Water Research 212 (2022) 118101

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Water Research
journal homepage: www.elsevier.com/locate/watres

Making waves: Defining advanced reduction technologies from the

perspective of water treatment
Stanisław Wacławek a, *, Xingmao Ma b, Virender K. Sharma c, Ruiyang Xiao d, Kevin E. O’Shea e,
Dionysios D. Dionysiou f, *
a
Institute for Nanomaterials, Advanced Technologies and Innovation, Technical University of Liberec, Studentská 1402/2, 461 17, Liberec 1, Czech Republic
b
Department of Civil and Environmental Engineering, Texas A&M University, College Station, TX 77843, USA
c
Department of Environmental and Occupational Health, School of Public Health, Program for the Environment and Sustainability, Texas A&M University, 212 Adriance
Lab Rd., 1266 TAMU, College Station, TX 77843, USA
d
Institute of Environmental Engineering, School of Metallurgy and Environment, Central South University, Changsha 410083, China
e
Department of Chemistry and Biochemistry, Florida International University, Miami, FL 33199, USA
f
Department of Chemical and Environmental Engineering (ChEE), Environmental Engineering and Science Program, University of Cincinnati, Cincinnati, OH 45221-
0012, USA

A R T I C L E I N F O A B S T R A C T

Keywords: Studies related to advanced reduction technologies (ARTs) have grown exponentially since the term was first
Advanced reduction technologies coined in 2013. Despite recent interests in ARTs, the conditions and requirements for these processes have yet to
Water treatment be defined and clarifed. In comparision to well defined advanced oxidation technologies/processes (AOTs/AOPs)
Hydrated electron
which involve the generation of hydroxyl radical as the common characteristic, ARTs function by electron
Emerging contaminants
donation from a variety of reducing agents and activators. Based on an extensive literature review, we propose
that ARTs be defined as processes employing strong chemical reductants with E◦ ≤ − 2.3 V vs. normal hydrogen
electrode at 25 ºC. While extensive studies have revealed critical fundamental details of AOTs/AOPs mediated
processes, there are still significant gaps in elucidation of the mechanistic details of reductive degradation/
transformation of highly toxic compounds by ARTs. A significant number of pollutants and toxins resistant to
AOTs/AOPs treatment are effectively degraded by ARTs. A great leap is needed on understanding ARTs to fully
utilize their potential to efficiently remediate recalcitrant compounds of different sources and structures.

Extensive exploration and development of technologies to address
widespread pollution of the Earth have been underway for several de­
cades. Among various compounds hazardous to humans, animals and
the environment are toxic metals, oxyanions and organic contaminants
of emerging concern (CECs) (He et al., 2021; Wacławek et al., 2019).
Unfortunately, conventional remediation methods often fail to remove
or transform CECs because of their environmental stability, often caused
by strong bonds associated with these chemicals (for example, C-F bonds
in perfluorinated alkyl compounds, PFAS). For treatment of such sub­
stances, even advanced oxidation technologies/processes (AOTs/AOPs)
and sulfate radical-based advanced oxidation technologies/processes
(SR-AOTs, SR-AOPs) that rely primarily on the hydroxyl radical (⋅OH)
and sulfate radical anion (SO4⋅− ), will not lead to effective degradation.
While reductive transformation of chemical substartes has been
studied for centuries, it was not until 2013 that Vellanki suggested a new
class of remediation technologies involving reductive processes, i.e.,
advanced reduction technologies (ARTs) (Vellanki et al., 2013). ARTs
have shown promising potential for environmental remediation and
other fields such as materials science. Several important reviews have
been published on ARTs (Wu et al., 2021; Yang et al., 2016, 2020);
however, a clear definition of ARTs is absent in the literature. Herein, we
propose to globally define ARTs as processes employing strong reducing
agents with standard reduction potentials E◦ ≤ − 2.3 V vs. normal
hydrogen electrode at 25 ºC [which is the potential equal to or lower
than that of hydrated electron (eaq− ) or its conjugate acid (H⋅)]. An
advantage of the hydrated electron over other radical species for
reacting with halogenated compounds is its ability to remove halide
anions via dissociative electron capture [Eq. (1), (von Sonntag, 2006)],

* Corresponding authors.
E-mail addresses: stanislaw.waclawek@tul.cz (S. Wacławek), samuelma@tamu.edu (X. Ma), vsharma@tamu.edu (V.K. Sharma), xiao.53@csu.edu.cn (R. Xiao),
osheak@fiu.edu (K.E. O’Shea), dionysios.d.dionysiou@uc.edu (D.D. Dionysiou).

https://doi.org/10.1016/j.watres.2022.118101
Received 9 October 2021; Received in revised form 21 December 2021; Accepted 16 January 2022
Available online 18 January 2022
0043-1354/© 2022 Elsevier Ltd. All rights reserved.
S. Wacławek et al.
Fig. 1. Molar absorption coefficient of eaq− from the wavelength of 420 nm to
1050 nm. Data were taken from Hare et al. (2008) (Copyright American
Chemical Society).
resulting in faster reaction kinetics between the hydrated electron and
halogenated species (compared to the sulfate and hydroxyl radicals).
eaq − + R − Cl→R⋅ + Cl− (1)
The eaq is one of the most powerful reducing agents having E aq/e of
− ◦
-2.9 V. The approximate half-life of eaq− in pure water is more than ~102
μs, relatively long lived in comparison to hydroxyl radical (~10− 3 μs)
and sulfate radical (~101 μs) exploited in AOPs and SR-AOPs, respec­
tively (Krawczyk et al., 2020). The longer lifetime of eaq− could be ad­
vantageous for more effective degradation of targeted pollutants.
Homogeneous and heterogeneous processes have been employed for the
generation of eaq− . For example, hydrated electrons can be generated
directly by ionization of water or indirectly through the electron
detachment from a specific dissolved substance, separating electron
from the parent compound. A number of dissolved reducing agents are
effective for ARTs, including sulfite, iodide, ferrocyanide, dithionite, or
organics such as indole and phenol. Among these reductants, sulfite
anion has been applied for in-situ reduction of inorganic contaminants.
In pure water, eaq− can be determined by spectrophotometry at
~718 nm [molar absorption coefficient (ε) = 1.9 × 104 M− 1 cm− 1] (Loh
et al., 2020; von Sonntag, 2006), in contrary to H⋅, which only absorbs
electromagnetic radiation < 250 nm making it challenging to monitor. A
later study using pulse radiolysis reevaluated the value of εe− (Hare
et al., 2008). The obtained values of εe− in the visible wavelength region
are presented in Fig. 1; giving 2.27 × 104 M− 1 cm− 1 at 720 nm and
20 ◦ C. It appears that earlier values of εe− were underestimated by about
10–20 %. Consequently, in the studies in which k/εe− as the actual pa­
rameters were measured, reported values of rate constants may be lower
than actual rate constants by 10–20 %.
Pulse radiolysis has been used to study reaction pathways and
determine the rate constants of hydrated electron reactions von Sonn­
tag, 2006) with an extensive number of compounds. Hydrated electrons
react primarily via a one-electron transfer process, with reactivity
depending on the availability of an empty molecular orbital on the
target contaminant. The rate constants of eaq− reactions vary consider­
ably from 10 to ~1010 M− 1 s− 1 (von Sonntag, 2006). The primary
mechanism for initiating ARTs relies on the interaction of a reducing
agent (RA) with electromagnetic radiation to generate RA radical spe­
cies and hydrated electrons (Eqs. (2)–((7)).
SO3 2− +hv→SO3 ⋅− + eaq − (2)
I− + H2 O + hv→I• H2 O− ∗
(3)
I• H2 O− ∗ →(I• , e− ) + H2 O (4)
2
Water Research 212 (2022) 118101
(I• , e− )→I• + eaq − (5)
the bracket represents the solvent cage where I⋅ + eaq− are generated in
pairs.
Fe(CN)6 4− +hv→Fe(CN)6 3− + eaq − (6)
S2 O4 2− +hv→S2 O4 ⋅− + eaq − (7)
Plasma and electrochemical methods can also be employed to
initiate processes of ARTs. The eaq− readily reacts (often at or near
diffusion-controlled rate constants) with ground-state dioxygen
∑
(3 − g O2 , Eq. (8)), and a variety of functional groups such as − NO2,
− C≡N, − C=O, resulting in the formation of corresponding radical an­
ions. These radical anions typically are very strong reducing agents and
can promptly donate an electron to other substances, which leads to a
variety of competing reactions (von Sonntag, 2006).
eaq − + O2 →O2 •− (8)
ART reactions are highly dependent on the solution pH. The hy­
drated electron is the conjugated base of H⋅ with a pKa = 9.1 (von
Sonntag, 2006); therefore, the hydrated electron is protonated in acidic
solutions, whereas H⋅ converts to eaq− at higher pH values (von Sonntag,
2006). As mentioned above, eaq− is a powerful reductant (E◦ = − 2.9 V).
Its conjugate acid (H⋅) has slightly higher E◦ of − 2.3 V. Thus, the
remediation efficiency of ARTs is generally enhanced at higher solution
pH due to the more negative reduction potential of eaq− , and the absence
of protonated species of RA. For example, when SO32− is used as a RA, at
lower pH values, HSO3− instead of hydronium ions can scavenge eaq−
(Maza et al., 2019).
Molecular oxygen is a typical component of water and can influence
ART reactions significantly by consuming eaq− (Wu et al., 2020). Satu­
ration of the solution with O2 in the concentration of 2.5 × 10− 3 M (i.e.,
slightly higher than the solubility of O2 at 25 ◦ C and 1.0 atm of O2
pressure) converts eaq− into HO2⋅/O2⋅− [pKa(HO2⋅) = 4.8; (k = 1.9 ×
1010 M− 1 s− 1) (Eq. (8)) (von Sonntag, 2006)].
When the sample is saturated with a 4:1 N2O/O2 mixture, eaq− is
transformed almost entirely into ⋅OH (von Sonntag, 2006). As a result, in
the presence of molecular oxygen, an ART process like UV/SO32− may
be utilized as conventional AOP (Cao et al., 2021a), or SR-AOP (Cao
et al., 2021b). Water matrix substituents and common scavengers of
species also affect the performance of ARTs. Influence of natural organic
matter (NOM) on the reduction of environmental chemicals by ARTs has
been examined (Jung et al., 2017). Concentration of NOM was deter­
mined to be critical. A positive influence of NOM on ART was notably
observed at low NOM concentrations, whereas a negative influence was
observed at higher NOM concentrations (> 5 mg/L) (Jung et al., 2017).
The effect of inorganic water constituents on ART is not fully understood
but corresponding studies are underway.
Detailed studies on the application of ARTs to remediate contami­
nants have been investigated only in the last few years (Cui et al., 2020).
Some research has been performed with emerging contaminants, but
most efforts have been on PFAS, which are persistent, toxic and preva­
lent in groundwater and surface water worldwide. Perfluoroalkyl groups
are resistant to natural degradation because of the strong C-F backbone
in their structure. ARTs appear to enable efficient reduction of haloge­
nated compounds, which could be particularly useful when dehaloge­
nation of the parent compound decreases its toxicity. AOPs are usually
not very appropriate for the efficient remediation of halogenated com­
pounds such as PFAS (Lutze et al., 2018). In general, the degradation
efficiency of PFAS by ARTs depends on their head groups, pH, RA dose,
dissolved oxygen, NOM, other anions, and temperature (Cui et al.,
2020). For example, almost complete degradation of perfluorooctane
sulfonate (PFOS) and perfluorooctanoic acid (PFOA) degradation by the
UV/SO32− system was reported (Gu et al., 2017b, 2017a). Another
example is the reduction of PFOA concentration from 10 mg/L to 60
S. Wacławek et al.
Fig. 2. Comparison of the published EEO values of different ARTs, AOPs and
SR-AOPs. For almost all AOP systems, the median value was taken from a recent
article (Miklos et al., 2018). The other values were taken from works con­
cerning UV/peroxymonosulfate (PMS) (Olmez-Hanci et al., 2011), UV/SO32−
(note that even lower values are reported there for SR-AOP (Liu et al., 2015))
median value for UV/I− (Rasolevandi et al., 2019), and UV/S(sulfoxylate)/P
(phenol) (Asgari et al., 2020). The ARTs were highlighted in the graph
in turquoise.
ng/L by ARTs relying on a novel ternary self-assembled micelle com­
posite (Chen et al., 2020). In such ART systems, organic photosensitive
substances are often used as initiators (Chen et al., 2021). It was also
determined that the second order rate constant (k) of the PFAS and eaq−
reactions decreases with the shortening of the perfluorinated chain. For
example, k of CF3COO− degradation by hydrated electrons was reported
to be about 1.9±0.2 × 106 M− 1 s− 1, whereas the k values are 7.1±0.3 ×
106 M− 1 s− 1 and 1.7±0.5 × 107 M− 1 s− 1 for C3F7COO− and C7F15COO− ,
respectively (Huang et al., 2007). Regardless, these values are orders of
magnitude higher than those from sulfate radical reactions (even more
from hydroxyl radical reactions) with perfluorinated carboxylic acids, i.
e., ≈ 104 M− 1 s− 1 (Lutze et al., 2018).
Overall, ARTs have exibited effectiveness in the degradation of
various organic CECs such as perfluorinated compounds, pentachloro­
phenol (PCP), diclofenac and carbamazepine (Wu et al., 2021). A
number of toxic inorganic substances, e.g., nitrate, arsenite, and
bromate have been efficiently transformed by ARTs as well. Moreover,
the electrical energy per order (EEO) (Bolton et al., 2001) of ARTs
[depending on various conditions, e.g., some RA cause increase of EEO
value (Liu et al., 2015)] is within the range of reported values for AOPs
(UV, electro-based; Fig. 2).
Conclusions
• ARTs can be defined as processes utilizing strong chemical
reducing agents with E◦ ≤ − 2.3 V.
• Limitations of common remediation technologies for decontami­
nation of persistent pollutants such as PFAS call for the development of
new water treatment strategies. ARTs appear effective and/or efficient
for remediation of a number of halogenated organic compounds. How­
ever, ARTs may not be suitable for mineralization of compounds
compared to oxidation processes.
• The effects of common water matrix constituents (primarily NOM)
on ARTs need to be investigated to understand their potential negative
effects on ARTs.
• Further research could focus on improving the cost-effectiveness of
ARTs, by finding strategies to utilize less energy-demanding activation
methods (e.g., visible light). The findings learned so far on activation
methods under laboratory conditions may be extended to water samples
of contaminated sites.
3
Water Research 212 (2022) 118101
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
This work has been supported by grants (projects LTAUSA18078,
LM2018124) from the Ministry of Education, Youth and Sports of the
Czech Republic. This work was also partly supported by the Grant
Agency of the Czech Republic (GA ČR), project number GJ20–17028Y.
D. D. Dionysiou also acknowledges the support from the University of
Cincinnati through the Herman Schneider Professorship in the College
of Engineering and Applied Sciences.
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