Chemical Engineering Journal 426 (2021) 130821

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Chemical Engineering Journal

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Zero-valent iron mediated biological wastewater and sludge treatment

Xingdong Shi, Wei Wei *, Lan Wu, Bing-Jie Ni *
Centre for Technology in Water and Wastewater, School of Civil and Environmental Engineering, University of Technology Sydney, Sydney, NSW 2007, Australia

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

Keywords: In quest of meeting the requirements of sustainable development, coupling zero valent iron (ZVI) with micro­
Zero-valent iron organisms has attracted extensive attentions for enhancing biological wastewater and sludge treatment in terms
Biological wastewater treatment of microbial growth, nutrients removal, and resources recovery. Given to the significant role of ZVI playing in
Sludge reduction
biological wastewater and sludge treatment, a thorough evaluation of the associated interactions among ZVI and
Anaerobic digestion
Removal mechanism
microorganisms is necessary to further scale-up the application of ZVI-based biotechnologies. To this end, this
Phosphorus recovery review comprehensively summarizes the mechanisms of ZVI for enhancing nutrients removal (i.e., C, N, S and P)
in several typical biological wastewater treatment processes, discusses the role of ZVI in improving the excess
sludge reduction by dewatering or anaerobic digestion for methane production, and analyzes the feasibility of
recovering phosphorus from anaerobic sludge digestion system in the form of vivianite through using ZVI.
Knowledge gaps regarding the application of ZVI in sludge or wastewater treatment are also identified in this
review to facilitate the further development of the ZVI-based biological technology.

1. Introduction anaerobic ammonium oxidation (Anammox) is used to remove nitrogen

Carbon (C), hydrogen (H), nitrogen (N) and phosphorus (P) account
for>95% of the total biological composition. Most of them will move
into the biological chain and eventually enter the sewage. Discharging
large amounts of organic-rich wastewater causes a massive consumption
of dissolved oxygen in the water due to microbial catabolism, resulting
in the death of aquatic life and the deterioration of water bodies
consequently. Similarly, high levels of N and P in wastewater effluents
lead to eutrophication, harmful algal blooms and dead zones in aquatic
environment [1]. Sulfate-rich seawater has been widely applied for
toilet flushing and fire extinguishing in various coastal cities, which
leads to sulfate intrusion into wastewater system [2]. High contents of
sulfate are responsible for pipeline corrosion and hindering microbial
processes [3]. As such, removing organics, nitrogen, phosphorus, and
sulfate is the most important objective in wastewater treatment plants.
Biological treatment technology is the main method for the removal
of aforementioned nutrients from wastewater in wastewater treatment
plants due to its low operating costs compared with physical/chemical
treatment. Anaerobic digestion is a highly effective way for biological
sludge treatment, which has the advantages of low energy consumption,
high sludge reduction, and substantial biogas production. After nearly a
hundred years of development, various strategies have been formed to
adapt to treating different wastewater and sludge. For example,
in wastewater containing high ammonium but low organic carbon [4].
High-strength organic wastewater or sludge are usually treated by
anaerobic treatment process [5,6].
Despite of its long history and many outstanding merits, biological
wastewater and sludge treatment technology still faces enormous chal­
lenges to meet today’s increasing demand for wastewater reuse and
energy recovery [7]. A potential strategy is to improve the living con­
ditions of relative microorganisms by constructing a reducing environ­
ment to enhance the efficiency of biological treatment through chemical
intervention cost-effectively. Given zero-valent iron (ZVI) possesses high
reducibility (E0 = − 0.44 V [8]) and easily available characteristics,
adding ZVI to the biological wastewater and sludge treatment process is
considered as an ideal chemical intervention [9]. ZVI is a multifunction
chemical agent. In general, ZVI can remove a variety of contaminants by
acting as catalyst via promoting some oxidants or dissolved oxygen to
release reactive oxygen species [10,11], adsorbent [12], or coprecipi­
tator [13]. Therefore, ZVI has been widely used in biologically treating
wastewater and sludge for past decades to remove varieties of organic
matters [14,15] and heavy metals [16].
The inherent chemical properties of ZVI also have positive impacts
on the biological wastewater and sludge treatment process. For example,
Karri et al. [17] revealed that ZVI can act as an electron donor to
enhance the anaerobic treatment process, and increased methane yield

* Corresponding authors.
E-mail addresses: wei.wei@uts.edu.au (W. Wei), bingjieni@gmail.com (B.-J. Ni).

https://doi.org/10.1016/j.cej.2021.130821
Received 28 March 2021; Received in revised form 18 May 2021; Accepted 9 June 2021
Available online 16 June 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
X. Shi et al.
and sulfate reduction efficiency. Previous research suggests that multi­
ple mechanisms are responsible for the enhancement of biological pro­
cesses by ZVI including decreasing the level of oxidation reduction
potential of mixed liquor [18], providing electron for functional bacte­
rial [19], enhancing the transformation of electron among different
microbial species [20], etc. Besides enhancing biological process
directly, some indirect chemical and physical processes (i.e. adsorption
and redox) resulting from ZVI are also the possible explanations for
promoting pollutants removal from wastewater [21,22]. Up to now, ZVI
has been widely used for improving sulfate-reducing process [5],
dehalogenation [23,24], denitrification [25], heavy metal immobiliza­
tion processes [26,27], and aerobic granular sludge [28].
Comprehensively summarizing the research advance of ZVI-based
biological process is significant for guiding future research direction.
Although several reviews on ZVI-based biological process have been
published previously, most of them are mainly focused on the perspec­
tive of pollutants removal [29-32]. Considering different biological
processes are dominated by different functional microorganisms, the
mechanisms involved in the typical biological wastewater and sludge
treatment processes would be distinctive. However, there is still a lack of
review focusing on the enhancement of biological wastewater and
sludge treatment by ZVI, although the studies concerning the dose­
–effect of ZVI on its relationship among corresponding microorganism
has been intensively examined. In addition, the development of ZVI
based technology is eventually for full-scale industrial applications.
However, its actual industrial applications in bio-based process have
currently not been demonstrated yet due to the existing knowledge gaps.
This review is thus urgently required to summarize the available and
unavailable knowledges to facilitate its potential application in near
future.
In this review, the chemical and physical properties of ZVI will be
firstly discussed to establish the foundations for further digging the role
of ZVI in either wastewater or sludge treatment. The typical applications
of ZVI to these two biological processes along with corresponding
mechanisms are then deeply summarized. Anammox, phosphorus
removal, sulfate reduction and aerobic granular sludge are chosen as the
typical biological processes to illustrate how ZVI addition improves the
organics, nutrients and sulfate removal during wastewater treatment.
Herein, the potential interaction mechanisms of intensified performance
of wastewater treatment and other sludge variation including extracel­
lular polymeric substances and granulation will be analysed in detail. As
for the impact of ZVI on sludge treatment, this paper will start with the
analysis regarding the enhancement of CH4 yield from anaerobic
digestion after dosing ZVI, followed by discussing the phosphorous re­
covery caused by ZVI-induced vivianite formation, and end up with the
evaluation of sludge dewaterability in the presence of ZVI. Finally, the
future research directions would be proposed to facilitate the future
application of ZVI in wastewater or sludge treatment.
2. ZVI properties in biological wastewater and sludge treatment
systems
2.1. The chemical and physical process of iron release and oxides
formation
ZVI is unstable even under anaerobic conditions, which would react
with water, contaminants and even trace dissolved oxygen (DO < 0.2
mg/L) in the wastewater and/ or sludge system. [11,33]. According to
these oxidation processes, ZVI would be firstly transformed into Fe(II)
(Eqs. (1)-(4)). Under natural or slight acidic conditions (pH > 5.8), Fe(II)
would hydrolyze and form Fe(OH)2 (Eq. (5)). Fe(OH)2 and Fe(II) are
sensitive to dissolved oxygen thereby forming Fe(III) followed by the
conversion to precipitation or iron oxides at the surface of ZVI due to
hydrolysis when pH level is higher than 3.7 [34]. The type of oxide film
on the surface of ZVI varies with the available dissolved oxygen in the
water. The high concentration of dissolved oxygen results in high
2
Chemical Engineering Journal 426 (2021) 130821
oxidation rates and would favor FeOOH or Fe(OH)3 formation (Eqs. (6)
and (7)) [35], while Fe3O4 would be the product under anoxic or
anaerobic conditions (Eq. (8)) [36]. The formation of this oxide film
would require few hours or a couple of days to occur and thereby
decrease the reactivity of ZVI called “aging” (Fig. 1) [37]. Of note is that
structural divalent iron (Fe(II)) has the reducibility to pollutant [38].
Therefore, the reduction reaction among Fe(II) and some organic mat­
ters would be the main removal mechanism under anoxic conditions. In
the case of oxic conditions, the Fe(II) would be rapidly oxidized to Fe
(III), resulting in ineffective adsorption and co-precipitation. However,
Tang et al. (2015) observed enhanced chloroacetic acids removal rate
after raising dissolved oxygen from 0 to 1.52 mg/L, which was decreased
with further elevating the concentration of dissolved oxygen [39]. This
initial improvement but final decreases are attributed to different
structures of iron corrosion coatings between anoxic and oxic condi­
tions. Higher but not excessive O2 availability can lead to a larger
volumetric expansion and longer migration path which is essential for
chemical reduction [40].
Albeit some co-existing anions might affect the ZVI performance of
pollutant removal in pure chemical/ physical processes [41,42], the
positive or negative function of these anions could not be determined in
the biological process. This is because some ions such as HCO–3, SO2–4 and
NO–3 are the essential nutrients to microorganism growth. In this case, it
is difficult to judge whether the overall performance change is attributed
to limited microbial metabolism or the restricted chemical process of
ZVI. Therefore, we will not discuss the influence of co-existing anions on
the bio-ZVI system in our review.
Fe0 + 2H2 O→Fe2+ + H2 ↑ + 2OH− (1)
Fe0 + 2H+ →2Fe2+ + H2 ↑ (2)
2Fe0 + 2H2 O + O2 →2Fe2+ + 4OH− (3)
2Fe0 + 2H+ + O2 →Fe2+ + H2 O2 (4)
Fe2+ + 2H2 O→Fe(OH)2 ↓+2H+ (5)
4Fe2+ + 10H2 O + O2 →4Fe(OH)3 ↓+8H+ (6)
4Fe2+ + 6H2 O + O2 →4FeOOH↓+8H+ (7)
6Fe2+ + 6H2 O + O2 →2Fe3 O4 ↓+12H+ (8)
2.2. The categories of ZVI and its prime enhanced mechanisms in
biological wastewater and sludge treatment systems
Based on the particle size, the type of ZVI can be divided into nano-
sized ZVI (nZVI) and micro-sized ZVI (mZVI) which is relatively larger
than previous one [8]. In addition, nZVI could also increase the abun­
dance of some functional bacteria by stimulating their enzymatic ac­
tivity in bioreactor [43]. Compared to mZVI, nZVI exhibited higher
efficiency to promote biological process due to its smaller size [34]. In
detail, the large specific surface area possessed by the small particle size
of nZVI (1–100 nm) can lead to better physical and chemical properties
thereby inducing higher reactivity for the remediation of pollutants
[44]. Also, benefiting from nano size, nZVI is more easily to diffuse into
cells and directly acting on protein (enzyme) production. The free pas­
sage of nZVI in cells also results in a high toxicity with lower dosage than
mZVI. In sum, the overall performance of biological wastewater and
sludge treatment could be significantly promoted by mZVI or nZVI
despite the possible negative effects exerted by this Fe-rich material on
microbiome.
Generally, both mZVI and nZVI are the accelerators to various
chemical and biological reactions. For example, the Fe contained in ZVI
have made such material became an efficient activator and catalyst for
X. Shi et al.
Fig. 1. Schematic diagram of ZVI corrosion in aqueous phase of biological wastewater and sludge treatment systems.
improving the decomposition of hydrogen peroxide and persulfate to
generate free radicals, thereby promoting pollutants degradation and
sludge dewatering accordingly [43]. In addition, nZVI could also in­
crease the abundance of some functional bacteria by stimulating their
enzymatic activity in bioreactor [44]. Compared to mZVI, nZVI
exhibited higher efficiency to promote biological process due to its
smaller size [33]. In detail, the large specific surface area possessed by
the small particle size of nZVI (1–100 nm) can lead to better physical and
chemical properties thereby inducing higher reactivity for the remedi­
ation of pollutants [45]. Also, benefiting from its nano size, nZVI is more
easily to diffuse into cells and directly acting on protein (enzyme) pro­
duction. The free passage of nZVI in cells also results in a high toxicity
with lower dosage than mZVI. In sum, the overall performance of bio­
logical wastewater and sludge treatment could be significantly pro­
moted by mZVI or nZVI despite of the possible negative effects exerted
by this Fe-rich material on microbiome.
The overall enhanced mechanisms by ZVI (nZVI and mZVI) in bio­
logical wastewater and sludge treatment systems could be summarized
into two aspects, i.e., improving the habitat and encouraging functional
microorganisms’ growth by promoting protein production. Fig. 2 shows
all these mechanisms with detailed descriptions. Note that the intensi­
fied bio-treatment process caused by ZVI should be attributed to afore­
mentioned mechanisms occurring simultaneously or sequentially.
Improving the habitat of various microorganisms and bio-chemical
processes are the most obvious advantages of ZVI addition. ZVI
benefiting from reducibility could significantly drop the oxidation
reduction potential (ORP) in the wastewater or sludge treatment system,
thereby stimulating the growth of microorganisms and contaminant
removal. One obvious example is that H2, a common reductant, gener­
ating from iron corrosion via Eqs. (1) and (2) can be utilized by various
autotrophic and heterotrophic bacteria to reduce pollutants. Aside from
Fig. 2. The enhanced mechanisms in the ZVI-biological system.
3
Chemical Engineering Journal 426 (2021) 130821
H2, the aforementioned iron oxides like Fe(OH)2 are also responsible for
the ZVI-created reductive environment. Another performance on facil­
itating living environment is that ZVI can stabilize pH level at near
neutral or weak acidic conditions, which is attributed to alkaline release
(Eqs. (1) and (3)) and proton consumption (Eqs. (2) and (4)). Generally,
some carboxylic acid (e.g., acetic acid, propionic acid, etc.) would be
formed in the anaerobic fermentation process. Over time, the accumu­
lation of these acids occurring in the extraction-lacking system would
induce the drop of pH level, under which biological metabolism could be
totally inhibited. In contrast, ZVI addition could prevent this pH from
falling and facilitating microorganism growth [46].
Additionally, iron element released from iron corrosion is also the
crucial factors on either catabolism or anabolism because it is the main
central metal element in various functional enzymes such as hydroxyl­
amine redox enzymes and hydrazine oxidase in Anammox bacteria [47].
Except for compositing vital enzymes, ZVI could significantly stimulate
the performance of some other non-Fe functional enzymes. For example,
Wang et al. (2021) reported that nZVI increased the activity of pyruvate
formate-lyase (PFL) in formic acid production [48]. Note that enhanced
enzyme production would lead to the high metabolic activity of the
corresponding microorganism, shaping the microbial community in the
system subsequently. Moreover, H2 and ZVI can be directly utilized by
hydrogen-utilizing methanogens and iron-reducing bacteria to improve
pollutant removal [49]. Overall, ZVI promotes some functional micro­
organism growth thereby improving corresponding performance in
biological wastewater and sludge treatment systems.
3. Enhanced biological wastewater treatment by ZVI
At present, ZVI-based biological wastewater treatment process has
been widely used in chemical oxygen demand (COD), nitrogen and
X. Shi et al.
phosphorus removal [50]. Several mechanisms are responsible for
enhancing biological wastewater treatment by adding ZVI. Table 1
summarizes the current application of ZVI for the removal of various
nutrients and the corresponding mechanisms. Overall, such enhance­
ment is the result of multiple biological, physical, and chemical pro­
cesses occurring simultaneously or in a certain order [50]. Therefore, it
is necessary to summarize the synergistic effects of ZVI and various
biological wastewater treatment processes on removing various pollut­
ants. The following representative biological wastewater treatment
processes will be analyzed regarding the impact of ZVI on these
processes.
3.1. ZVI facilitates Anammox process for nitrogen removal
Anammox as a promising nitrogen removal process is considered to
be one of the most energy-saving processes for nitrogen removal due to
the saving of carbon source and oxygen [4]. However, the long start-up
time and the inadaptability to low temperature have limited the full-
scale applications of Anammox [51]. ZVI has been proved to be an
Table 1
The summary of the ZVI-enhanced biological pollutant removal and the pro­
posed mechanisms.
Pollutants Processes Proposed explanations
Nitrogen Denitrification (1) Microorganisms directly
extracted electrons from ZVI.
(2) Hydrogen production by ZVI
reacting with water.
Hydrogen could be used as
electron donor to reduce
NO–3.
(3) Fe(II) released from ZVI
could also act as electron
donor
Anammox (1) Enhance the synthesis of
heme-containing enzymes.
(2) Shortening the start-up
period.
(3) Enhancing aggregation
properties of anammox
sludge.
Autotrophic (1) ZVI used as electron donor in
denitrification nitrate reduction process.
(2) Change the denitrification
process to more efficient
pathway
Sulfate Sulfate (1) Decreasing OPR to facilitate
reduction SRB.
(2) Hydrogen produced by ZVI
reacting with water supplied
electron to SRB.
Perchlorate Reductive (1) H2 provided from ZVI could
dechlorination serve as an electron donor for
reduction of chlorinated
contaminants.
(2) ZVI improve the cell density
Heavy Sulfate (1) Enhanced SRB activity
metal reduction provided S2- to precipitate
metals.
(2) ZVI improved the stable of
metal precipitation
Organic Anaerobic (1) ZVI could increase the
matter process abundance of methanogens
(2) Enhanced SRB could utilized
COD and decreased the
competition of SRB and
methanogens to electrons
Phosphors Phosphor (1) Released Fe(II)/Fe(III)
removal species could bind PO3−4 .
(2) Multiple physical and
chemical process including
surface precipitation and
absorption
Chemical Engineering Journal 426 (2021) 130821
effective method to enhance the activity of anaerobic ammonium
oxidation bacteria (AnAOB) [50]. Table 2 exhibits the improved per­
formance including start-up time and nitrogen removal efficiency by ZVI
addition. Overall, the enhancement mechanism can be attributed to
three aspects: 1) releasing dissolved iron to promote the growth of
AnAOB by participating in the synthesis of heme-containing enzymes; 2)
shortening the start-up period of Anammox reactor; and 3) enhancing
aggregation properties of Anammox sludge.
As described in Section 2, ZVI would be oxidized to ion form by
water, pollutants and even trace dissolved oxygen (Eqs. (1)–(3) and Eq.
(9)) due to its strong reducibility [11]. Fe(II) would be initially formed
and then oxidized to Fe(III). Fe is the component of the most important
enzymes like heme cytochromes and iron‑sulfur proteins [47] in
AnAOB, enhancing the metabolism of Anammox process accordingly
(Fig. 3) [52]. Recent study showed that the anammoxosome, an essential
organ in AnAOB, contains iron particles and could function in iron
respiration [53]. Thus, an appropriate amount of iron would promote
the Anammox process. Liu and Ni [54] systematically studied the effects
of different concentration of Fe(II) (0.03 to 0.18 mM) on Anammox
process. The results showed that the AnAOB showed a high specific
Anammox growth rate of 0.172 d− 1 under 0.09 mM Fe(II) condition.
Note that a higher concentration of ZVI (1 g/L) would initially inhibit
the reproduction of Anammox, but later enhanced their growth [55].
Except for enhancing metabolism process, ZVI would also improve
Ref. overall total nitrogen removal rate. The theoretical maximum total ni­
[148] trogen removal rate of Anammox is 88.8%, because Anammox process
will generate 0.26 mol nitrate (per mol ammonium) that cannot be used
by AnAOB (Eq. (10)) [56]. As described by the Eq. (11), ZVI could react
with nitrate to form ammonium then utilized by AnAOB [57].
4Fe0 + 8H+ + SO2−4 →4Fe2+ + 4H2 O + S2− (9)
− − −
NH+ +
4 + 1.32NO2 + 0.066HCO3 + 0.13H →1.02N2 + 0.26NO3
+ 0.066CH2 O0.5 N0.15 + 2.03H2 O (10)
[52,61]
4Fe0 + 10H+ + NO−3 →NH+
4 + 3H2 O + 4Fe
2+
(11)
In addition, the nanoscale ZVI (nZVI) also stimulates the Anammox
process, which would be more beneficial than the regular scale ZVI. The
main advantage of nZVI is that it is easy to diffuse into cells then be
[149,150] further used by organisms. Moreover, the high specific surface area
provides higher activity for biological reactions compared with the
mZVI [58]. Previous work compared the effects of microscale ZVI
(mZVI) and nZVI on the start-up of anammox process and showed nZVI
[151] exhibiting a shorter start-up period [57]. However, nZVI likely interacts
with various microorganisms to limit microbial activity [59]. This in­
hibition is caused by membrane disruption, DNA damage and the
inactivation of enzyme triggered by the small size nZVI. The research of
[152 153] nZVI toxic effect revealed that both 20 and 50 mg/L nZVI have negative
effects on the performance of continuous-flow Anammox reactor, but
the performance would return to normal shortly [60]. The author
pointed out that this short-term inactivation might be attributed to the
[78] under-expression of iron assimilation and utilization genes [60]. How­
ever, more evidence should be provided in the follow-up study to verify
this hypothesis. Overall, although ZVI has some negative reports on
Anammox process, it still be the best candidate to accelerate the full-
[5,6] scale application of Anammox process.
In fact, ZVI could also increase Anammox activity by indirectly
affecting sludge characteristics and extracellular polymeric substances
(EPS). The level of ζ potential reflects the tendency of sludge aggrega­
tion. Adding Fe(II) could compress the electrical double layer and
[63] neutralize charge, inducing decrement in ζ potential of microbial floc,
denoting microorganisms would be more likely to gather together [58].
In this way, the slow-growing microorganisms like AnAOB will be more
difficult to be washed out and hardly eliminated by the reactor, thus
ensuring the better growth environment of Anammox microorganisms.
4
X. Shi et al. Chemical Engineering Journal 426 (2021) 130821

Table 2
The performance of Anammox process (start-up time and nitrogen removal efficiency) by ZVI addition.
type Reactor Dosage seed sludge Strat-up time Performances Ref.

mZVI ASBR 5.3 g/L activated sludge (2 g-MLSS/L) 105 d (shortened by 90.9% or NH4 - N and 91.9% for NO2-N [57]
16.7%)
nZVI 84 d (shortened by 90.3% for NH4 - N and 90.2% for NO2-N
33.3%)
iron scraps SBR 30 g/L Aerobic sludge (5.43 g-MLVSS/L) Around 100d a Improve total nitrogen removal rate by 29.45% [149]
ZVI serum 100 mg/L Anaerobic granular sludge (8 g- 96 d >85% [55]
powder bottlesb 1 g/L MLVSS/L) 87 d
nZVI SBR 0.04–5000 enriched Anammox culture — Improved ammonium and nitrite removal rates [58]
ppb by 58%

Note:
a
The start-up time is estimate from the original figure with the standard of above 90% total nitrogen removal rate.
b
The working model of serum bottles is a continuous flow model. (Abbreviation: ASBR: anaerobic sludge blanket reactors. SBR: sequencing batch reactor)

Fig. 3. Schematic diagram of iron assimilation and utilization in anaerobic ammonium oxidation (Anammox) bacteria proposed in literature [47], with permission
from Elsevier. Copyright © 2017 Elsevier B.V. All rights reserved.

In addition, ZVI could also stimulate the secretion of EPS from Anammox
microorganisms, which is manifested by increasing the polysaccharides
[61]. The increase of polysaccharides in EPS represents higher sludge
hydrophobicity [62]. High level of EPS also means better Anammox
sludge sedimentation and less inhibition to enzymes during long-term
operation of the Anammox reactor. Therefore, the microbial floc
would agglomerate and adhere together then finally form large-size
Anammox granular sludge for better nitrogen removal performance.
3.2. ZVI enhances phosphorus removal from wastewater
Phosphorus is the main nutrient causing eutrophication in a water
environment. In general, the enhanced biological phosphorus removal
(EBPR) and chemical phosphorus removal (CPR) processes are widely
applied for phosphorus removal in wastewater treatment [63]. Gener­
ally, limited by the low efficiency of biological phosphorus removal,
wastewater treatment plants usually need to dose iron salts to further
eliminate phosphate. This is the most effective method for enhanced
biological phosphorus removal. In this enhanced process, the Fe(III) is
the main iron species that plays an important role in phosphorus

5
X. Shi et al.
removal [64]. ZVI and nZVI could also act as this reactive iron source for
removing phosphorus [65]. Phosphorus removal resulting from ZVI or
nZVI is mainly attributed to precipitation, electrostatic adsorption and
the formation of Fe-P complexes (Fig. 4, Eqs. (12) and (13)) [66]. Recent
research investigated the effects of ZVI on the UASB reactor performance
to treat wastewater contained Vitamin C. They observed that the phos­
phate removal efficiency was significantly improved from 68.5% to
85.2% [67]. The enhanced performance is attributed to the iron chem­
istry. The releasing Fe(III) or Fe(II) from ZVI would be oxidized to Fe(III)
oxides which absorb phosphate in water [68]. Abdala et al. [69] found
that P and iron oxides can form different surface complexes through
extended X-ray absorption fine structure spectra, i.e., bidentate mono­
nuclear, bidentate binuclear and monodentate mononuclear surface
complexes. The types of the formed complexes depend on the kind of
iron oxides and solution conditions [69]. The formation of these com­
plexes can then lead to the enhanced removal of phosphate by ZVI.
PO3−4 + 3Fe2+ →Fe3 (PO4 )2 ↓ (12)
PO3−4 + Fe3+ →FePO4 ↓ (13)
The process of phosphorus removal by adding ZVI is complicated.
Except for absorption, surface precipitation also contributes to the high
removal rate of phosphorus by ZVI [63]. Solid shell would be developed
after surface precipitation, preventing the precipitated phosphorus from
desorbing and avoiding the occurrence of equilibria within the solution
[70]. The Fe resulting in surface precipitation also comes from ZVI
particles. The surface precipitation can explain why nZVI has a high
adsorption capacity (245 mg P/g), even if its specific surface area (27.6
m2/g) is not enough [71]. Therefore, the process of ZVI-based removal
of phosphate can be described as follows. At the early stages of the
removal process, the phosphate would be adsorbed by the iron oxides
from ZVI until the adsorption capacity is saturated. After that, the sur­
face precipitation will gradually replace the adsorption to further
remove phosphate, allowing ZVI to exceed its adsorption capacity to
remove phosphorus.
In addition, Fe releasing from ZVI would also stimulate several bio­
logical processes such as iron-dependent autotrophic denitrification and
process involved with dissimilatory iron-reducing bacteria. The overall
performance of the reactor would be augmented thereafter. Simulta­
neous removal of nitrogen and phosphorus can even be attained after
ZVI dosage [72]. Table 3 shows the phosphorus removal efficiency in
some microbial treatment after ZVI addition. The performance of bio­
logical process was overall improved, but the chemical and/or physical
characteristics of ZVI are responsible for enhanced phosphorus removal.
Fig. 4. Schematic diagram of ZVI-mediated phosphate removal.
6
Chemical Engineering Journal 426 (2021) 130821
3.3. ZVI improves biological sulfate reduction process
Sulfate-reducing bacteria (SRB), a specialized group of dissimilatory
bacteria, is exclusively responsible for sulfate reduction in natural sub­
surface systems [73]. These bacteria utilize organic matter (Eq. (14)) or
hydrogen (Eq. (15)) as the electron donor to reduce sulfate under
anaerobic conditions [74]. The performance of the sulfate reduction by
SBR can be improved by ZVI addition [75]. Fig. 5 shows the enhanced
mechanisms of sulfate reduction process. As described in Section 2, ZVI
would be oxidized to Fe(II) and discharge hydroxyl ions (OH–) and H2
via Eq. (1) under the hypoxic environment. Given these benefits, ZVI is
an ideal reactive media in permeable reactive barriers (PRB) for
groundwater treatment. The consumption of H2 by SRB could alleviate
pressure in PRB, thereby prompting the stability of PRB for long-term
running [21]. Another evidence that ZVI promotes the growth of SRB
is that its microbial abundance is 1 to 3 orders of magnitude higher than
that of the control group [76]. However, these fast-growing microor­
ganisms would lead to a rapid rate of ZVI corrosion and precipitate
formation. The precipitate could then further affect the reaction effi­
ciency of ZVI [77]. Therefore, how to balance the pros and cons of ZVI is
a problem that needs to be solved in the future.
Simultaneously removing heavy metals is an additional benefit of the
improved sulfate reduction. The sulfide would be initially formed from
SRB under anaerobic conditions (Eqs. (14) and (15)). Then heavy metals
will react with sulfides to constitute stable sulfide precipitates and be
removed from the water. In general, ZVI would increase the stability of
precipitates compared with SRB system alone [78]. In this case, metal
ions are more difficult to return to water. ZVI strengthens heavy metal
removal and sulfate reduction, not through single precipitation. It
should be a combination of multiple biochemical processes. For
example, some specific metals (e.g. Cu(II)) can be reduced and con­
verted to more stable precipitates by ZVI [79]. Moreover, the ferrous
sulfide formed by the reaction and the EPS around SRB both are excel­
lent adsorbents for heavy metals [80]. Overall, the removal of heavy
metals in the SRB system in the presence of ZVI is a combination of
chemical reduction and biosorption.
SO2−4 + 2CH2 O→H2 S + 2HCO−3 (14)
SO2−4 + 4H2 + 2H+ →H2 S + 4H2 O (15)
The mechanism of ZVI-enhanced sulfate reduction mainly includes
two aspects: abiotic and biological reaction [75]. ZVI can directly or
indirectly provide electron to convert sulfate via Eq. (16) and Eq. (17).
The existence of sulfide will inhibit the activity of SRB, but Fe(II) formed
X. Shi et al.
Table 3
The phosphorus removal efficiency coupling with microbial treatment by ZVI addition.
Addictive Initial concentration Removal efficiency
carbon source/ZVI materials 5 mg PO3-
4 -P /L 0.21 ± 0.07 mg PO3-
4 -P/(L⋅h)
nZVI/Ni 100 mg/L 92.5%
nZVI 50 mg/L >60%
nZVI 5 mg/L 96%
mZVI 23%
nZVI 10 mg/L 91%
Fig. 5. Schematic diagram of ZVI-mediated sulfate reduction process.
by ZVI can react with it to generate iron sulfide precipitates. This re­
action is beneficial for SRB because it reduces the risk of toxic sulfide
(Eq. (18)). Previous research has shown that the sulfate decreased
minimally after sterile ZVI addition, while a higher sulfate reduction
rate was obvious with SBR existence [17]. These results indicated that
the sulfate reduction by ZVI enhancement mediated by biological re­
action mainly.
2−
4Fe0 + SO4 + 8H+ →FeS + 3Fe2+ + 4H2 O
4Fe0 + 2H2 O→Fe2+ + H2 + 2OH−
2−
2Fe2+ + SO4 + 4H2 →FeS + 4H2 O
3.4. ZVI promotes aerobic granular sludge process for nutrients removal
Aerobic granular sludge (AGS) technology has increasingly attracted
research interest in the last two decades. Similar to the hierarchical
structure of anaerobic granular sludge, AGS can also form a specific
layered structure, the aerobic outer layer and the anaerobic inner layer
[81]. Owing to this special hierarchical structure, AGS can simulta­
neously remove carbon, nitrogen, phosphorus and other pollutants in a
single sludge system [82]. However, the AGS technology still has the
disadvantages of poor stability and long start-up time.
The first study of using ZVI to enhance aerobic granulation was
conducted by Kong et al. [83]. ZVI could significantly reduce the start-
up time and this improvement is mainly attributed to more EPS release
(especially protein). Other research indicated that Fe(III) and Fe(II)
released by ZVI could prompt the size and stability of AGS but had no
obvious effects on the granulation time [84]. In addition to ZVI, nZVI
could also accelerate the formation of aerobic granulation to<50 days
[85]. Albeit all current research indicated that ZVI and nZVI have ad­
vantages of reducing granulation time and stimulating some functional
microorganisms in AGS, the dosage of ZVI should be expanded to reveal
the boundary concentration that promoted but not inhibited AGS in the
future study. Note that a high concentration of Fe(II) and Fe(III) have
side effects on various functional bacteria (e.g., nitrifying bacteria [86],
Anammox organisms [87] and denitrifiers [88]) due to the toxicity of
Chemical Engineering Journal 426 (2021) 130821
Dosage Reactor Removal mechanisms Ref.
30% ZVI weight ratio batch adsorption and precipitation [154]
0.5 g/L batch complexation and co-precipitation [155]
1 g/L batch adsorption [156]
400 mg/L batch adsorption [157]
5 g/L
200 mg Fe/L batch adsorption and precipitation [158]
iron. These functional microorganisms can also be alive in the AGS
system, thus on-going evaluation of influence of ZVI on AGS from the
perspectives of enzymatic activity and microbiology is deemed
necessary.
As discussed above, increased EPS content is one of the mechanisms
for enhancing aerobic granulation by ZVI. The EPS matrix as an
important component of AGS plays an important part in microorganisms
aggregation, granule formation and structural stability [81]. EPS can
aggregate microorganisms to form granular through the characteristics
of adhesion. In addition, the hydration of granule surfaces caused by EPS
can also stimulate the resistance of AGS to shear stress [89]. In fact, the
impact of ZVI on AGS is no single. The mechanism of enhancing AGS also
includes that, 1) Fe(II) released by ZVI can bind with proteins or poly­
saccharides in EPS [90], 2) promoting the microbial growth [91], 3)
improving the microbial agglomeration [83] and 4) some precipitates
converted from Fe(III) or Fe(II) can also be attached by microorganisms
to serve as seed aggregates and growth cores [92].
Except for influencing the characteristics of EPS and microbial
agglomeration, the ZVI could also change the microbial community of
AGS. Some studies have found that iron can inhibit the growth of fila­
mentous bacteria whose growth is the main reason for the collapse of the
AGS structure [93,94]. This means ZVI would favor the formation of
granules with smooth and compact structures, but solid evidence is still
lacking to support this assumption.
(16)
4. Enhanced biological sludge treatment by ZVI
(17) 4.1. ZVI enhances anaerobic sludge digestion for methane production
(18) Recently, numerous studies aimed to improve the efficiency of AD by
introducing ZVI into the system [95]. Table 4 summarized the methane
production performance of AD with the addition of ZVI. Most of them
showed that adding ZVI to AD could elevate the methane yield to
different degrees with different particle sizes and dosages. Evidence
provided by a two-stage reactor (combining with acidogenic reactor and
methanogenic reactor) indicated that the enhanced methane yield could
be attributed to the improvement of hydrolysis and acidification process
via introducing ZVI into acidogenic reactor instead of methanogenic
reactor [96]. In the end, the methane production rate improved by
16.1% resulting from less propionate and more acetate in acidogenic
reactor by ZVI. Acetate is more favorable for methane production than
propionate. Therefore, optimized fatty-acid products stimulated the
substrate utilization leading to the increased methane yield. Moreover,
another research also observed simultaneous enhancement of methane
production and sulfate reduction [5]. Specifically, ZVI-added reactor
shown 91% sulfate removal rate and 0.21 L/g-COD CH4 production rate,
which were 1.7 and 2 times higher than those in control system [5].
However, Yang et al. [97] found negative effects of ZVI addition on AD.
In their research, 1 mM and above nZVI could reduce methane pro­
duction by>20% and the inhibitory effect on CH4 increased with the
concentration rising. The disruption of cells and rapid H2 production by
nZVI are responsible for this inhibition. Therefore, more research is
needed to focus on the toxicity of nZVI to methanogens.
3Fe0 + 4H2 O→4H2 + 4Fe3 O4 (19)
7
X. Shi et al. Chemical Engineering Journal 426 (2021) 130821

Table 4
Enhanced methane production performance of AD by ZVI.
Waste Volume Reactor Size Dosage Temp. Performances Ref.

PWDD batch 100 mesh 6 g/L 35 ◦

C + 15.2% BMP [159]
WAS 0.5 L batch 50 nm 30 mM 35 ◦
C + 37.5% CH4 yield [160]
cattle dung slurry 10 L batch 9 nm 20 mg/L 37 ◦
C + 59% CH4 yield [161]
WAS 0.25 L batch 0.2 nm 20 g/L 35 ◦
C + 43.5% CH4 yield [49]
digested sludge 0.4 mL batch 55 ± 11 nm 1 mM 37 ◦
C − 20.3% CH4 yield [147]
10 mM − 20.3% CH4 yield
30 mM − 69.1% CH4 yield
< 212 μm 30 mM +9.7% CH4 yield
WAS 2L+6L two-stage 0.2 mm 20 g/L 15–20 ◦ C + 16.1% CH4 yield [96]
swine manure 1.5 L batch 0.5–10 μm 5 g/L 37 ◦ C +54.2% CH4 yield [97]
dewatered sludge 0.5 L batch 50 nm 0.5% 37 ◦ C +45.8% CH4 yield [65]
food waste — batch 40 nm 5 g/L 35 ◦ C +62.58% biogas yield [162]
2 g/L 55 ◦ C +26.87% biogas yield
anaerobic granular sludge 9.4 L UASB — 300 g 35 ◦ C +90.0% CH4 yield [5]

Note: PWDD: Pre-concentrated domestic wastewater; BMP: biomethane production potential; WAS: Waste activated sludge; SCFR: Semi-continuous flow reactors.

4H2 + CO2 →4CH4 + 2H2 O (20)
Note that ZVI could also alleviate the adverse influences of sulfate
reduction on methanogenesis in the AD system containing high-
concentration sulfate. Aforementioned SRB possess a high affinity for
some organic substrates and H2, resulting in competition with metha­
nogens for these electron donors [98]. Aside from this substrate
competition, hydrogen sulfide produced from SRB is an inhibitor on AD,
especially for acetogens and methanogens steps [5]. With respect to the
first obstacle, ZVI could release H2 via Eqs. (1) and (2) and promote the
transformation from propionate to acetate, supplying more electron
donors to both SRB and anaerobic microbes [49]. Simultaneously, toxic
hydrogen sulfide would be consumed by ferrous ions released abidingly
from ZVI corrosion, which could significantly alleviate this toxicity [99].
Considering a higher growth rate and higher affinity for substrates [98],
there must be other rationales to clarify why methanogens are still the
dominated microorganisms in this promoted sulfate reduction system.
Recently, scientists pointed out that the DIET of methanogenesis is a
potential answer to clarify this enhanced methane production under SRB
stress [100].
The Fe(II) released by ZVI can be oxidized to Fe(III) under anaerobic
conditions and generate hydrogen through the Schikorr reaction (Eqs.
(17) and (19)). The produced hydrogen can be further utilized by
methanogens to convert into methane (Eq. (20)), promoting interspecies
hydrogen transfer (IHT) subsequently [101]. IHT between fatty acid-
oxidizing bacteria and methanogens is critical for methane produc­
tion. H2 and formate whose formation occurs only at a trace concen­
tration of substances, which works as diffusive electron shuttles for
methanogens [102]. Therefore, AD system without ZVI may lead to an
extremely low electron transfer efficiency [103]. Differently, ZVI as a
conductive material was thought to be the electron bridge via DIET, and
thereby stimulating the electron transfer efficiency [104]. These elec­
trically conductive materials instead of electron shuttles will allow
electrons coming from pre-fermented bacteria to directly move to
methanogens [105]. In this case, this DIET could overcome the draw­
back of slow rate and the lack of energy resulting from trace concen­
tration of substances [105]. Three theories have been suggested to
explain the mechanism of DIET (Fig. 6): 1) related functional bacteria
attaching to conductive materials to transfer electrons; 2) forming an
electron conduit; 3) replacing membrane-bound electron transport
proteins with nano-sized conductive materials [106]. However, there is
still a lack of literature to reveal the role of ZVI in DIET and this part
needs be further investigated.
Notably, current research only detected DIET related microorgan­
isms to indirectly indicate DIET process. Generally, two types of DIET-
related bacteria are responsible for DIET, including electron-donating
bacteria and methane-forming archaea. The most common electron-
donating bacteria are Geobacter metallireducens and Geobacter
hydrogenophilus, while Methanosarcina barkeri and Methanosarcina
harundinacea are their corresponding methanogens partners [107].
Other potential DIET microorganisms are identified by modern molec­
ular biology technology, which are Thauera [108,109], Corynebacte­
rium [110], Clostridium [111], Coprothermobacter [112], and
Syntrophomonas [113] species. Correspondingly, its methane-forming
partners include Methanosaeta [114], Methanospirillum [113], Meth­
anobacterium [105], Methanolinea [109], and Methanoregula [115].

Fig. 6. Three mechanisms of DIET via (A) conductive materials; (B) conductive pili on the associated organisms and (C) replacing conductive pili with nano-sized
conductive materials.

8
X. Shi et al.
Aside from promoting DIET-related microorganisms, the addition of
ZVI could stimulate the growth of some functional microorganisms such
as hydrogenotrophic methanogens, SRB etc. [44,116]. ZVI seems to
have fully positive effects on all steps of AD. Separate bacterial con­
sortium analysis indicated that three functional microbiomes including
organic pollutant-utilized bacteria, fatty acid-producing microorgan­
isms and methanogenesis significantly increased in a ZVI-mediated AD
reactor feed with coking wastewater [117]. In addition, benefiting from
enhanced H2 releasing (Eqs. (1) and (2)), some hydrogenotrophic
methanogenesis process would be promoted. Indeed, it was verified in
various mZVI-based AD [118]. However, research indicated that nZVI
addition seems to have negative effects on hydrogenotrophic meth­
anogenesis. For example, the abundances of methanobacterium dropped
from 26.98% to 15.31% after introducing GAC/nZVI into AD [119]. Pan
et al. suggested that this inhibition is resulted from rapid H2 formation
spurred by dissolution of nZVI, whereas we suggest the toxicity of nZVI
to these hydrogenotrophic methanogenesis might be more reasonable
explanation [120]. More evidence is needed to verify all these
hypotheses.
4.2. ZVI facilitates vivianite formation for phosphorus recovery in sludge
treatment
Vivianite (Fe3(PO4)2⋅8H2O), a kind of iron phosphate mineral, is
considered as one of the most stable Fe(II) orthophosphates over a broad
pH range [121]. Vivianite can be formed under the conditions of an
anaerobic, nonsulfidic and high ferrous and phosphate concentration
environment [63]. Vivianite shows a huge potential of phosphorus re­
covery in sludge treatment due to its wide applications such as pigments
[122], fertilizers [121] and manufacturing high energy density energy
storage materials (LiFePO4) [123].
Fig. 7. The biosynthesis process of vivianite in the existence of ZVI. Designed originally according to the description of Li et al, [168].
9
Chemical Engineering Journal 426 (2021) 130821
In recent years, various forms of iron have been introduced into
anaerobic sludge digestion for producing vivianite [124,125]. Fe(III)
and Fe(II) are the most popular iron species in P recovery from waste­
water as vivianite [126]. The maximum phosphorus recovery efficiency,
62.1% of TP in municipal wastewater reached by Li, Wang and Li [127].
However, there is limited research applying ZVI as the iron source to
form vivianite. Puyol et al. [128] observed the formation of vivianite
when studying the effect of ZVI on anaerobic digestion. nZVI could also
promote the formation of vivianite at the elevated nZVI dose [129].
Notably, current research indicated that Fe(III) is superior to ZVI in
releasing iron ions leading to a low available concentration of Fe(II) by
using ZVI [130]. However, the cheaper ZVI would still be an ideal
supplementary iron source to produce vivianite by the iron-containing
sludge from the chemical phosphorus removal process.
The main components of vivianite (Fe3(PO4)2⋅8H2O) are iron and
phosphorus. In wastewater treatment plants, Fe usually comes from the
iron flocculant used for phosphorus removal or sludge dewatering. The
iron usually exists as Fe(III) in water environment including the ion
form, Fe(OH)3 precipitation and ferric oxide [63]. Notably, the oxida­
tion state of Fe in vivianite is + 2. Therefore, it is necessary for vivianite
formation to reduce Fe(III) to Fe(II). This process could be completed by
dissimilatory metal-reducing bacteria (DMRB) [131]. Moreover, organic
phosphorus which cannot use as the P source to form vivianite could be
transformed into inorganic phosphorus by anaerobic microorganisms
[126].In this case, Fe(II) and P will gradually accumulate. Once the
concentration of Fe(II) and PO3- 4 reaches the vivianite solubility product
(Ksp = 10-36 [132]), the vivianite will be formed. Fig. 7 and Eqs. (21)-
(23) show this formation process of vivianite. The formation of vivianite
could be divided into three parts, i.e., the formation of Fe(III)-P complex,
the reduction of Fe(III) by DMRB and the re-precipitation of vivianite. In
the anaerobic fermenter where phosphate is released by phosphate
X. Shi et al. Chemical Engineering Journal 426 (2021) 130821

accumulating organisms, the free phosphate would be adsorbed by the
surface Fe(III) oxide shell of ZVI or would co-precipitated with Fe(III) to
form various Fe(III)-P complex (Fig. 7A). Herein, the Fe(III)-P complex
are further reduced into its corresponding Fe(II) complex by the function
of DMRB (Fig. 7B). Once pH level decreasing, Fe(II)-P complex dissolves
and Fe(II) and orthophosphate releases into the supernatant. Eventually,
these ions reprecipitate to form vivianite by simply adjusting pH level to
8 (Fig. 7C).
OrganicP ⇒anaerobicmicroorganisms PO3−4 (21)
Fe(OH)3 + 3H+ + e− ⇒DMRB Fe2+ + 3H2 O (22)
3Fe2+ + 2PO3−4 + 8H2 O→Fe3 (PO4 )2 ∙8H2 O↓ (23)
In fact, DMRB is another microorganism that can benefit from
enhanced IHT except for methanogens. The typical DMRB including
Geobacter and Shewanella can utilize organic matter and H2 to reduce Fe
(III). In this process, Fe(III) is the electron acceptors while organic
matter or H2 is the electron donor. Therefore, it can be foreseen that ZVI,
which has an enhanced electron transfer effect, can strengthen the
DMRB process thereby improving the generation of vivianite. However,
the researcher seems to have not got ideal results on ZVI [130]. This is
mainly due to the low Fe(II) releasing rate of ZVI. Therefore, further
research should address the problem of ZVI dissolution such as using the
smaller nZVI.
4.3. ZVI improves sludge dewaterability for sludge treatment
It is reported that ZVI could act as a catalyst to decompound peroxide
for generating free radicals to stimulate sludge dewaterability
[133,134]. Generally, the moisture content of waste sludge in the
wastewater treatment plants is above 80%. The characteristics of high
moisture content have led to high transportation and treatment costs.
Therefore, enhancing sludge dewatering by ZVI is an ideal strategy for
reducing these burdens and promoting sludge treatment efficiency.
Generally, the method to activate peroxide (e.g persulfate (PS) and
hydrogen peroxide (HP)) to generate free radicals includes transition
metal catalyst [135] and energy activation (heat, ultrasonic and ultra­
violet) [136]. Among them, ZVI has been recognized as a powerful and
attractive method to active peroxide due to its non-toxic and cheap
properties. It is reported that using ZVI as the catalyst could reduce total
costs by 30% compared with Fe(II) as the catalyst [137]. More impor­
tantly, some studies observed enhanced sludge dewatering in ZVI/
peroxide system even under neutral pH and the capillary suction time
(CST) of sludge could reduce by 90% [138]. This means that the ZVI/
peroxide system could eliminate the costs of adjusting pH because the
traditional Fenton reaction must occur in an acidic condition [139].
Multiple researchers have investigated the impact of ZVI and nZVI on
sludge dewatering. Table 5 summarized the dewatering performance by
using ZVI/ nZVI coupling with peroxide. Overall, the ZVI/ peroxide
system could significantly improve sludge dewaterability. For example,
after treated by 0.6 g ZVI /g total solid and 0.08 g H2O2/g total solid, the
water content (Wc) decreased from 91.2% to 68.6% [140]. However, the
research conducted by Zhen et al. [141] indicated that the effect of the
ZVI/PS system on waste active sludge treatment was statistically insig­
nificant. They suggested that this insignificant efficiency resulted from
the low dissolution speed of ZVI due to the oxide iron layer above the
ZVI surface. Although some methods like decreasing pH level or ZVI
addition in batches could relief this drawback [141], there are still need
to further improve the sludge dewaterability.
In general, mechanical dewatering (e.g. filtration and centrifugation)
can easily remove free water and a part of bound water in the sludge.
However, the sludge dewaterability is hard to be further increased
because EPS accumulates around the bacterial and form a protective gel
like reservoir for preventing water outflow [142]. In addition, EPS
containing carboxyl, hydroxyl and amino are negative charge leading to
bacterial forming a stable flocs and prevent the release of water [143].
These drawbacks could be relieved at the presence of free radicals
generating from ZVI/ peroxide system. Hydroxyl radicals (•OH) is the
main free radicals in the ZVI/ HP system (Eq. (24)), while sulfate radical
(SO-•
4 ) is the responsible radicals in the ZVI/ PS system (Eq. (25))
[137,144]. •OH (E0 = 1.7–2.8 V) or SO-• 4 (E0 = 2.5–3.1 V) have such a
high oxidation potential that they can easily oxidize the pollutants in
water [145]. Similarly, these strong oxidative free radicals could also
disrupt sludge floc and oxidize EPS to further release interstitial water
and bound water. The variation of EPS is the main reason for enhanced
sludge dewaterability. In general, EPS around bacteria are a two-layer
structure, i.e., loosely bound EPS (LB-EPS) and tightly bound EPS (TB-
EPS). LB-EPS could bind water by hydrogen bond forces while TB-EPS
also play an adhesion role in combining microorganisms [146]. Recent
research demonstrated that TB-EPS could be transformed into LB-EPS by
the treatment of nZVI/ PS system [133]. This result indicated the
enhanced sludge dewaterability was attributed to the changes the af­
finity of EPS for water and increased the possibility of EPS dissolution. In
fact, except for EPS variation, free radicals could also improve the
permeability of the cell membranes leading to stimulate the intracellular
water releasing [146].
Fe2+ + H2 O2 →Fe3+ + OH + OH− (24)
Fe2+ + S2 O2−8 →Fe3+ + SO−4 + SO2−4 (25)
5. Knowledge gaps and opportunities
ZVI has aroused extensive attention recently as a promoter to

Table 5
The effects of treatment by peroxide coupling ZVI on sludge dewatering.
Catalyst Peroxide pH Raw WC Treated sludge Ref.

WC CST reduction SRF reduction

15 g/L ZVI 4 g PS/ L — — — 50% — [137]

0.5 g/L ZVI 0.25 g HP/L 2 — — 50% — [144]
0.6 g ZVI /g TS 0.08 g HP/g TS 3 91.2% 68.6% 50.7% 41.4% [140]
0.3 g ZVI/g DS a 0.03 g HP/g DS 2.5 97.2% 44.2% — 93.60% [163]
2 g ZVI/ g TS 0.5 g PS/g TS — 88.1% 71.2% 42.5% — [164]
0.05 g ZVI /g TS 0.1 g PS/g TS — — — 80% — [165]
63 mg ZVI /g TS 30 mg O3/g TS 2 — — 84.4% 41.9% [166]
0.35 g ZVI/g DS 0.15 g PS/g DS — 98.6% 83.7% — — [167]
2.0 g ZVI/g TS 0.5 g PS/g TS neutral 97.2% — 90% — [138]
G-nZVI b PS 7.73 — — — 93.8% [133]

Note:
a
The treatment method is a combination of ZVI/H2O2 and anaerobic mesophilic digestion.
b
G-nZVI refers to nanoscale zero valent iron modified by Ginkgo biloba L. leaf and the ratio of G-nZVI with PS is 1:1. (Abbreviation: Wc: water content; CST:
capillary suction time; SRF: specific resistance of filtration; TS: total solid; DS: dry solids; HP: hydrogen peroxide; PS: persulfate)

10
X. Shi et al.
improve biological wastewater treatment and excess sludge reduction.
However, despite that considerable efforts have been dedicated to the
potential of using ZVI-based technology to treat wastewater or sludge,
several knowledge gaps have yet to be demonstrated with further
investigation.
The biggest bottleneck of using ZVI to enhance biological wastewater
treatment is the secondary treatment of wastewater due to the formation
of iron-containing sludge and the color of final water caused by the Fe
(III) ions. More importantly, although nZVI with nanoscales has superior
performance on biological wastewater treatment, this small size also
helps nZVI to better survive in the environment, inducing higher nZVI
accumulation in the biological chain subsequently. Some reactors like
UASB or EGSB will cause a long stay of eco-toxic nZVI due to their high
sludge residence time in the systems. Therefore, the cumulative toxicity
of nZVI should be fully understood. In addition, developing in-situ
separation methods of ZVI-based material and improving reuse perfor­
mance are essential for mitigating environmental risks and reducing
running costs. Although the mechanism of ZVI for various wastewater
biological treatment technologies has been well explained at chemical
and macro-biological level, its potential mechanism of interaction in
molecule-level depth is still unclear. For example, studies have found
that ZVI can promote the removal of phosphorus in bioreactors due to
biological synergistic effects, but limited articles report the impact of
ZVI on phosphorus accumulating bacteria. Some molecular biology
techniques such as transcriptomics, proteomics and metabolomics are
attractive approaches to investigate the said bioprocess.
It is worthy of recognition that ZVI plays a positive role in promoting
sludge dewatering and improving anaerobic sludge digestion. However,
some studies still observed statistically its insignificant promotion of
sludge dewaterability [141] and negative effects on AD [147]. More
investigations are warranted to explain these negative phenomena
happened during digestion after ZVI dosage. Improving the dissolution
rate of ZVI is a possible solution to address such issue, but the following
effect is still not satisfactory. Therefore, follow-up studies need to
further explore mitigation measures to improve the efficiency. ZVI has
the potential to replace conventional iron sources in vivianite formation,
but there is a lack of data to demonstrate the efficiency of ZVI. In
addition, the passivation effects also exist in the vivianite formation for
phosphorus recovery by using ZVI. Hence, some improvements are still
needed to enhance and maintain the reactivity of ZVI.
6. Conclusion
The enhancement of biological wastewater treatment caused by ZVI
addition can be generally summarized into following aspects. For
granular sludge-based treatment technologies such as Anammox and
AGS, ZVI can strengthen sludge granulation to enhance the retention
capacity of sludge. It is very crucial for functional bacteria with longer
generations because these bacteria can better play the role of treating
pollutants in the system. Secondly, ZVI can also change EPS to improve
the aggregation characteristics of the sludge. Most importantly, the
impact of ZVI on wastewater biological treatment is usually multiple.
For example, ZVI enhances sulfate reduction while improving the heavy
metal removal capacity in wastewater treatment. In addition, simulta­
neous removal of nitrogen and phosphorus has been observed in the
bioreactor due to the enhanced iron-dependent autotrophic denitrifi­
cation and the dissimilatory iron-reducing process by ZVI.
ZVI could also improve the sludge treatment and resource recovery
including sludge dewaterability, anaerobic digestion and phosphorus
recovery. The enhancement of sludge dewaterability is mainly attrib­
uted to the free radical generation via catalyzing peroxide by ZVI. These
radicals could disrupt sludge floc and oxidize EPS to release interstitial
water and bound water. Superior DIET instead of IHT resulted from the
addition of ZVI stimulates the bioconversion including the methanogens
to promote the CH4 production. Moreover, DMRB also benefits IHT,
which promotes the generation of vivianite in anaerobic iron-rich sludge
11
Chemical Engineering Journal 426 (2021) 130821
digestion thereafter. In theory, we believe that ZVI can promote the
biosynthesis of vivianite to a huge degree. In fact, although studies have
found vivianite production during the ZVI-fed AD, the recovery rate is
still not satisfactory. In addition, low dissolution rate of ZVI and the
passivation effects are the main problems that need to be solved urgently
to improve the performance of sludge treatment and resource recovery.
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.
Acknowledgement
This work is supported by an Australian Research Council (ARC)
Future Fellowship (FT160100195). Ms. Lan Wu was supported by China
Scholarship Council (File No. 201806330112) for a PhD scholarship at
the University of Technology Sydney.
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