrations where dissolution was incomplete, and
oxalic acid more prevalent at higher catalyst concentrations after nickel alloys, fuel cladding, etc.), potentially resulting in iron and
almost complete desulfonation occurred68. Feng separately found transition metal rich organic wastestreams53. Depending on the
oxalic, formic, acetic and propionic acids as degradation products nature of the chelating agent used (e.g. EDTA, citric acid, oxalic
(with oxalic acid resistant to further oxidation)69. acid, picolinic acid, etc.), these may be suitable for wet oxidation,
These degradation products fit well with extensive literature on though some, particularly oxalic acid, can be relatively resistant to
Fenton oxidation of aromatic substances, particularly phenolic conventional Fenton oxidation processes.
substances, where carboxylic acids are known to be end Direct wet oxidation of organic complexants in radioactive
products49,70. Fe is known to be lost from the system via waste has not been widely studied; however, a wide range of
complexation with these organic acids, affecting redox cycling literature related to wet oxidation of organic compounds exists for
and reducing achieved mineralisation. Work to improve this non-radioactive wastes, particularly as many occur as intermediate
includes photo-Fenton to regenerate iron47–49, increasing reaction or final decomposition products of wet oxidation of other
temperatures beyond 100 °C71,72, or coupling to a high pressure/ pollutants. It is commonly found that low molecular weight acids
temperature wet-oxidation system73,74. (LMWA—maleic, oxalic, acetic, formic, etc.) build-up with dark
The final degradation products from ion-exchange resin Fenton, affecting final achievable organic mineralisation levels.
treatment usually require disposal or further treatment. A typical These and their Fe(III) complexes only weakly react with HO*90,
homogeneous wet-oxidation setup can result in the formation of and have been shown to form as decomposition products from a
iron hydroxide sludges from catalyst precipitation; however, spent wide range of compounds including (and not limited to)
ion-exchange resins will also contain various radionuclides, phenol49,91,92, nitrophenol70, ethylene glycol93, sawmill waste-
dependant on usage. Resins from fuel cooling ponds will likely water94, H-acid95 and ion-exchange resins68,96.
contain Cs and Sr, whereas resins for purifying steam turbine Various improvements have been sought to enhance the
water might contain more dissolved metallic ions such as Fe, Ni degradation of these acids. They can be almost completely
and Co. Neutralisation of waste liquors can encourage precipita- mineralised with a photo-Fenton process47,49,68,70,90–93,97 or solar
tion of some radionuclides as lower soluble hydroxides, with solids electro-Fenton process98, forming only as intermediate com-
and liquors (or partially dewatered solids) immobilised within a pounds during reactions. Research into oxalate and other LMWAs
cementitious matrix12,13,75,76. Neutralisation is also favoured to has also been spurred by their utilisation to improve the photo-
enable compatibility with alkali cement powders and ensure a Fenton process, (e.g. via Fe(III)-oxalate reduction to Fe(II) under
stable product. specific UV/light irradiation), including extension of photo-Fenton
The presence of small quantities of these metal hydroxides are to more neutral pH ranges48,99–101. Another route to increase
unlikely to cause issues for cemented products; however, cation degradation has been to increase reaction temperatures. Although
resin degradation results in a high level of sulfate residues left not as reactive to dark-Fenton processes, LMWAs can be more
after oxidation. Sulfates will greatly affect the setting character- readily degraded with an increase in temperature towards
istics of cements, with sodium and ammonium sulfates known to 70–90 °C42,71, with even better mineralisation if able to reach
scavenge Ca to form gypsum (CaSO4·2H2O), lengthening setting 120–130 °C71,102. Equally, different catalysts can also have an effect
times and deleteriously affecting longer-term strength77. If sulfates on LMWA degradation, with most research being undertaken
are neutralised to calcium sulfates, these may also react, as they using Fe catalysts. Research suggests Cu(II)-carboxylate complexes
are known setting regulators in Portland cements. Small quantities are more easily attacked, accelerating mineralisation23,98,103.
of calcium sulfates (gypsum, hemihydrate and anhydrite) are Mixed Fe–Cu–Mn catalysts have shown good results over a range
interground during cement manufacture to regulate tricalcium of organic acids, with Mn performing particularly well with oxalic
aluminate setting (Ca3Al2O6, a component of cement clinker), with acid, especially when coupled with elevated temperature31,104.
the complicated interplay (and dosage) of these various sulfates Less studied is degradation of EDTA; however, this appears to
helping to avoid both flash and false setting78–80—addition of be capable of at least partial mineralisation utilising both
calcium sulfates from wastes may upset this balance. Large conventional and hetero-, photo- and sono-Fenton process,
additions of calcium sulfates can cause later expansive reactions including with recovery of complexed elements (i.e. Tl, Ni, Co)
through formation of excessive quantities of ettringite from the resulting treated water47,105–110. This has been particu-
(Ca6Al2(SO4)3(OH)12·26H2O)81, although cements blended with larly demonstrated via the removal of radioactive 60Co from EDTA
high quantities of blast furnace slag are typically more resistant82. solutions utilising a heterogeneous Fenton reaction with an iron-
Certain types of ‘supersulfated’ cements with very high slag silicate catalyst39
contents make extensive use of calcium sulfates as an integral part Research on simulant and real radioactive waste effluents
of the hardening process83,84, though these are not conventionally containing organic acids and chelating agents generally result in
utilised materials. high levels of organic destruction13,111–115. Utilising a combined
Equally, any residual organic material left after oxidation may Fe–Cu catalyst, JGC claim 97–100% decomposition of EDTA,
interact with cementation reactions, either as free carboxylic acids, formic, citric and oxalic acid at temperatures up to 100 °C114.
or as salts (i.e. oxalic acid or calcium oxalate if neutralised with Ca Lower levels of mineralisation (although still >80%) have been
(OH)2). Oxalic acid is known to accelerate cement setting and reported for dark-Fenton trials by KAERI for oxalic acid, ascorbic
increase the heat of hydration via enhancing alite (Ca3SiO5) acid and EDTA decontamination solutions, utilising an Fe catalyst
dissolution from the cement clinker, with precipitation of calcium at 90 °C115. This system was improved with the addition of a UV-
oxalate monohydrate85–87. Additions of calcium oxalate itself are TiO2 system post-treatment, greatly reducing residual organic
unlikely to affect cement due to low solubility, but more soluble contents115.

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 S.A. Walling et al.
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Contaminated solvents Other wastes
Fenton processing of radioactive solvents and co-occurring A few other radioactive wastes have been trialled for Fenton
chemicals typically fall into two categories: treatment of oxidation. Cellulose wastes, in the form of contaminated
research/medical/industry solvents, or treatment of spent nuclear protective clothing126, filter aids/precoats127,128 and paper—
fuel reprocessing solvents. although often co-mixed with other wastes13. Small-scale pilot
The former of these: non-reprocessing solvents, includes a wide trials treating mixed organic ion-exchange resins and cellulosic
range of organic materials such as toluene, acetone, liquid filter aids have been successful127,128. Laundry waste from a
scintillation cocktails, chlorinated solvents, etc. These are often Finnish nuclear power plant were also trialled for Fenton
complex mixtures from a variety of sources. There have been treatment. These wastes contain organic surfactants, along with
several trials utilising scintillation wastes13,116, toluene116, acet- associated radioactivity. Utilising a dark-Fenton process up to 70%
one116 and chlorinated solvents mixed with oils (with biodegrada- COD/TOC reduction was possible129.
tion after to destroy oil)117. High levels of carbon reduction have
been claimed, though increasing volatility with higher tempera- NUCLEAR APPLICATIONS—PILOT-PLANTS AND
ture processing affected toluene degradation116. INSTITUTIONAL TRIALS
Destruction of spent nuclear fuel reprocessing solvents has
Outside of academic research, several national nuclear research
been subject to more extensive research. Typically, the wastes are
institutions and companies around the world have trialled larger-
a combination of a solvent (tri-butyl phosphate (TBP), dibutylpho-
scale applications of Fenton processes to specific nuclear wastes.
sphate (HDPB), tricapryl amine (TAA), tri-n-octylamine (TAA)) and This has resulted in several pilot and small-scale plants utilising
either kerosene (OK), n-dodecane, or other alkyl aromatic Fenton chemistry being commissioned, all using homogeneous
hydrocarbons. Techniques for treating these consist of either catalysis. Substantial interest was garnered from the 1980s
treating as a whole118–121, or initial distillation to remove less through to the 2000s, with strong interest from Sweden, Italy,
reactive hydrocarbons prior to Fenton reaction76,122. Some UK, USA and Japan. Overall none of these trialled systems appears
research has been undertaken on removal of TBP from waste- to have entered full commercial operation outside of limited
waters containing surfactants123. testing, although significant experience and knowledge has been
Overall Fenton oxidation is capable of successfully destroying acquired from these research programmes.
the solvents TBP, HDPB, TCA and TAA at temperatures ~100 °C,
typically with an iron catalyst118–122,124, though a chromium Sweden
catalyst has been trialled125. TBP degradation results in decom-
One of the earliest Fenton wet-oxidation plants mentioned in
position to CO2, inorganic phosphates (postulated as iron
open literature was the ASEA-ATOM/Vattenfall pilot plant in
phosphate), and phosphoric acid118,119. Degradation of combined
Sweden, operating in the 1980s75. This consisted of a pilot plant at
TBP/OK has reported to result in the formation of acetic acid, 50% scale, capable of handling 100 kg of waste at a time, with a
n-hexadecanoic acid, small amounts of formic acid, and other focus on spent ion-exchange resin treatment resulting from
minor organics. More volatile species are found in condensate commercial operation of light water reactors. The plant imple-
liquid, including phosphoric acid, acetone, butanal and acetalde- mented a conventional homogeneous Fenton system, utilising
hyde119—other researchers have also found some oil/TBP carried sulphuric acid to lower pH, heating to 90 °C, adding a ferrous
over from the reaction solution121. Kerosene and n-dodecane sulfate catalyst, and continuously applying H2O2 over a 5 h
often remains atop the reaction solution, with little reactivity, even reaction time (at least during cold testing). Details of experimental
if well emulsified118. conditions discussed in their patent are in Table 2.
No widespread treatment of any solvent wastes with Fenton In addition to cold tests, several different active wastes were
oxidation is currently operational; however, Italian researchers trialled. These comprised Cs/Sr selective IER media from the
undertook pilot-plant trials for spent reprocessing solvent Forsmark nuclear power plant (treated successfully with no
destruction, described in more detail within the country specific detected radioactivity carryover to off-gas system), and resins
sections. from the startup of the Italian Caorso BWR nuclear power plant.

Table 2. Summary of experiments undertaken by ASEA-ATOM and ENEA.

Waste Active Oxidant Catalyst pH Temp Duration

ASEA-ATOM
130,131
IERs (100–500 g L−1 water) N H2O2 (50%) Fe3+ (sulfate, nitrate, or Initial 2 100 °C ’some hours’
25–50 g kg−1 IER acetate) using H2SO4
Continuous addition 5-20 g kg−1 IER
ENEA
76
Simulant reprocessing waste N H2O2 (40%) FeSO4·7H2O – – –
18–25 kg L−1 organic waste 20 g L−1 waste
76
Active reprocessing waste Y H2O2 (40%) Ferrous sulfate – 100 °C –
(100 mL) 100 mL h−1 (cont feed) 20 g L−1
120
Simulant solvent waste N H2O2 (36%) FeSO4·7H2O addition of 100 °C –
(5 L) 55 L @ max 10 L h−1 100 g each cycle × 3 cycles H2SO4
118
TBP-n-dodecane mix N H2O2 (36%) Varying catalysts: – – –
Varying ratios of organic to None,
H2O2 CuO–Cu2O,
2−30 mL h−1 Pt-C,
FeCl3
118
n-dodecane N H2O2 (36%) FeSO4·7H2O – – –

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The latter waste comprised 10 × 200 L drums of resin, resulting in wet oxidation, and cement encapsulation of the residues from this
1 drum of treated, cemented product. Post-treatment, the process to form a disposable product. Hot distillation trials using
resultant liquor has its pH raised to 9.5–11 with either NaOH, 5 L of real solvent material (total α/β: 900–950 kBq L−1, total γ:
KOH or NH4OH, resulting in precipitation of the poorly soluble 222 kBq L−1) were successful, resulting in the majority of activity
transition metal hydroxides, which comprise the core of the remaining in solvent waste / residue—rather than in the distillate
radioactivity within these resins130,131. This leaves a sulfate rich (allowing for distillate incineration)76,122.
supernatant, along with radio-caesium and strontium, which Benchtop wet-oxidation trials began with inactive simulant
requires disposal. The disposal solution was to either add excess material, resulting in >95% organic removal with an iron catalysed
of non-radioactive strontium or barium (SrSO4/BaSO4 solubility is system (FeSO4 + H2O2), although with a high TOC remaining in
limited, an excess of Sr/Ba would likely coprecipitate radio- the aqueous distillate. The researchers noted that vigorous stirring
strontium as a sulfate, removing it from solution), or to elute this is necessary, and that 2–3% of the initial volume remains as a
supernatant through Cs/Sr selective IER. This was claimed to only viscous unreactive residue after treatment76,136. Post-treatment
use a small capacity of the IER resin, resulting in only minor waste solutions were neutralised with NaOH, followed by addition
additional wastes75,130,131. The resulting waste residues were of Ca(OH)2 to precipitate sulphates and phosphates. Cement
immobilised within a cement, with a claim of high volume powder was added to the solutions, and rapidly solidified (in a few
reduction compared to conventional cementation of Swedish minutes). Benchtop active trials followed in three batches, using
nuclear power plant resins, with a proposed volume reduction of a 100 mL real waste each. In this setup, the distillate was condensed,
factor of 1575. with the aqueous phased collected, and the organic phase
recirculated to the reactor. Mixing was undertaken using N2
Italy bubbling, though this did not result in vigorous mixing, and was
believed to affect the final result of only 80% organic removal76,136
The problem of spent ion-exchange treatment spurred Italy into
A summary of experimental conditions for these, and previous
developing wet oxidation from the late 1980s. Spent IERs
trials are noted in Table 2.
consisted a large fraction of radioactive wastes from NPPs in Italy,
A full-scale treatment plant was planned, utilising the same
with a BWR plant (Montaltao di Castro NPP) scheduled to come
reactor for both distillation and later wet oxidation (plant scheme
online in 1988. Due to disappointment with direct cementation of
shown in Fig. 4). The overall proposed mass balance for the EUREX
resins, the option of wet oxidation was explored for volume
waste was 25 m3, distilled to 3 m3 of organic residue (for wet
reduction132. An added advantage was the option to re-treat
oxidation) and 22 m3 organic distillate (mostly kerosene, tri-
spent IERs from the Caorso NPP. Those resins were partially
methylbenzenes and some small percentage of TBP, for incinera-
treated with a urea-formaldehyde process, which by 1987 were
tion). Wet oxidation would result in 6 m3 aqueous residue
unable to conform to incoming regulations, with re-conditioning
(containing almost all the activity, for cementation), <150 L
required. To realise this goal, an industrial development program
viscous organic residue, ~50 m3 aqueous distillate, and a yet to
was funded by ENEA’s Industrial Promotion Programme (with
be determined volume of scrubbing solution from off-gas
FBM-Hudson Italiana as industrial partners) from 1985. A pilot
treatment76. Plans for a plant were described, althought it does
plant was envisaged, operating up to 100 kg dry resin in each
not appear that the wet oxidation programme progressed further
batch, at the cost of 6000 million Lire (US$ 4.5 million), with a
than these hot benchtop trials.
startup of 1990 planned132. Construction of demonstration plants
due in this programme (for 1987) were deferred due to the
Chernobyl accident, and the programme does not appear to have UK
been restarted. The UK has over the years been one of the more enthusiastic
In 1989 ENEA looked again at wet oxidation, undertaking proponents of wet oxidation. Research into application of this to
several studies into the destruction of other organic materials, UK wastes has taken two paths—a chromium catalysed system for
including olive processing wastes, atrazine, PCBs and solvent destruction of waste alkyl phosphate (e.g. tri-butyl phosphate
wastes, to determine if this treatment method might find (TBP)) from fuel reprocessing, and a more conventional iron
application for additional wastestreams in Italy118,120,133. These catalysed system for spent ion--exchange destruction, the latter of
studies led onto inactive and active trials of homogeneous wet which has resulted in various research programmes and pilot
oxidation for the destruction of waste reprocessing solvents, for plants over several decades.
which a disposal route had not been decided. This waste resulted Research into a Cr catalysed system is first recorded in a patent
from the EUREX pilot nuclear reprocessing facility at Saluggia in granted to Interox in 1988, detailing the usage of hydrogen
Italy, which operated from 1970–1983, during which 600 materials peroxide and sodium/potassium chromate for destruction of alkyl
testing reactor elements from national research reactors, and 1.5 phosphates mixed with hydrocarbons (TBP in OK (odourless
tonnes of irradiated CANDU fuel were reprocessed134,135. After kerosene) is one example detailed), operating at slightly lower
closure of this facility, 25 m3 of spent reprocessing solvents temperatures (65–75 °C), below the flash point of the hydrocarbon
required disposal, comprising a mixture of tri-butyl phosphate, solvent125. This was claimed to only degrade a small amount of
tricapryl amine, kerosene and various alkyl-benzene isomers76,122. the hydrocarbon, allowing incineration afterwards. A range of
ENEA noted that incineration of these wastes would be catalysts were tested, including Fe, Cu, V, Co, W, Mo, Ru, Mn and
challenging due to corrosion from phosphoric acid resulting from Cr, with Cr showing superior performance. With pH control to 7.0
tri-butyl phosphate destruction, a problem which had stimulated the authors claim 99% TBP destruction with usage of K2CrO4, with
research into alternative disposal process across Europe. At that a small-scale active test retaining 99% of radioactivity within the
time, various alternative technologies existed for the treatment of aqueous phase125.
similar wastes, including the EuroWatt Process (BE) for pyrolysis, British Nuclear Fuels Limited (BNFL) also similarly undertook
and the Silver II electrochemical process undertaken at Dounreay research on alkyl phosphate degradation with a chromium
(UK). ENEA decided to trial a multi-stage process of distillation, Fenton-like process, following the cessation of sea discharge of
followed by wet oxidation, coupled with incineration and waste reprocessing solvents in 1983137. This culminated in two
cementation76. As the distribution of radionuclides was not patents in 1992 and 1996 which utilise a chromium catalyst, but
homogeneous within these mixtures, distillation would allow the claim various claimed improvements. The first utilises NaOH to
re-routing of low contamination kerosene to conventional hydrolyse the alkyl phosphate, before decanting the hydrocarbon
incineration, with contaminated remaining solvents undergoing solvent (reducing fire hazards—peroxide and hydrocarbons

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 S.A. Walling et al.
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Fig. 4 Simplified plant scheme for ENEA distillation/wet-oxidation system76. Fig. notations: R—reboiler for distillation and reactor for wet-
oxidation. CR—packed column for distillation. C—condenser. SR—phase separator to allow recirculation of various liquids. CL—washing
column for off-gas. S1—waste feed tank. S2—H2O2 storage tank. S3—organic residue tank (interim waiting for wet oxidation). S4—aqueous
residue tank (interim from wet-oxidation, awaiting cementation). S5—organic distillate interim storage (for incineration). S6—aqueous
distillate interim storage (for discharge). Reproduced with permission from ref. 76, copyright (EC, 1995).

boiling together were not deemed to be acceptably safe)138. The

sodium alkyl phosphate is then oxidised with peroxide and a
combined Cr + Cu catalyst (combined Cr with V or Fe are also Table 3. Input/output for proposed CEGB wet-oxidation plant64.
suggested, but not as effective) at circumneutral pH. The second
patent applies the chromium/peroxide oxidation process to Inputs Outputs
organic complexants in aqueous solution (e.g. EDTA and citric 3
1 m Lewatit resin 950 kg CO2
acid) and BUTEX reprocessing solvent, with a suggestion that Cr
could converted to Cr(III) and precipitated after post-processing to 2 m3 water 400 kg O2
avoid environmental discharge139. None of these processes found 10 kg FeSO4 6300 kg steam
widespread usage in treatment of waste reprocessing solvents, 5000 kg H2O2 60 kg NaSO4
with further research into wet oxidation in the UK focussing on 60 kg CaSO4
volume reduction of solid organic materials. 10 kg Fe2O3
In the late 1980s, the Central Electricity Generation Board (and
later, its successor company, Nuclear Electric) began looking for 300 kg water
technologies for treatment/disposal of spent ion-exchange resins Final product
accumulating at nuclear power stations in the UK. This was both 730 kg BFS/OPC 0.6 m3 wasteform
with the aim of volume reduction, and to address concerns about
the potential for organic material to enhance radionuclide
and were stored in tanks on-site. They comprised 65% powdered
mobility in a waste repository140. The preferred method was
ion-exchange resins (Powdex, 2:1 cation:anion), 20% hydrated
cementation, but wet oxidation was studied as a contingency,
with a preference for a mobile plant where appropriate64. A wide lime (added to reduce supernatant activity, allowing sea discharge
range of experiments were undertaken, both at 1 g to 1 kg scale, of liquors), 5% corrosion product oxides (Fe, Cu, Ni, Mn, V), 3%
and 10 kg pilot scale operations. The researchers determined that diatomaceous earth, 2% cellulose and various decontamination
for cationic resins, FeSO4 alone was a suitable catalyst, whereas liquors (various organic acids, nitric acid and ammonium
anionic resins demonstrated a strong synergy when FeSO4 and oxalate)142,143. Wet-oxidation trials of these wastes started with
CuSO4 catalysts were utilised in combination. Pilot-plant scale inactive lab-scale testing followed by a 1–10 kg pilot plant, then a
studies were undertaken at the Berkley Nuclear Laboratories, 200 kg scale demonstration plant—with the aim of developing
using a 0.1 m3 reactor, with combined liquid circulation loop, a full-scale plant coupled up to a cementation plant141. This was a
condenser, gas analysis train and off-gas treatment loop64. batch operation process, with no initial acidification or catalyst
Batches of up to 10 kg of resin were treated, with achieved added (trials were performed with both catalyst and acid, but with
destruction rates of 2–2.5 kg h−1 (damp resin) for Lewatit DN little improvement). Carbon removal of ~96% was achieved, with
resins, although noting some reduction in efficiency if resins the ability to reach 99% although this required a high volume of
contained vanadium from decontamination. Cementation of the peroxide. Hot trials were undertaken using 100 kg of real waste,
oxidation residues was proposed (using a blast furnace slag (BFS)/ resulting in a 60% reduction in total solids141. Post-processing
Portland cement (OPC) blend), with a flowsheet for plant inputs/ analysis showed 100% of the initial α activity was retained within
outputs produced—Table 3. details the mass balance of inputs/ precipitated solids, though β and γ activity were split between
outputs for treatment of 1 m3 IER in the proposed plant.Also in the solids and supernate141.
late 1980s, the UK Atomic Energy Authority (UKAEA) and Nuclear Following lab-scale testing, a 1/15th scale demonstration plant
Electric began scoping treatment options for sludges arising from was developed, capable of operating under reflux. This was
the Steam Generating Heavy Water Reactor (SGHWR) at Win- completed in 1989 and designed to operate with batches of
frith141. These sludges arose from plant operations (moderator 200 kg sludge (with 300 g kg−1 solids content). Building on this
purification, pond cleanup, and primary circuit decontamination) experience, a design study for a full-scale plant was

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 S.A. Walling et al.
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Fig. 5 AEA mobile wet-oxidation rig. Plant within mobile transportation (a), reaction vessel and main plant section (b)13. Reproduced with
permission from ref. 13, copyright (EC, 1996).

commissioned, with the preferred option to retrofit a wet- Cu2+ catalysts (sometimes equilibrated with wastes for up to
oxidation system to the head end of a cement encapsulation 24 h beforehand). The rig was heated to 90 °C, pH adjusted to a
plant (under construction at the time). Within this plant set point (and adjusted throughout, mostly with alkali additions
specification was an overall claimed potential volume reduction otherwise highly acidic conditions prevailed), then peroxide
of at least 2.5, with reduced organics and potential cost saving— added at a constant rate. Anti-foaming solution was added when
although volume reduction would be limited due to inorganic required, and post-processing the resultant liquid/sludge was
content within the wastes141. neutralised to pH 7–8 with Ca(OH)213. A packed tower scrubbing
Ultimately the decision was made not to pursue wet oxidation column was required for off-gas treatment, with 10% sulphuric
for SGHWR sludges, opting for decay storage of wastes until 2012, acid utilised to neutralise ammonia/amines from anionic IER
then cementation143. The cementation route was, however, degradation. Overall the majority of radioactive species
cancelled due to changes in waste acceptance criteria at the UK remained in the supernatant / sludge—however, some 60Co
Low Level Waste Repository (too high 63Ni and 14C levels for was noted to carryover to aqueous distillate, especially in
disposal). Cementation was later re-adopted, with an on-site frothing samples, along with ~90% of tritium in treated samples.
cementation plant constructed, cementing the sludge into 500 L A summary of wet-oxidation trial experimental conditions are
drums142,144. These drums are themselves packed into 2/3 height noted in Tables 4 and 5.
IP-2 ISO containers (which will be grouted prior to disposal)— Further testing, including active tests using ion-exchange resins
resulting in a final packaged volume of 1974 m3 (from an original were conducted using the pilot plant throughout 199463. Non-
volume of 330 m3 prior to treatment145) and consigned to the UK active trials included mixed ion-exchange resins from Magnox
Low Level Waste Repository (LLWR, having now decayed enough plant condensate polishing/steam boiler cleanup, steam generator
and diluted by cementation)144. decontamination liquor simulant, and simulated SGHWR sludge.
Although an alternative route was selected for the SGHWR Treatment of the mixed IERs claimed a 96–99% carbon removal,
sludges, research on a wet-oxidation rig was continued by with a 86–92% volume reduction (dry product), with residues
UKAEA’s recently formed commercial arm AEA Technology consisting of a mix of calcium/metal sulfates, calcium hydroxide
through the 1990s as part of a European Commission R&D and organic residue in a weakly ammoniated aqueous phase.
programme. This programme of work spanned over 4–5 years, Active trials consisted of 250 L of PWR mixed bed resins from
with the aim to review suitable wastes for wet oxidation, scale cooling pond water cleaning (IRN 77 and IRN 78), spent IER from
testing at both inactive and active level, then construction of a decontamination of a small PWR reactor containing organic
mobile wet-oxidation pilot plant capable of processing was at a chelating agents (likely submarine origins), and active SGHWR
rate of 50–100 kg d−1 13,63,136,146–148. Initial literature studies sludge13,63. Hot tests were particularly successful, with an average
concluded that wet oxidation of IERs held the most promise, ~95% original carbon removal, with 63–69% peroxide utilisation
followed by treatment of transuranium contaminated cellulosic efficiency (e.g. ~4 t 50% H2O2 m−3 flooded PWR resin), although
wastes, and decontamination liquids/scintillation cocktails not problems were encountered monitoring pH in situ (high dissolved
currently compatible with existing disposal routes146. Small-scale organics, suspended solids, high temperature).
trials were undertaken using Fe2+ and mixed Fe/Cu catalysts, with This project resulted in a final technical report in 1996
a semi-continuous process chosen for H2O2 efficiency146. By 1992 entitled’Wet oxidation of organic radioactive waste’, detailing
the design of a mobile wet-oxidation plant was completed, along the 5 year programme, technical data on experimental runs, and
with further lab trials on suitable wastes—with claimed’efficient mass balances for wastes13. The report also summarises the
organic removal’. They trialled the decomposition of Lewatit DN previous lab-scale experiments, with the most successful experi-
ion-exchange resins, and Lewatit DN + inorganic zeolites (both ments arising from this programme detailed in Table 4. The final
used for 137Cs removal in fuel storage ponds in UK)147. conclusions of this report note the success of wet oxidation for
Construction of a mobile pilot plant was completed in 1993, several organic radioactive wastes, with an achievable throughput
with first reactions using inactive IX resin as part of commission- of 30–50 L organic waste in an 8 h day, using a semi-continuous
ing148. The plant was fully contained in one ISO container, with a process. No detectible emissions above background were
jacketed reaction vessel, waste feed hopper, feed/discharge detected from gaseous emissions, with secondary liquid wastes
pumps, and coil heat exchanger—shown in Fig. 5. It was suitable for discharge to a standard radioactive effluent treatment
designed for up to 50–100 kg d−1 throughout, with a maximum system. Cementation of solid wastes claimed to be successful, with
activity of 0.1 TBq as 60Co. The container also included a distillate a full-scale oxidation plant estimated to reduce the volume of
tank, packed tower acid scrubbing column and HEPA filters for conditioned IER resins by 65% compared to direct cementation,
gaseous discharges. The main hazard was determined to be dose with cost savings due to reduced space required in a deep
to workers; however, the system could be remotely controlled to geological disposal facility. The implementation of this mobile rig
manage dose uptake148. The wet-oxidation rig utilised sulphuric was detailed in the final report, with extensive information about
acid and Ca(OH)2 solution for pH control, along with Fe2+ and mass balance for proposed waste treatment, noted in Table 6. The

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Table 4. Most successful (highest % organic carbon reduction) lab-scale runs from first AEA wet-oxidation programme13.

Waste Active Oxidant Catalyst pH Organic carbon reduction

Lewatit DN (cation IER) N H2O2 50% Fe2+ 4.7 kg m−3 2.0 99%
5.1 t m−3
Amberlite IRN150L (mixed IER) N H2O2 50% Fe2+ 4.0 kg m−3 4.0 96%
6.6 t m−3 Cu2+ 1.0 kg m−3
Powdex (mixed IER) N H2O2 50% Fe2+ 2.4 kg m−3 4.0 95%
5.64 t m−3 Cu2+ 0.6 kg m−3
Lewatit/AW500 (3:1 organic: inorganic) N H2O2 50% Fe2+ 1.0 kg m−3 3.5 88%
4.8 t m−3 Cu2+ 1.0 kg m−3
Lewatit/Descalo Y (3:1 organic: inorganic) N H2O2 50% Fe2+ 1.0 kg m−3 3.5 86%
4.8 t m−3 Cu2+ 1.0 kg m−3
SGHWR sludge (semi-cont reaction) N H2O2 50% None added, present in waste 3.5 93–96%
2.0 t m−3
Lewatit DN (semi-cont reaction) N H2O2 50% Fe2+ 1.2 kg m−3 2.0 95%
3.6 t m−3
Trawsfynydd resin (Lewatit/AW500) Y H2O2 50% Fe2+ 1.0 kg m−3 3.5 97%
5.0 t m−3 Cu2+ 1.0 kg m−3
Cellulose waste (paper, tissue, cloth) N H2O2 50% Fe2+ 2.5 kg m−3 3.0 95%
1.4 t m−3 Cu2+ 2.5 kg m−3
1% citric acid N H2O2 50% Fe2+ 0.2 kg m−3 2–4 99%
0.044 t m−3 Cu2+ 0.2 kg m−3
1% formic acid N H2O2 50% Fe2+ 0.1 kg m−3 2–3 99%
0.018 t m−3
1% EDTA N H2O2 50% Fe2+ 0.2 kg m−3 3–4 99%
0.05 t m−3 Cu2+ 0.2 kg m−3
Scintillant residue (1% organics) N H2O2 50% Fe2+ 0.2 kg m−3 2–3 94%
0.084 t m−3 Cu2+ 0.2 kg m−3

treatment of ~1100 kg waste would require 4000–5000 kg of 50% issues relating to extra temporary shielding requirements, and
H2O2, resulting in 5000–7000 kg of aqueous distillate, along with outdoor operation/situation of the rig. The development of the
~600–1100 kg of treated product, itself predominantly water, modular rig did not appear to continue much further in the UK
sulfates, calcium and residual carbon amongst other minor after this project finished, despite achieving the goals of successful
components. waste treatment.
Testing of the AEA wet-oxidation rig continued with another 4 The ModulOx system was, however, tentatively planned for
year EC project, looking at application to a wider range of organic usage in treatment of specific UK nuclear submarine ion-exchange
wastes in Europe, including ion-exchange resins from the German resins. These MODIX resins (Multi-stage Oxide Decontamination
Krümmel and UK Oldbury NPPs, and liquid wastes at the Belgian with Ion eXchange) had been utilised as part of reactor
BelgoProcess site149,150. Various modifications and upgrades to decontamination, principally to remove 60Co151,152. The 14C
the rig (now called ModulOx) were undertaken to improve content of these spent resins, and presence of chelating agents
throughput and control systems (waste feed improvements, pH resulted in these being excluded from the UK Low Level Waste
measurement, improved logging system, etc.). Overall the system Repository (LLWR), and requiring treatment. The ModulOx pilot-
chemistry remained largely the same, utilising 50% H2O2 with plant at Winfrith was scoped for potential usage, though over the
sulphuric acid and Ca(OH)2 or NaOH for pH control. Fe2+ and Cu2+ timeframes involved the Winfrith site entered widescale decom-
were utilised as catalysts, with cementation of sludge/residue missioning prior to advancement of this plan152,153. An additional
formed from IER destruction150. opportunity arose when a ModulOx rig was shipped to the USA for
The system successfully completed a trial run of dried mixed treatment of ion-exchange resins at Oak Ridge National Lab
bed resins shipped from the Krümmel NPP to the UK, with waste (ORNL), then to Idaho National Laboratory (INL) for tank waste
sludge encapsulated within a BFS:OPC cement blend to German remediation154. Ultimately this rig was not utilised for planned
standards allowing disposal at Morsleben, with a claimed 80% waste treatment at either location due to project amendments or
waste volume reduction compared to direct cementation of usage of alternative technologies.
untreated resins. The rig was also transported to Oldbury NPP in In 2014, the UK Nuclear Decommissioning Authority reviewed
the UK for similar treatment of spent lithiated IERs; however, this experience of mobile ILW plants in Britain, coming to a pessimistic
time occurring on-site as a demonstration of the mobile aspect of conclusion on mobile wet-oxidation plants14. Originally designed
the rig. Treatment was successful, with resultant waste encapsu- to avoid large fixed installations and to allow acceleration of
lated in a PFA:OPC (Pulverised Fuel Ash) cement blend, with a hazard reduction programmes, mobile rigs suffered from pro-
claimed 49% final product volume reduction. Further demonstra- blems due to their compact size. This resulted in low throughput,
tion of the mobile rig occurred at the BelgoProcess site in Belgium, hazardous maintenance due to tightly packed equipment, higher
where ~2900 L aqueous liquid wastes containing up to 68,000 mg operator dosage (or requirement for shielding to be constructed),
L−1 COD (Chemical Oxygen Demand) were treated to a resultant staffing issues and potential lack of flexibility with various
COD of 70–114 mg L−1, with resultant effluents directed into the wastestreams. Delays on one site would impact another, and
existing site effluent treatment system150. Overall the trial discharge permits might require alteration due to a change of
treatment of various wastes was deemed successful at the various process on-site (i.e. amendment to gaseous discharge licence). The
sites, with rig portability firmly established, though with some initial wet-oxidation rig, though designed for a 100 L IER per day,

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Table 5. Wet-oxidation trials at plant operation level 13,63
.

Waste Active Oxidant Catalyst pH Organic carbon Duration

reduction

Spent PWR resins (250 L) Y 50% H2O2 Unspecified – 96% 2× semi-cont runs over 48 h
1t runtime
Small PWR reactor decontamination Y 50% H2O2 Unspecified – 95% 3× semi-cont runs over 58 h
resins (360 L) 1.6 t
SGHWR sludge (177 kg inactive, 1 kg Y 50% H2O2 Unspecified – 94% 18 h
active) 480 kg
Lewatit DN KR cation resin (113 L) N 50% H2O2 Unspecified – 94% 45 h
591 kg
Steam generator decontamination N H2O2 56 kg CuSO4 and FeSO4 – 99.1% 3h
liquor simulant (CuSO4, FeSO4, EDTA, (unspecified %) (0.48 t in liquor
ammonia, water) (116 L) m−3)
Mixed bed IER (IRA 900 and Ambersep N 50% H2O2 CuSO4·5H2O and 3.5 ~97% Semi-cont runs, average 13 h
IR252) (520 L total over 4 runs) 2.9 t m−3 at 0.5 kg FeSO4·7H2O reaction time over multiple
min−1 days excluding heating/
cooling
Run 1 (103 L) N 50% H2O2 FeSO4·7H2O (740 g) 3.5 99.2% 10 h
(2.7 t m−3) CuSO4·5H2O (150 g)
Run 2 (125 L) N 50% H2O2 98% 12 h
(2.9 t m−3)
Run 3 (125 L) N 50% H2O2 97% 11.5 h
(2.7 t m−3)
Run 4 (165 L) N 50% H2O2 96% 18 h
(3.2 t m−3)

Table 6. Mass balance for treatment of 1 m3 various wastes in a mobile wet-oxidation plant, data taken from13.

Inputs (kg)
Waste Water H2O2 (50%) Acid/alkali Additivesa Scrubber liquor

PWR IX resin 1100 700 4000 1302 44 200

Spent IX resin (mixed decon) 1100 1551 4600 1451 44.2 200
SGHWR sludge 1200 559 3171 1938 35.53 71
Lewatit DN KR cation resin (inactive only) 1150 1820 5260 1637 141.5 0
Outputs (kg)

Treated product total Largest components of Aqueous distillate Off gas Scrubber liquor
treated product

PWR IX resin 601.22 391 water 54 calcium 5538 1026 208

122 sulfate 11 carbon
Spent IX resin (mixed decon) 581.77 378 water 66 calcium 7007 1171 208
102 sulfate 11 carbon
SGHWR sludge 848.10 551 water 98 calcium 5172 814 74
159 sulfate 25 other ions
Lewatit DN KR cation resin (inactive only) 1116.00 725 water 64 calcium 7624 1396 0
259 sulfate 44 sodium
a
Additives largely comprising water, anti-foaming agents and catalysts (Fe, Cu sulfates).

only treated 360 L over its lifetime (due to never seeing full moving into an industrial setting, and further advancements
operation), and the rig still required an encapsulation plant to largely led by the Japan Gasoline Corporation (JGC), along with
solidify the residues. On a more positive note, it was concluded some research by other industrial sector companies. This early
that trials on fixed wet-oxidation plants appear to suffer from research was detailed by Kubota at JAERI, resulting in the
fewer concerns than fully modular systems14. publication of two Japanese patents in 1982. The first details
destruction of a cationic resin with hydrogen peroxide and a
chromium or iron nitrate catalyst155, the second details destruc-
Japan tion of an anionic resin with peroxide and chromate/bichromate
Wet oxidation in Japan was initiated at the Japan Atomic Energy ions156. Alongside this was a 1983 paper detailing investigation
Research Institute (JAERI) in the early 1980s, with research quickly into cation exchange resin degradation with H2O2 and Fe3+ 11. In

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 S.A. Walling et al.
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large reactor (effective volume of 111.4 m3) is mentioned two
years later, for treatment of liquid effluents, coupled to a UV
system for complete decomposition. This second system also
utilised Fe and Cu catalysts, but with continuous feeding of waste,
50% H2O2, anti-foaming agent addition and pH control to 3–4
with H2SO4114. It is unclear whether these processes were
developed further than pilot scale, with little publicly available
information since 1990.
Later, the JGC wet-oxidation process was re-assessed for
application in volume reduction of spent ion-exchange resins at
the Tsuruga nuclear power plant in Japan. This is the oldest
commercial reactor in Japan, with unit 1 currently undergoing
decommissioning. A suitable solution was required for stored IERs
and filter sludge on-site (>500 m3 combined volume in 2003)127.
Though the IERs were wholly organic, the filter sludge was a
combination of cellulose, diatomaceous earth, metal oxides and
IERs. It was concluded that a ‘conventional’ H2O2 + ferric/ferrous
ion Fenton system would be suitable for waste volume reduc-
Fig. 6 Effect of Cu:Fe catalyst ratios on decomposition and sludge tion127. This option does not appear to have gained further
formation. Data adapted from ref. 59 for clarity. traction, however, the option of Tsuruga NPP IER treatment using
wet oxidation was revived again in 2011, with JGC and JAPC
the same year Nippon Atomic Industrial Group and Tokyo undertaking further research. Pilot scale tests were claimed to be
Shibaura Electric Co briefly stepped into this research, being successful, with wastes compatible with super-cement solidifica-
granted a patent detailing IER decomposition with H2O2 and a tion (an alkali activated cement developed in Japan)128,169. Since
ferric sulfate solution, although with no noticeable innovations this time Tsugura unit 1 is undergoing decommissioning, but no
over the JAER patents157. This was followed by two further patents public information regarding any implementation of wet oxidation
in 1984 detailing ion-exchange treatment with ferric sulfate and is available.
peroxide158, and a patent utilising Cu ions as catalysts for anion- Although the bulk of open research has been undertaken by
resin degradation with an electrochemical method of Cu JGC, several other groups in Japan have researched or been
recovery159. granted patents on wet oxidation of nuclear wastes. As noted
The Japan Gasoline Co. continued this line of research, earlier, Nippon Atomic Industrial Group and Toshiba have been
publishing a wealth of patents and conference papers detailing granted several wet-oxidation patents157–159, although one of the
their research from 1983 onwards. These heavily focus on more notable achievements was by Fuji Electric. In 1988 they were
destruction of ion-exchange resins, usually for volume reduction granted an extensively researched patent for Fe/Cu catalysed
purposes. Their rational stems from the claim that many oxidation of IERs170 (1989 for US patent59). Innovations in this
alternative treatment options for IERs either require very strong patent include crushing of IER prior to oxidation, resulting in
acids and result in highly corrosive liquids/gases, or risk radio- reduced H2O2 required and lower foaming. A net weight of H2O2
nuclide migration into gases from high-temperature processes, to dry IER no higher than 17 (i.e. 17/1) was recommended,
requiring complicated off-gas systems. Many of the patents detail
preferably between 10 and 4, or with citric acid adsorbed onto
conventional Fenton-like systems, utilising a transition metal
IERs prior to decomposition. It was noted that Fe and Cu catalysts
catalyst (typically ferric sulfate) and hydrogen peroxide at, or near-
combined can work at neutral pH, but lower pH is needed to avoid
boiling temperature. Ion-exchange resins, chelate resins and
the build-up of sludge (so recommended to keep pH 2–3). Mixed
various organic filter aids are decomposed. Several patents also
catalysts were found to work better than Fe or Cu alone, although
detail equipment setup for oxidation, then drying and solidifica-
the molar fractions were not important. A 9:1 Cu:Fe catalyst was
tion systems coupled to this.
found to work just as well, but with less sludge formation (which
A notable finding by JGC (and echoed elsewhere) is the relative
was directly proportional to Fe content in catalyst—noted in Fig.
difficulty of anion-resin degradation compared to cation resins.
6). The composition of anion resins was also found to be crucially
Their method claimed to improve degradation by addition of even
important, with anion IER decomposition decrease in efficiency
a small amount of Co or Mn, or by co-processing anion and
from citric acid > SO4 > OH > Cl types. From this they claim that
cation resins together. It was claimed that co-processing even 1%
citric acid sorbed onto resins prior to treatment resulted in high
cation resins alongside anion resins results in a marked increase in
degradation efficiency59, with this potentially being due to
degradation160,161. Efficiency improvements were sought, with
reduced sludge formation.
several patents describing usage of refluxing vessels rather than
Despite a wealth of patent literature and widescale research, no
condensation and collection of distillate162,163, along with various
large-scale deployment of Fenton-like wet oxidation in Japan on a
processes for continuous feeding of waste and/or peroxide into a
commercial scale is evident from open literature.
reactor vessel164, one of which specified an average residency of
2–6 h161. JGC further outlined a full system for decomposition,
then drying and packing of wastes for solidification165. USA
Aside from treatment of solid organic material, JGC also Fenton-like wet-oxidation processes have not found sure footing
adapted their Fenton system for the treatment of various within the USA. Several pilot scale trials have been undertaken
radioactive waste liquors (detergents and/or liquid organics)166, with wastes, with wet oxidation scoped for technology develop-
and for treatment of decontamination agents, including organic ment—but has not progressed beyond this. The US Atomic Energy
acids (EDTA, citric acid, etc.), the latter utilising Cu and Fe Commission obtained a patent for Fenton oxidation of spent ion-
catalysts167. This treatment of decontamination agents appears to exchange resins in 1972171. This was, however, for removal and
have been taken further, up to pilot-plant scale treating 150 L of retrieval of nuclear material from IERs (Pu, U, Th, Ac) rather than
solution. The system utilised combined Fe and Cu catalysts to with a focus on waste reduction. The method envisages dissolving
almost completely decompose organic acids, with a claimed resins in nitric acid and hydrogen peroxide, catalysed by
efficiency of 5–10 kg of 35% H2O2 kg−1 of decomposed EDTA168. A potassium ferrocyanide, with several examples showing Pu

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 S.A. Walling et al.
15
removal from resin. Overall this particular process neither appear programme at INL had treated over 61,000 L of waste by 2007,
to have been further built upon, nor enjoyed industrial- with post-sparged wastes mixed with a water absorbent material
scale usage. and disposed of at the Idaho CERCLA Disposal Facility (ICDF),
Interest was later gathered for the demonstration of wet- ultimately resulting in no need for usage of the AEA rig177.
oxidation technology in the 1990s. The Mixed Waste Management The only other publicly cited use of Fenton oxidation for nuclear
Facility (MWMF) was planned to be built at Lawrence Livermore waste or site cleanup in the USA was a brief demonstration of
National Laboratory (LLNL), and envisaged as a national test bed subsurface decontamination at the Savannah River Site (SRS) in
for four different demonstration technologies, all aiming to treat 1997. Organic destruction for soil remediation using peroxide and
low-level waste arising from sites in the USA172,173. This included iron catalysts is a proven technology with commercial vendors,
molten salt oxidation (MSO), mediated electrochemical oxidation having been applied to a range of challenging organics178–180. At
(MEO), ultraviolet photolysis (UVP) and wet oxidation (WOX). The SRS, dense non-aqueous phase liquids (DNAPL) were targeted for
UVP system was to be utilised on effluents from the WOX system, in situ destruction using a combination of H2O2 and FeSO4
as an organic polishing system to further reduce organic material injected underground. Destructive efficiency of 94% for DNAPLs
down to regulatory limits. Unfortunately, this facility does not was achieved, but with a lasting impact on soil pH due to acidic
appear to have been constructed in its envisaged form, with media utilised180,181.
budget amendments focussing efforts on molten salt oxidation Overall Fenton oxidation processes have never fully been
only, and WOX work closed out per Department of Energy utilised for large-scale waste processing in the USA, although the
guidance by 1997 onwards174. AEA rig nearly found usage for dealing with several niche
Interest was renewed in utilisation of Fenton chemistry in the wastestreams. A particularly complicating factor in assessing
early 2000s, with laboratory scale testing undertaken for destruc- Fenton and Fenton-like oxidation processes in the USA is the
tion of wastes at Oak Ridge175. A mix of transuranic sludges and usage of the term’wet oxidation’ for both a Fenton-like process,
organic IERs were located in underground storage tanks (T1 and and for higher pressure/temperature catalytic wet oxidation using
T2 tanks) in the Melton Valley watershed. It was determined that air/oxygen. There is also some confusion within literature between
not enough plutonium could be leached from the wastes using a Fenton-like process and catalysed acidic chemical oxidation (also
acid or chelates to render the waste non-transuranic in classifica- known as ‘direct chemical oxidation’), such as the Delphi Detox
tion, therefore destruction of the resins remained the only option, process which gained some traction for organic waste disposal in
enabling the wastes to then be treating using on-site facilities. the USA182–184.
Lab-scale testing, then active pilot scale testing was undertaken
using real waste. AEA Technology was chosen to build and
Canada
operate a full-scale system to treat both tanks, along with the
nearby High Flux Isotope Reactor (HFIR) tank waste. Treatment of Although never operating a commercial Fenton-like wet-oxidation
tanks was planned for 2004, with a large modular skid mounted process, Canada requires recognition for operating a ‘WETOX’
oxidation rig constructed and delivered to site154,175 (photograph process, which has sometimes been confused for a Fenton-like
of reactor module in Fig. 7). Further characterisation, however, system. In the 1980s the Ontario Research Foundation undertook
determined that wet oxidation was not required to meet waste research and early commercialisation of a higher pressure and
acceptance criteria, with wastes suitable for treatment at the on- temperature wet air oxidation system (350–400 °C, 40 bar) for
site LLW evaporator, with tanks subsequently grouted176. treatment of aqueous wastes185,186. This was continued by Ontario
This rig, based on AEA’s ModulOx technology, quickly found Hydro, whom in the mid 1990s operated a plant at the Bruce NPP
another use, and was shipped to Idaho National Laboratory (INL) for processing wastes containing high concentrations of EDTA and
for usage in treating V-Tank waste154. The modular system metal ions (principally iron and copper) from cleaning steam
included a 2.27 m3 (600 gallon) internal volume reactor (operating generators187. This plant utilised high pressure steam at 250 °C
in reflux mode) with scrubbing system, off-gas skid (with HEPA and pressures of 5 MPa, with the plant treating >5 million litres
and GAC filter), control trains, along with a steam generator and before shutdown and decommissioning188.
chilling system. The rig was to act as a backup secondary
treatment of V-tank wastes if air/ozone sparging of wastes was not
ECONOMICS
fully successful in reducing VOC content enough for disposal.
Despite intermittent operation of sparge treatment, the The principal economic driver for Fenton oxidation of radioactive
organic wastes is the potential for the volume reduction of wastes.
If wastes are to be consigned to engineered disposal facilities (e.g.
shallow burial for lower activity wastes, or deep geological
disposal for higher activity), these may entail significant costs
per cubic meter of waste. Additionally, if these facilities are not yet
operational or accepting wastes, ongoing costs from interim
storage in suitable facilities may be incurred.
Cost estimates for treatment of nuclear wastes have varied
greatly, and few reports have assigned full costings to waste
treatment—instead focussing on estimates of volume reduction. A
1987 Swedish study claimed a volume reduction factor of 15 was
achievable75, while a 1989 initial study in the UK estimated
volume reductions of a factor of 5 were achievable, with
subsequent cementation of the wastes resulting in a net saving
on storage and disposal costs, although no final figures were
reported64. A UK pilot-plant wet-oxidation rig operating in the
1990’s claimed a 66% volume reduction for organic ion-exchange
resins with cementation of partially dried sludges, versus direct
cementation. Drying then compaction of the wastes without
Fig. 7 Photograph of reactor module at Oak Ridge154. (Copyright cementation was claimed to result in a 95% volume reduction13.
© by WM Symposia. All Right Reserved. Reprinted). The authors calculated upfront capital costs, staffing,

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 S.A. Walling et al.
16
maintenance, discharge licences, chemicals, etc.—noting this was pilot plants, but strict environmental discharge limits for radio-
in addition to cementation post-treatment. Costings for a 1/ active material will likely necessitate further processing of these
10 scale pilot plant (in 1995 GBP£) resulting in £42,000 m−3 of ion- wastes either in an enhanced Fenton process, or in additional
exchange resin treated, with a full sized mobile plant costing treatment facilities. Further processing is also required for solids
£11,000 m−3. Overall this resulting in an estimated 51% saving generated, with larger plants typically envisaged to be operated at
compared to direct cementation of the resins, principally coming the head-end of a cementation facility. Due to these additional
from the reduced final volume of the wasteforms. wastes, longer-term understanding of any final waste-wasteform
No more recent open literature assessments of waste treatment interactions is required (e.g. between precipitated sulfates and
economics using Fenton oxidation are available, and economics cement), or research into alternative wasteforms (i.e. glass or
are highly likely to vary from country to country, and waste to ceramic materials) for wastes generated. An original hope for wet-
waste. Equally, other regulatory concerns will factor into waste oxidation facilities was for smaller, mobile plants which could treat
treatment options other than straight economics. There may exist varied wastes across different sites, however, challenges in
limits on the type and quantity of organic material permitted operating and licencing modular wet-oxidation systems are likely
within an engineered repository, particularly for chelating to limit future usage outside of larger fixed plants.
organics. These are of concern due to the risk of enhancing On a more positive perspective, the ability of Fenton wet
radionuclide mobility and may, for example, push regulators oxidation to degrade material at lower temperatures is of
towards recommending various thermal treatment technologies particular interest for wastes containing volatile radioisotopes,
for waste treatment. for which high-temperature processes may require extensive off-
gas systems. Opportunities exist for optimising degradation
reactions with varied catalysts (including metal ions not favoured
CONCLUSIONS during typical wastewater treatment, such as copper and
Fenton and Fenton-like wet oxidation of radioactive wastes has chromium), optimising the quantity of H2O2 utilised to reduce
been championed for destruction of organic materials for around secondary wastes, co-treatment with other organic materials or
40 years, due to the attractive option to significantly reduce solid integration into an alternative waste immobilisation process (e.g.
waste volumes and potentially re-categorise wastes for accep- head-end of a hot isostatic pressing system).
tance into national repositories. The presence of organics, Due to the continued presence and generation of organic
especially organic complexants, are sometimes restricted due to radioactive wastes, and a drive towards safe, final disposition of
concerns over flammability, degradation of organics over time and nuclear wastes, Fenton and Fenton-like wet-oxidation research will
potential increased mobility of radionuclides. likely continue to offer solutions and opportunities for nuclear
Extensive trials on the implementation of wet oxidation have waste management. The potential for lower temperature proces-
been undertaken in Italy, Sweden, Japan, USA and the UK. sing, with significant reduction in resultant solid wastes could
Laboratory scale research, pilot plants and multinational trials provide another technology in the toolbox of treatment options.
have determined that volume reduction and adequate destruction
of certain materials are achievable. Wastes targeted in these trials
include ion-exchange resins, waste reprocessing solvents, sludges DATA AVAILABILITY
and decontamination liquors. Typically wastes have been treated No datasets were generated or analysed during this study.
in batch, or semi-batch processes, with remnant solids sent for
cementation and liquid effluents disposed via other routes. Received: 12 February 2021; Accepted: 2 August 2021;
Many of these national trials have focussed on specific
challenging wastes (e.g. EUREX solvents in Italy). The most
extensive testing at varying levels has been in the UK, with
several scale pilot plants and mobile plants, which have treated
varying ion-exchange resin, sludges, cellulosic waste and liquid REFERENCES
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wet-oxidation plants were planned for construction, usually 2. Nuclear Decomissioning Authority & Department of Business Energy & Industrial
utilising conventional Fe–H2O2 Fenton chemistry. None of the Strategy. 2019 UK radioactive waste inventory. (NDA / BEIS, 2019).
3. Ojovan, M. I., Lee, W. E. & Kalmykov, S. N. An Introduction to Nuclear Waste
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AUTHOR CONTRIBUTIONS
S.W.—-manuscript preparation, formal analysis, reviewing, editing. W.U.—-reviewing,
editing. C.C.—-reviewing, editing. N.H.—-supervision, reviewing, editing. © The Author(s) 2021

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