Science of the Total Environment 864 (2023) 160820

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Phosphorus immobilisation in sediment by using iron rich by-product as

affected by water pH and sulphate concentrations
⁎
Lei Xia , Toon van Dael, Benoit Bergen, Erik Smolders
Division of Soil and Water Management, KU Leuven, Kasteelpark Arenberg 20, 3001 Leuven, Belgium

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Water acidification increased P mobilisation

from unamended sediment under anoxic
conditions.
• Water acidification accelerated reductive
dissolution of Fe(III) under anoxic condi-
tions.
• P mobilisation from amended sediment was
more affected by higher water pH.
• High sulphate promoted P release from
unamended sediments under anoxic condi-
tions.

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

Editor: Filip M.G. Tack Iron (Fe) rich by-product from drinking water treatment plants can be added to rivers and lakes to immobilise phos-
phorus (P) in sediment and lower eutrophication risks. This study was set up to investigate the P immobilisation effi-
Keywords: ciency of an Fe rich by-product as affected by the pH and sulphate (SO4) concentration in the overlying water. Both
Fe rich by-product factors are known to inhibit long-term P immobilisation under anoxic conditions. A static sediment-water incubation
Sediments
was conducted at varying buffered water pH values (6, 7 and 8) and different initial SO4 concentrations (0–170 mg SO4
Phosphorus
pH
L−1) with or without Fe rich by-product amendment to the sediment. In the unamended sediment, the P release to the
Sulphate overlying water was highest, and up to 6 mg P L−1, at lowest water pH due to higher reductive dissolution of Fe(III)
oxyhydroxides. The Fe rich by-product amendment to the sediment largely reduced P release from sediment by factors
50–160 depending on pH, with slightly lowest immobilisation at highest pH 8, likely because of pH dependent P sorp-
tion. The total sulphur (S) concentrations in the overlying water reduced during incubation. The P release in un-
amended sediments increased from 2.7 mg L−1 to 4.2 mg L−1 with higher initial SO4 concentrations, suggesting
sulphide formation during incubation and FeS precipitation that facilitates release of P. However, no such SO4 effects
were found where Fe rich by-product was applied that lowered P release to <0.1 mg L−1 illustrating high stability of
immobilised P in amended sediments. This study suggests that Fe rich by-product is efficient for P immobilisation but
that loss of Fe in low pH water may lower its long-term effect.

1. Introduction reduced functioning, biodiversity and water quality deterioration

Excessive phosphorus (P) loading into water systems causes eutrophica-
tion which poses a series of threats to the water ecosystems, including
⁎ Corresponding author.
E-mail address: lei.xia@kuleuven.be (L. Xia).
(Schoumans et al., 2014). Moreover, the associated harmful algal
blooms produce toxic substances to animals and humans (Carpenter,
2005; Ding et al., 2022). Therefore, P loading must be reduced to con-
trol eutrophication. The P sources in surface waters are categorised as
external P, such as wastewater discharge and run-off from agricultural
fields, and internal P, which is P released from the sediment resulting

http://dx.doi.org/10.1016/j.scitotenv.2022.160820
Received 19 September 2022; Received in revised form 18 November 2022; Accepted 6 December 2022
Available online 13 December 2022
0048-9697/© 2022 Elsevier B.V. All rights reserved.
L. Xia et al.
from historical loading. Internal P can be released under anoxic conditions:
e.g. the decay of algae may lead to depletion of oxygen in the water, which
in turn can cause reductive dissolution of iron (Fe)(III) oxyhydroxides and
subsequent liberation of P that previously accumulated in the sediment.
This way, internal P loading can prolong eutrophication risk for several
decades ahead (Chen et al., 2018).
Chemical immobilisation by using Fe rich sorbents is often used
approach to control internal P loading (Cooke et al., 2005; Wang et al.,
2021). This is because Fe rich sorbents not only have a strong affinity for
P, but also have no toxic effects on the natural environment when added
appropriately (Randall et al., 1999), they are readily available and thus
are beneficial to low-cost eutrophication mitigation. One of the Fe rich sor-
bents that has received considerable attention is the Fe rich by-product gen-
erated from treatment of drinking water. When the anaerobic groundwater
is pumped up from an aquifer, the ferrous Fe (Fe(II)) in the raw water is
oxidised to ferric Fe (Fe(III)) and amorphous Fe(III) oxyhydroxides form
as sludges or coated on filter sand (Chardon et al., 2012). This Fe rich by-
product has high P adsorption capacity, and has been used to immobilise
P in the lake sediments and P rich soil (Koopmans et al., 2020; Wang
et al., 2017), to remove P from wastewaters (Lambert et al., 2021) and ag-
ricultural drainage (Vandermoere et al., 2018). Previous studies show that
the P adsorption capacity of this Fe rich by-product is positively related to
the amount of reactive Fe (i.e., oxalate extractable Fe) and surface area
(Bai et al., 2014), and its Fe stability is negatively related to the amount
of bioavailable Fe (i.e., citrate-ascorbate extractable Fe (unpublished
data)). Therefore, Fe rich by-products with relatively high oxalate extract-
able Fe but low citrate-ascorbate extractable Fe should be priorly selected
as P sorbent for sediment remediation.
Apart from the inherent properties of the Fe rich by-product, environ-
mental factors, such as water pH, temperature and redox conditions may
also strongly affect the efficiency of the Fe rich by-products (Wang et al.,
2016). In general, acid conditions are beneficial to P adsorption by Fe
rich by-product as protonation of mineral surfaces enhances sorption of
negatively charged phosphate ions through electrostatic adherence (Bai
et al., 2014; Yang et al., 2006). However, acid conditions can promote the
reductive dissolution of Fe(III) oxyhydroxides, thereby facilitating release
of P that is previously bound to the Fe(III) minerals (Tang et al., 2020).
Consequently, the net effect of pH of overlying water on sediment P release
following Fe rich by-product treatment remains uncertain.
In addition to pH, the effect of sulphate (SO4) reduction to sulphides on Fe
reduction in sediment and subsequently P release needs attention because
SO4 might accumulate in freshwaters due to acid depositions and industrial
wastewater input (Zak et al., 2006). It is well established for marine sedi-
ments that the high SO4 concentrations have a role on limiting P immobilisa-
tion, less of this is clear in wetlands or freshwater sediments with lower SO4
concentrations. Several lines of evidence suggest that increasing SO4 might
mobilise P because of different potential pathways including (1) Fe(II)
sulphides precipitation lowering Fe(II) and facilitating Fe(III) reductions;
(2) sulphide reducing Fe(III) minerals to soluble Fe(II) with concurrent P
release with sulphide oxidised to elemental sulphur (S) (Peiffer et al., 2015;
Zhang et al., 2022). Sulphate reduction is affected by the SO4 concentration,
with increasing SO4 concentrations, more P is mobilised (Chen et al., 2016;
Kwon et al., 2014). At very high SO4 concentration, high SO4 reduction in
the deep anoxic sediments may influence P release from surface sediments
under oxic conditions (Hansel et al., 2015). For instance, Chen et al. (2021)
showed that internal P loading increased by a factor six when the SO4 concen-
tration increased from 970 to 2600 μM under oxic conditions. Hence, it is nec-
essary to investigate what extent of SO4 concentration would impact such P
release in sediments amended with high Fe rich by-product.
The objective of this study was to investigate the impact of water pH
and increasing SO4 concentrations on P dynamics at the sediment-water in-
terface (SWI) after Fe rich by-product amendment. A microcosm incubation
experiment was performed at three pH levels and three SO4 levels. Overly-
ing water sampling, high-resolution diffusive equilibrium in thin film (DET)
and microelectrode techniques were employed to capture the dynamic
character of P, Fe, as well as dissolved oxygen (DO) at a fine scale.
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Science of the Total Environment 864 (2023) 160820
2. Materials and methods
2.1. Materials
Surface sediment samples were collected from a stream in an agricul-
tural area (50°58′50.5”N, 3°16′29.3″E) in Flanders, Belgium. The stream
has a high long-term total dissolved P (TDP) concentration of 1.4 mg P
L−1 (van Dael et al., 2020). Sediment was collected from the top 5 cm
using a shovel and stored in a box at 4 °C. Before use, the sediment was
wet sieved (6.3 mm) to remove gravel and undecomposed organic debris
and homogenized. This sediment was chosen based on its significant respi-
ration rate in an earlier incubation experiment (Van Dael et al., 2020), indi-
cating that anoxia was likely to occur. A sub-sample of sediment was
extracted with 0.2 M acid ammonium oxalate (pH = 3) in the dark at a
solution-solid ratio of 50 L kg−1 under 2 h of shaking, to determine the
content of poorly crystalline Fe and the associated P (Schwertmann,
1991). The used sediment has oxalate extractable Fe (Feox) of 5.8 mg g−1
and oxalate extractable P (Pox) of 1.2 mg g−1, which is equivalent to a
molar P/Fe ratio of 0.37.
A high Fe and slightly alkaline by-product was collected from the drink-
ing water facility of De Watergroep in Belgium. It contained 234 mg Fe g−1,
1.3 mg Al g−1 and 1.1 mg P g−1 measured by Inductively Coupled Plasma
Mass Spectroscopy (ICP-MS, Agilent 7700×, Agilent Technologies) after
aqua regia digestion. Most of Fe in collected by-product (40 %) was amor-
phous Fe(III) oxyhydroxides, i.e., oxalate extractable Fe. The pH of the pure
Fe rich by-product is 8.3. A phosphate adsorption study was performed
showing that this product has a high P sorption capacity (8.3 g P kg−1 prod-
uct), a high affinity at low P concentration (i.e., solid-liquid distribution
coefficient KD, 2.1 L g−1) while ascorbic acid reducible Fe is 22 % of oxalate
extractable Fe (Xia, 2022). The Fe rich by-product was sieved over 2 mm
before use.
2.2. Microcosm experimental setup
The effects of the pH and SO4 concentration on P immobilisation by Fe
rich by-product under anoxic conditions were studied in a sediment incuba-
tion experiment. The homogenized sediments were put into 1.1 L polypro-
pylene pots (diameter 9.5 cm) to a height of 5 cm (550 g wet sediment and
54 % moisture content). The Fe rich by-product was added and mixed with
the top layer of sediment (0–1 cm). The Fe rich by-product was added to the
sediment at a dose of 6 %, that dose decrease the average sediment molar
P/Fe ratio of the total 5 cm sediment from 0.37 to 0.2, this dose was
found to be efficient for P immobilisation in previous study (unpublished
data). The sediment not amended with Fe rich by-product served as a con-
trol treatment. Then about 600 mL (about 6 cm height) of 1 mM CaCl2
solution with different pH or SO4 concentrations was gently added, without
disturbing the sediment, to all control and Fe rich by-product treatments.
The addition of 1 mM CaCl2 to the overlying water was used to mimic the
ionic strength of most freshwaters and was used on line with earlier and
similar sediment incubation experiments (Smolders et al., 2017). Two
experimental groups were prepared: (1) pH group: the water pH of 6, 7
and 8 were maintained by using 5 mM of 2-(N-morpholino) ethanesulfonic
acid (MES buffer, pH 6), 3-(N-morpholino) propanesulfonic acid (MOPS
buffer, pH 7) and 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid
(HEPES buffer, pH 8), respectively. The pH adjustment was conducted
daily with 0.1 M NaOH or 0.1 M HCl; (2) sulphate group: the overlying
water (without pH buffer) was supplemented with different levels of SO4,
i.e., no addition, 90 mg SO4 L−1 (i.e., 30.0 mg S L−1) and 170 mg SO4
L−1 (i.e., 56.7 mg S L−1), by dissolving Na2SO4 in the overlying water.
These SO4 levels were selected based on the mean value and 95 percentile
of SO4 concentrations in Flemish surface waters (https://www.vmm.be/).
Each treatment was performed in duplicate.
The pots were closed with lids to avoid aeration and were incubated in
controlled temperature rooms (20 ± 1 °C). During the incubation, the over-
lying water was sampled after 3, 5, 7, 11, 15, 19, 23, 27 and 31 days. Water
samples were taken at 1 cm above the SWI, then filtered (0.45 μm), and
L. Xia et al.
measured for soluble reactive P (SRP) by using the molybdate blue method
(Murphy and Riley, 1962). A subsample was acidified (1 % HNO3) and
analysed for major elements (total dissolved Fe) and total sulphur (TS)
using ICP-MS. The pH of overlying water was measured daily by using a
pH meter (Metrohm, Belgium) inserted at about 1 cm above the sediment
surface. The DO profile was measured at 0.2 cm intervals from the top
down to the SWI after 7, 19 and 31 days of all treatments by using a O2
micro sensor (tip diameter 100 μm; Unisense, Denmark) mounted on a
motor driven micro manipulator.
The diffusive equilibrium in thin film (DET) was used to measure the P
concentration in sediment pore water at mm-scale vertical resolution. The
DET devices were prepared according to Baken et al. (2015b), i.e., a plastic
probe of 17 cm long and 3.5 cm wide (DGT Research Ltd) was assembled
with a polyacrylamide diffusive gel and covered by a cellulose nitrate mem-
brane (Amersham™ Protran®, 0.45 μm pore size). The principle of DET is
the equilibration of the diffusive gel with the surrounding water, which al-
lows to retrieve a snapshot of the local concentration in sediment pore
water (Davison et al., 2002). All DET probes were soaked in 0.01 M NaCl
solution and deoxygenated using nitrogen gas for at least 16 h prior to de-
ployment in the sediment. The DET probes were inserted into the sediment
at day 19. After a 24 h deployment, the probes were retrieved and immedi-
ately dismantled. The diffusive gel was cut into slices of 3 mm × 18 mm
with a cutter. Each slice of DET diffusive gel was eluted in 1 mL of 1 M
HCl for at least 24 h and the elution was measured for total dissolved P
(TDP) and total dissolved Fe by using ICP-MS.
2.3. Data analyses
The P reduction factor quantifies the reduction of SRP after addition of
Fe rich by-products and is calculated by Eq. (1).
Pcontrol
P reduction ¼ ð1Þ
Ptreatment
where, Pcontrol and Ptreatment are SRP concentrations in the control and Fe rich
by-product treatments, respectively (mg P L−1).
Statistical analyses were performed using the JMP® Pro version 16.0.0.
The treatment effects on P and Fe in the overlying water and porewater
were analysed with general linear regression models with time and depth
added as a random factor. The effects of pH/sulphate concentrations, Fe
rich by-product addition and their interaction on P and Fe in the overlying
water and pore water were analysed with two-way ANOVA followed by
Tukey HSD post-hoc test. The correlation between water properties was
analysed with Pearson correlation.
3. Results
3.1. Phosphorus mobilisation as affected by water pH
3.1.1. pH and DO concentrations in overlying water
The solution pH values closely matched the target pH values within
0.3 pH units during the entire period (Fig. S1), mean pH values in the un-
amended sediments were 6.2, 7.0 and 7.9 while in Fe rich by-product
amended ones the mean values were 6.3, 7.2, and 7.9. In general, the
most acid pH 6.0 required daily acidification while the most alkaline one
needed daily alkalinisation to limit pH drifts. The DO in the water layer
above the sediments readily decreased with depth and was already
completely depleted by day 7 at 1–2 cm above the SWI (Fig. S2). The DO
at 1–2 cm above SWI remained extremely low until the end the experiment,
and the DO above that layer was also generally decreasing with time.
3.1.2. Concentrations of P and Fe changes in the overlying water
The treatment effects water pH and Fe rich by-product addition had a
significant effect on P and total dissolved Fe dynamics in the overlying
water (Fig. 1, Table 1). Acidification of overlying water significantly
enhanced the internal P release (Table 1). The average concentrations of
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Science of the Total Environment 864 (2023) 160820
SRP at pH 6 increased by 70 % compared to that at pH 7 and pH 8. No sig-
nificant difference in SRP release was found between pH 7 and pH 8 (p >
0.05). Amending Fe rich by-product to sediments sharply decreased SRP
concentration at all pH conditions (Fig. 1b), with P reduction factors
50–160 depending on pH (Table S1). The effect of pH on SRP concentration
in the Fe rich by-product treatment was opposite to that in the control,
i.e., P release increased with increasing pH of the overlying water.
Unlike SRP, the release of Fe was only affected by water pH and pH ×
Fe rich by-product, but not by Fe rich by-product alone (Table 1). The dis-
solved Fe concentration and the rate of Fe release were considerably higher
at pH 6 compared to that at pH 7 and 8, while no significant Fe release were
found in the Fe rich by-product treatment at pH 7 and 8, compared to the
control at same pH conditions (p > 0.05 for both pH conditions, Fig. 1d).
3.1.3. Vertical distribution of P and Fe in sediment-water profiles
The effect of pH and Fe rich by-product addition on the vertical distribu-
tion of TDP and total dissolved Fe at SWI is shown in Fig. 2. Only the TDP
and total dissolved Fe concentrations of the surface sediment layer
(at SWI to 1 cm below SWI) were selected to test the treatment effects
(Table 1) because the treatment effects on porewater TDP and total dis-
solved Fe dynamics in this layer were expected to be the most significant
due to direct contact with buffer solution and due to Fe rich by-product
addition to surface layer. There was no significant pH effect on TDP concen-
tration in the deeper layer (i.e., 10 mm below the SWI) (p > 0.05).
Similar treatment effects were found for total dissolved Fe in the pore
water as in the overlying water (Table 1), i.e., decreasing pH significantly
enhanced Fe in the sediment pore water (Fig. 2c-d), and Fe rich by-
product addition remarkably reduced TDP in the sediment pore water,
even below the 10 mm zone of Fe rich by-product incubation (Fig. 2b).
The acid reductive dissolution increased pore water TDP in the sediment
only in the control (Fig. 2a, p < 0.001), while no significant pH effect on
TDP concentration in the pore water was found in the sediment with Fe
rich by-product addition (Fig. 2b, p > 0.05).
3.2. Phosphorus mobilisation as affected by increasing SO4 concentrations
3.2.1. pH and DO concentrations in overlying water
The pH values were significantly higher in the Fe rich by-product treat-
ment than in the control at different SO4 concentrations (Fig. 3 and
Table 1). The pH of a pure Fe rich by-product in 0.01 M CaCl2 mixture
was 8.3, explaining the effect of Fe rich by-product on pH. The DO in the
water layer above the sediments readily decreased with depth and was
completely depleted at 1–2 cm above the SWI (Fig. S3). The DO concentra-
tion generally decreased with time and small differences in DO concentra-
tions were observed among treatments.
3.2.2. Concentrations of TS, P and Fe in the overlying water
The concentration of TS is the sum of concentration mainly SO4 and
traces of organic soluble S and sulphides. The TS decreased substantially
in the control and Fe rich by-product treatment with Na2SO4 addition
(Fig. 4). The theoretical starting TS is 30.0 mg L−1 (i.e., 0.9 mM, S1) and
56.7 mg L−1 (i.e., 1.8 mM, S2). That concentrations decreased by factor
2–3 in the unamended treatments while that decrease was smaller in the
Fe rich by-product amended ones.
Increasing SO4 significantly impacted SRP concentration in the overly-
ing water (Table 1), but only in the control, not in the Fe rich by-product
treatment (Fig. 4c-d). In the control, the P concentration in the overlying
water in the control_S2 was increased by about factor 2, compared to the
control_S0 (Fig. 4c). The Fe rich by-product addition significantly reduced
P concentration in the overlying water to, on average, below 0.1 mg P
L−1, and this P reduction by Fe rich by-product was not affected by SO4
concentrations (p > 0.05, Fig. 4d).
The total dissolved Fe concentration increased rapidly during the first
week to maximum values of about 6 mg L−1 in the control at all SO4 con-
centrations (Fig. 4e). The same trend of Fe release was found in amended
sediment as in the control, but with much lower concentrations (Fig. 4f).
L. Xia et al. Science of the Total Environment 864 (2023) 160820

Fig. 1. The effect of the pH in the overlying water on SRP and total dissolved Fe concentrations in the overlying water. The first column is the SRP (a) and Total dissolved Fe
(c) concentrations in the control. The second column is the SRP (b) and Total dissolved Fe (d) concentrations in the Fe rich by-product treatments. Error bars denote standard
error of the means (n = 2).

The maximum total dissolved Fe concentration only reached a maximal

1 mg L−1, and the peak values of total dissolved Fe were generally inversely
proportional to SO4 concentrations.
Table 1
Results of analysis of the effects of Fe rich by-product addition on surface and pore 3.2.3. Vertical distribution of P and Fe in sediment-water profiles
water P and Total dissolved Fe concentrations. Data were analysed with a two-way Similar treatments effects were found in TDP concentration in the sedi-
ANOVA with the amount of Fe (with or without addition) and environmental con- ment pore water as in the SRP concentration in the overlying water
−1
ditions (pH at 6, 7, 8 or SO4 addition at 0, 90 and 170 mg SO2−
4 L ) as fixed factors. (Table 1). Increasing SO4 concentrations enhanced TDP release from the
Overlying water Porewater (surface sediment in the control where the TDP concentration in the surface
to 1 cm below SWI) 10 mm layer in the control_S2 was factor 2 higher than in the control_S0
SRP (mg Fe (mg pH TDP (mg Fe (mg
(Fig. 5a). The Fe rich by-product addition also significantly reduced TDP
L−1) L−1) L−1) L−1) concentration in the sediment pore water (Fig. 4b), the vertical profile of
TDP was characterised by the absence of steep gradient at the SWI, remain-
pH treatment
Effect of pH p < 0.01 p< / p < 0.05 p< ing low and stable up to depths of 20 mm below the sediment.
0.001 0.001 The pore water total dissolved Fe concentrations increased with depth,
Effect of Fe rich by-product p< 0.579 / p< p< with a maximum concentration reached at 20–30 mm depth (Fig. 5c-d).
0.001 0.001 0.001
Amending Fe rich by-product to the surface sediment layer increased Fe
pH × Fe rich by-product p < 0.01 p < 0.01 / p< 0.494
0.001 concentrations in the pore water, while increasing SO4 concentration had
no effect on pore water Fe concentrations (Table 1).
Sulphate treatment
Effect of SO4 p< 0.814 0.448 p< 0.633
0.001 0.001 3.3. Relations between different overlying water properties
Effect of Fe rich by-product p< p< p< p< p<
0.001 0.001 0.001 0.001 0.001 The correlation analysis showed that pH played dominated role in total
Sulphate × Fe rich p< 0.902 p < 0.05 p< 0.886 dissolved Fe and SRP changes in the overlying water (Fig. 6). Overall, the
by-product 0.001 0.001
water pH was negatively correlated with total dissolved Fe in the overlying

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Fig. 2. The TDP in sediment pore water in the control (a) and Fe rich by-product treatment (b), and the total dissolved Fe in the sediment pore water in the control (c) and Fe
rich by-product treatment (d) at different pH after 19 days. The location of the sediment-water interface (SWI) is represented by zero. The Fe rich by-product was mixed in the
top 10 cm below the SWI. Error bars denote standard error of the means (n = 2).

water regardless of SO4 concentrations (Fig. 6a). The water pH was also
negatively correlated with SRP, but only in the control without amend-
ment, while a positive correlation between water pH and SRP was observed
in the Fe rich by-product treatments (Fig. 6b).
When analysing the correlations separately in the control and Fe rich
by-product treatments at different SO4 conditions (Table S2), we also
found that TS has significantly positive correlations with SRP in the control.
This correlation, however, was not present after Fe rich by-product addi-
tion. However, no correlations were found between TS and total dissolved
Fe in both control and Fe rich by-product treatment.
4. Discussion
4.1. The addition of Fe rich by-product consistently reduced P release from
sediments
In this study, the application of Fe rich by-product as amendment
strongly reduced P concentrations in the overlying water to below environ-
mental limit of 0.1 mg L−1, achieving P reduction factor of 50 to 160
depending on the pH and SO4 concentration in the overlying water
(Table S1), which confirms that Fe rich by-product addition can efficiently
reduce P release from sediments under anoxic conditions. This was
expected because the molar ratio of oxalate P over Fe in the sediment was
significantly reduced from 0.37 to 0.20 by adding this by-product to the
sediment (see Section 2.2). Kleeberg et al. (2013) showed that P can be
efficiently bound as long as the molar ratio of P/Fe in sediment was smaller
than 0.2. van Dael et al. (2020) also demonstrated that in anoxic sediment,
the P release remained below environmental limits if the molar P/Fe ratio
was lower than 0.12. At sufficiently higher molar P/Fe ratio, P released in
the sediment can still be bound to the residual Fe(III) oxyhydroxides even
though part of Fe(III) is reduced to soluble Fe(II). This also can be clearly
seen from the P and Fe changes in sediment with Fe rich by-product addi-
tion at pH 6 (Fig. 1) where the Fe release was about factor 2 higher in the
amended sediments, while the P was not released and the concentration
remined below 0.1 mg L−1, compared to unamended sediments.
Phosphorus dynamics from the sediment to overlying water are domi-
nated by concentration gradient induced pore water diffusion (Yao et al.,
2016). In unamended sediment, the P concentration depth profiles had
larger concentration gradients at the SWI (Figs. 2a and 5a), thus leading
to a stronger upwards diffusion of P towards the overlying water than in
amended sediment (Figs. 2b and 5b). This indicated that immobilisation
of TDP in the pore water by Fe rich by-product addition created a barrier

Fig. 3. The pH changes in the overlying water in control (a) and Fe rich by-product treatment (b) at increasing SO4 conditions during the 31 days of incubation. Error bars
denote standard error of the means (n = 2).

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L. Xia et al. Science of the Total Environment 864 (2023) 160820

Fig. 4. The effect of increasing SO4 concentration on the dynamics of TS (a), SRP (c) and total dissolved Fe (e) in the overlying water of control, and TS (b), SRP (d) and total
dissolved Fe (f) in the overlying water of Fe rich by-product treatment. Error bars denote standard error of the means (n = 2).

at several millimetres below the SWI, thus inhibiting the upward migration
of TDP from sediment to the overlying water. In addition, a Fe(II)/SRP
molar ratio in the porewater > 2 has been suggested to efficient removal
of released P by newly formed Fe(III) oxyhydroxides at the SWI (Gao
et al., 2020). In this study, the molar Fe/TDP ratio (as proxy of Fe(II)/
SRP) in amended treatments was mostly >4, while it was <2 in the control
(Figs. S4 and S5), indicating that upon reoxygenation of Fe(II), newly
formed Fe(III) oxyhydroxides at the SWI can efficiently scavenge upward
diffusing P and thus serve as an efficient “iron curtain” (Ma et al., 2017).
Overall, adding Fe rich by-product to the sediment can be an efficient
way to control the internal P release, thus mitigating eutrophication.
However, the efficacy of Fe rich by-product on internal P control can be
affected by water properties and needs to be discussed further.
4.2. The effect of pH on reductive dissolution of Fe and P immobilisation by Fe
rich by-product
The different total dissolved Fe concentrations and P reduction factors
by Fe rich by-product at different pH (Fig. 1 and Table S1) indicated that
the Fe and P release from sediment were largely affected by pH in the over-
lying water. In this study, higher Fe concentrations in the overlying water
and the pore water at pH 6 compared to these at pH 7 and pH 8 (Figs. 1

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Fig. 5. The TDP in sediment pore water in the control (a) and Fe rich by-product treatment (b), and the total dissolved Fe in the sediment pore water in the control (c) and Fe
rich by-product treatment (d) under increasing SO4 concentrations after 19 days. The location of the sediment-water interface (SWI) is represented by zero. Error bars denote
standard error of the means (n = 2).

and 2) illustrated that lower pH promoted reductive dissolution of Fe(III)
oxyhydroxides, as reported in many other studies (Khan et al., 2019;
Maranguit et al., 2017; Zhang et al., 2021). This is because more protons
can be provided at lower pH, thus facilitating microbial reductive dissolu-
tion of Fe(III) oxyhydroxides while degrading organic matter (CH2O)
(Eq. (2)).
4FeðOH Þ3 þ 8H þ þ CH 2 O→4Fe2þ þ CO2 þ 3H 2 O
In addition, decreased adsorption of reduced Fe(II) on the surface of
minerals at lower pH induced more Fe release to the overlying water
(Wang et al., 2018). At higher pH, lower Fe concentration in the overlying
water could be explained by a combination of reasons. On the one hand,
lower pore water Fe concentrations at higher pH than at lower pH
(Fig. 2) indicated that there is less Fe reduction at higher pH, thus less
reduced Fe diffusing to the overlying water. Flynn et al. (2014) showed
that microbial reduction of Fe(III) such as ferrihydrite and goethite was
less thermodynamically favorable when pH was higher than 7. On the
other hand, lower Fe concentration in the overlying water could be a conse-
quence of faster re-oxidation of Fe(II) at higher pH in the overlying water.
The first order rate constant kFe at which this re-oxidation occurs is depen-
dent on the DO concentration and the pH (Eq. (3)) (Baken et al., 2015a).
kFe ¼ k  ½O2   ðOH − Þ2 ð3Þ
Thus, under identical DO concentrations, the Fe re-oxidation rates are
factor 102 larger at pH 7 compared to that at pH 6. Similar observations
ð2Þ have been reported in the field, during summer (high pH and high temper-
ature), the dissolved Fe(II) is completely oxidised after surfacing (Van Der
Grift et al., 2014).
The concurrent release of P and Fe in overlying water and pore water
(Figs. 1 and 2), and their correlations in the unamended sediment
(Fig. S4a-c) illustrated that P concentration changes in response to changes
in water pH can be explained by the associated changes in the Fe concentra-
tion. The higher mobilisation of P under slightly acid conditions as com-
pared to that under neutral and slightly alkaline conditions indicated that
water acidification promoted the dissolution of Fe(III) oxyhydroxides and
subsequent P release. This effect has been well documented in flooded
acidic soils (e.g., paddy soils) where microbial-mediated reduction of Fe
(III) oxyhydroxides and associated Fe(II) mobilisation resulted in substan-
tial P release (Khan et al., 2019; Kögel-Knabner et al., 2010; Maranguit

Fig. 6. Correlations between the water pH and total dissolved Fe concentrations (a) and SPP concentrations (b) in the overlying water in control and Fe rich by-product
treatments at different pH values and initial SO4 concentrations in solution.

7
L. Xia et al.
et al., 2017). However, many other researchers found the opposite effect,
i.e., an increased P release with increasing pH (Gao, 2012; Wang et al.,
2013a; Wu et al., 2014). Wu et al. (2014) found that more P was mobilised
under alkaline conditions than acid conditions, and the least amount of P
was observed under pH neutral. This difference in pH effects on P release
from our study might be related to redox conditions. Their experiment
was conducted under aerobic conditions, which means that reductive disso-
lution of Fe(III) oxyhydroxides was unlikely to occur. Thus, the effect of pH
on P desorption due to ligand exchange between phosphate ions and
hydroxyl ions was more important than the availability of sorption sites.
However, the P mobilisation as effected by pH in the sediment with Fe
rich by-product addition was different from that in the control, i.e., P
release increased by increasing the pH of the overlying water, albeit that
this release is only minor, all P releases were 1–2 orders reduced due to
Fe rich by-product (Fig. 1). The higher Fe concentration in the pore water
of amended sediment at pH 6 compared to that at pH 7 and pH 8
(Fig. 2d) demonstrated that water acidification did enhance the reductive
dissolution of Fe(III) oxyhydroxides as discussed above, but at the same
time the associated P did not increase (Fig. 2b). This is because sufficient
Fe in the sediment amended with Fe rich by-product can effectively trap
released P even though the Fe(III) were partially reduced under anoxic con-
ditions. When P release is mainly controlled by P sorption, increasing pH
might release more P (Fig. 1b). The effect of increasing pH on P desorption
has also been reported from sediment amended with other P sorbents such
as lanthanum modified bentonite (LMB) (Kong et al., 2021), lanthanum
modified zeolite (Li et al., 2019) and aluminum (Al)-based materials
(Huser et al., 2016; Li et al., 2017). Kong et al. (2021) investigated the effect
of water pH (i.e., pH 6, 7, and 9) on P dynamics after LMB amendment at
the SWI and showed that the highest P release and lowest P immobilisation
efficiency were found at pH 9. This is because that the adsorption capacity
of LMB is largely reduced compared to the pH range of 5–7 as indicated by
Haghseresht et al. (2009). Similarly, Li et al. (2017) also found that in the
sediment with addition of zeolite/hydrous Al oxide composite, an increase
in P release with increasing pH was clear when pH exceeded 8. These could
be explained by the fact that appearance of hydroxyl ions at high pH may
compete for adsorption sites with P.
Taken together, within pH range of 6–8, the effect of pH on P release
from sediment depend on the P/Fe ratio in the sediment. In the unamended
sediment with less sorption sites (i.e., higher P/Fe ratio), the P release
under anoxic conditions was enhanced at more acid conditions, while for
the amended sediment with more sorption sites (i.e., lower P/Fe ratio),
the P release under anoxic conditions increased at more alkaline conditions.
However, on the long-term, higher reductive dissolution of Fe under more
acid conditions could result in faster loss of Fe, and thus loss of P retention
capacity, compared to more alkaline conditions, which would be detrimen-
tal the long-term efficiency of Fe rich by-product as a P binding remediation
technique.
4.3. The effect of increasing sulphate concentrations on Fe and P dynamics at the
SWI
A previous study has reported that intermediate SO4 concentrations
(9.6–28.8 mg SO4 L−1) in freshwater systems can already greatly promote
the release of internal P under anoxic conditions (Caraco et al., 1989).
Therefore, elevated SO4 concentrations and consequently enhanced SO4
reduction has gained interest as an important mechanism regulating the
biogeochemical cycle of P, especially under hypoxic conditions (Holmer
and Storkholm, 2001). In this study, the decreasing concentration of TS in
the overlying water (Fig. 4a-b) indicated the likely occurrence of SO4 reduc-
tion as a result of sediment respiration. The SO4 concentration is an impor-
tant factor determining the rate of SO4 reduction (Saxton et al., 2021). The
decrease in the SO4 concentration was larger at larger initial concentrations
indicating a higher SO4 reduction rate (Fig. S6), this was consistent with
other studies (Chen et al., 2016; Zak et al., 2006; Zhou et al., 2022).
The reduction of SO4 is mediated by SO4-reducing bacteria (SRB), and
higher SO4 concentrations can increase the numbers of SRB, which would
8
Science of the Total Environment 864 (2023) 160820
consequently enhance the SO4 reduction (Chen et al., 2016). In addition,
the slower decrease of TS (Fig. 4b) and lower SO4 reduction rate (Fig. S6)
in the sediment amended with Fe rich by-product compared to the sediment
without amendment indicated that the increase of Fe(III) in the sediment was
likely causing a delay in the reduction of SO4. Similar effects were found by
Xia et al. (2019) where a drop in SO4 concentration in the treatment with
Fe(III) was delayed for 7 days compared to the treatment without Fe(III).
When Fe(III) and SO4 are both available as electron acceptors, dissimilatory
Fe(III) reduction is preferred compared to SO4 reduction as indicated by the
reduction potential Eh and the Gibbs free energy ΔG (Peter et al., 2016;
Zhu and Schwartz, 2011). Hence, in the sediment with Fe(III) addition,
more Fe(III) would be reduced first and reduction of SO4 probably started
later when the Fe reduction reached equilibrium as shown in Fig. 4.
The correlation analysis for overlying water properties indicated that
most likely, the combined effects of Fe and SO4 reduction induced P
mobilisation in the sediment without amendment (Table S2). Previous stud-
ies demonstrated that the redox cycle of Fe(III) oxyhydroxides regulates P
dynamics (Chen et al., 2018). Here, the high P concentration in the overlying
water (Fig. 4) and sediment pore water (Fig. 5) under high SO4 concentra-
tion could be related to the sulphide-induced abiotic reduction of Fe(III)-P
complexes (Maynard et al., 2011). Similar effect of elevated SO4 on P
mobilisation has also been found in lakes (Chen et al., 2021, 2016), wetlands
(Maynard et al., 2011) and lowland rivers (Zak et al., 2006). In treatments
without SO4 addition, the P concentration decreased after a period of net
increase, a trend that was found in similar incubation tests (van Dael et al.,
2020; Xia et al., 2021). This decrease in P could be explained by re-
oxidation of Fe(II), forming Fe(III) which can re-immobilise P, or vivianite
precipitation. However, with SO4 addition, reduced sulphides can efficiently
precipitate Fe(II) and form FeS, leaving less Fe(II) to be re-oxidised to Fe(III)
and re-immobilise P or to precipitate with P as vivianite (Wu et al., 2019).
The reduction in TS over time (e.g decrease from 1.8 to 0.8 mM in Fig. 4a)
is clearly larger than the removal of Fe(II) from solution (about 0.1 mM in
control and even as low as 0.01 mM in Fe rich by-product treatments),
i.e., these trends do not obey FeS formation in water. However, the FeS
might precipitate in the sediment before Fe(II) is released to the overlying
water. This is quite likely as the pore water Fe concentrations peak to over
1 mM in the deeper horizons and are depleted at the surface, i.e., there is
considerable diffusion of Fe(II) from the sediment towards the SWI where
FeS might form. Our results indicate that current SO4 levels in freshwaters
such as Flemish lowland rivers are high enough to induce significant sul-
phate reduction in sediments and P release during summer low flow periods.
The P release from sediments with Fe rich by-product addition was con-
siderably decreased and was, in contrast to control, not affected by elevated
SO4 concentrations (Fig. 4d). The significantly low P release after addition
was mainly due to abundant Fe(III) oxides in the sediment to bind P as
discussed in Section 4.1. Besides, reoxidation of Fe(II) and subsequent P
adsorption to newly formed Fe(III) oxides could also lead to low P concen-
tration in the water column. The higher pH in the overlying water due to
the addition of the alkaline Fe rich by-product (Fig. 3b) resulted in lower
total dissolved Fe concentration in the overlying water (Fig. 4d) due to
faster Fe(II) reoxidation at higher pH (Flynn et al., 2014). This hypothesis
can be evidenced by higher total dissolved Fe concentration in the sediment
pore water (Fig. 5d), but lower total dissolved Fe concentration in the over-
lying water (Fig. 4f) in amended treatments, compared to non-amended
treatments (Figs. 5c and 4e). Therefore, a combination of abundant sorp-
tion sites, and faster Fe(II) reoxidation in amended sediment contributed
to low P release to the overlying water. Moreover, the P reduction by Fe
rich by-product was not affected by increasing SO4 concentrations. Wang
et al. (2013b) has shown that P immobilisation by Fe in drinking water
treatment residual had high stability under the effect of hydrogen sulphide.
This could be mainly explained by that Fe(III) in amended sediment was
efficient for P immobilisation even though part of Fe could be lost due to
Fe reduction and subsequent precipitation of Fe(II) with sulphide. There-
fore, providing new sorption sites by amending Fe rich by-product to sedi-
ment could be a promising technology for the control of internal P release in
high sulphate water columns.
L. Xia et al.
5. Conclusion
This study investigated the effect of pH and increasing SO4 concentra-
tion in the overlying water on P mobilisation in the sediment with and with-
out addition of Fe rich by-product from drinking water treatment under
anoxic conditions. Phosphorus release from the anoxic sediment was
affected by pH with the range of 6–8, but unamended and amended treat-
ments showed opposite trends. Decreasing the pH to 6 remarkably
increased Fe release and the associated P in the unamended sediment and
increasing solution pH to 8 increased P release in the sediment with amend-
ment although the highest Fe release still occurred at pH 6. Higher concen-
trations of SO4 significantly increased internal P release in the unamended
sediment. For sediment with Fe rich by-product addition, the P immobilisa-
tion was not affected by increasing SO4 in the overlying water, indicating
high stability of P immobilised by Fe in this Fe rich by-product. Therefore,
adding Fe rich by-product to eutrophic water systems could be a promising
technology for the control of internal P loading but the longevity of it in
more acid waters requires attention.
Data availability
Data will be made available on request.
Declaration of competing interest
The authors declare that they have no known competing financial inter-
ests or personal relationships that could have appeared to influence the
work reported in this paper.
Acknowledgements
We would like to thank the P team of KU Leuven for useful discussions
regarding the data interpretation. We also thank the ICP team for the ICP
measurements. We think the drinking water company De Watergroep
(Belgium) for kindly providing the tested material. We are also grateful to
the China Scholarship Council (No.201808510179) for granting a PhD
fellowship to the corresponding author.
CRediT authorship contribution statement
All authors contribute to the preparation of the previous and revised
manuscript, which can be seen as follows.
Lei Xia: Conceptualization, Methodology, Validation, Formal analysis,
Investigation, Writing-original draft, Writing-review & editing, Visualiza-
tion. Toon van Dael: analysis, discussion, Writing-review & editing.
Benoit Bergen: analysis, discussion, Writing-review & editing. Erik Smol-
ders: Conceptualization, Resources, Writing-review & editing, Supervision.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.scitotenv.2022.160820.
References
Bai, L., Wang, C., He, L., Pei, Y., 2014. Influence of the inherent properties of drinking water
treatment residuals on their phosphorus adsorption capacities. J. Environ. Sci. (China)
26, 2397–2405. https://doi.org/10.1016/j.jes.2014.04.002.
Baken, S., Salaets, P., Desmet, N., Seuntjens, P., Vanlierde, E., Smolders, E., 2015a. Oxidation
of Iron Causes Removal of Phosphorus and Arsenic From Streamwater in Groundwater-
fed Lowland Catchments. https://doi.org/10.1021/es505834y.
Baken, S., Verbeeck, M., Verheyen, D., Diels, J., Smolders, E., 2015b. Phosphorus losses from ag-
ricultural land to natural waters are reduced by immobilization in iron-rich sediments of
drainage ditches. Water Res. 71, 160–170. https://doi.org/10.1016/j.watres.2015.01.008.
Caraco, N.F., Cole, J.J., Likens, G.E., 1989. Evidence for sulphate-controlled phosphorus re-
lease from sediments of aquatic systems. Nature 341, 316–318.
9
Science of the Total Environment 864 (2023) 160820
Carpenter, S.R., 2005. Eutrophication of aquatic ecosystems: bistability and soil phosphorus.
Proc. Natl. Acad. Sci. U. S. A. 102, 10002–10005. https://doi.org/10.1073/pnas.
0503959102.
Chardon, W.J., Groenenberg, J.E., Temminghoff, E.J.M., Koopmans, G.F., 2012. Use of reac-
tive materials to bind phosphorus. J. Environ. Qual. 41, 636–646. https://doi.org/10.
2134/jeq2011.0055.
Chen, M., Li, X.H., He, Y.H., Song, N., Cai, H.Y., Wang, C., Li, Y.T., Chu, H.Y., Krumholz, L.R.,
Jiang, H.L., 2016. Increasing sulfate concentrations result in higher sulfide production
and phosphorous mobilization in a shallow eutrophic freshwater lake. Water Res. 96,
94–104. https://doi.org/10.1016/J.WATRES.2016.03.030.
Chen, M., Ding, S., Chen, X., Sun, Q., Fan, X., Lin, J., Ren, M., Yang, L., Zhang, C., 2018. Mech-
anisms driving phosphorus release during algal blooms based on hourly changes in iron
and phosphorus concentrations in sediments. Water Res. 133, 153–164. https://doi.
org/10.1016/j.watres.2018.01.040.
Chen, J., Zhang, H., Liu, L., Zhang, J., Cooper, M., Mortimer, R.J.G., Pan, G., 2021. Effects of
elevated sulfate in eutrophic waters on the internal phosphate release under oxic condi-
tions across the sediment-water interface. Sci. Total Environ. 790, 148010. https://doi.
org/10.1016/J.SCITOTENV.2021.148010.
Cooke, G.D., Welch, E.B., Peterson, S., Nichols, S.A., 2005. Restoration and Management of
Lakes and Reservoirs, Restoration and Management of Lakes and Reservoirs. CRC Press
https://doi.org/10.1201/9781420032109.
van Dael, T., De Cooman, T., Smolders, E., 2020. In-stream oxygenation to mitigate internal
loading of phosphorus in lowland streams. J. Hydrol. 590, 125536. https://doi.org/10.
1016/j.jhydrol.2020.125536.
Davison, W., Zhang, H., Grime, G.W., 2002. Performance characteristics of gel probes used for
measuring the chemistry of pore waters. Environ. Sci. Technol. 28, 1623–1632. https://
doi.org/10.1021/ES00058A015.
Ding, W., Zhang, C., Shang, S., 2022. The early assessment of harmful algal bloom risk in the
East China Sea. Mar. Pollut. Bull. 178, 113567. https://doi.org/10.1016/J.MARPOLBUL.
2022.113567.
Flynn, T.M., O’Loughlin, E.J., Mishra, B., DiChristina, T.J., Kemner, K.M., 2014. Sulfur-
mediated electron shuttling during bacterial iron reduction. Science 344, 1039–1042.
https://doi.org/10.1126/SCIENCE.1252066.
Gao, L., 2012. Phosphorus release from the sediments in Rongcheng swan Lake under differ-
ent pH conditions. Procedia Environ. Sci. 13, 2077–2084. https://doi.org/10.1016/j.
proenv.2012.01.197.
Gao, L., Li, R., Liang, Z., Yan, C., Zhu, A., Li, S., Yang, Z., He, H., Gan, H., Chen, J., 2020. Re-
mobilization mechanism and release characteristics of phosphorus in saline sediments
from the Pearl River estuary (PRE), South China, based on high-resolution measurements.
Sci. Total Environ. 703, 134411. https://doi.org/10.1016/J.SCITOTENV.2019.134411.
Haghseresht, F., Wang, S., Do, D.D., 2009. A novel lanthanum-modified bentonite, phoslock,
for phosphate removal from wastewaters. Appl. Clay Sci. 46, 369–375. https://doi.org/
10.1016/j.clay.2009.09.009.
Hansel, C.M., Lentini, C.J., Tang, Y., Johnston, D.T., Wankel, S.D., Jardine, P.M., 2015. Dom-
inance of sulfur-fueled iron oxide reduction in low-sulfate freshwater sediments. ISME J.
9, 2400–2412. https://doi.org/10.1038/ismej.2015.50.
Holmer, M., Storkholm, P., 2001. Sulphate reduction and Sulphur cycling in lake sediments: a
review. Freshw. Biol. 46, 431–451. https://doi.org/10.1046/j.1365-2427.2001.00687.x.
Huser, B.J., Egemose, S., Harper, H., Hupfer, M., Jensen, H., Pilgrim, K.M., Reitzel, K., Rydin,
E., Futter, M., 2016. Longevity and effectiveness of aluminum addition to reduce sedi-
ment phosphorus release and restore lake water quality. Water Res. 97, 122–132.
https://doi.org/10.1016/J.WATRES.2015.06.051.
Khan, I., Fahad, S., Wu, L., Zhou, W., Xu, P., Sun, Z., Salam, A., Imran, M., Jiang, M.,
Kuzyakov, Y., Hu, R., 2019. Labile organic matter intensifies phosphorous mobilization
in paddy soils by microbial iron (III) reduction. Geoderma 352, 185–196. https://doi.
org/10.1016/j.geoderma.2019.06.011.
Kleeberg, A., Herzog, C., Hupfer, M., 2013. Redox sensitivity of iron in phosphorus binding
does not impede lake restoration. Water Res. 47, 1491–1502. https://doi.org/10.1016/
j.watres.2012.12.014.
Kögel-Knabner, I., Amelung, W., Cao, Z., Fiedler, S., Frenzel, P., Jahn, R., Kalbitz, K., Kölbl, A.,
Schloter, M., 2010. Biogeochemistry of paddy soils. Geoderma 157, 1–14. https://doi.
org/10.1016/J.GEODERMA.2010.03.009.
Kong, M., Liu, F., Zhang, W., Xu, X., Chao, J., Wang, P., Wang, C., Gao, Y., 2021. High resolution
investigation of pH on control of mobile and organic phosphorus and associated release ki-
netics following lanthanum modified bentonite (LMB) amendment at the water-sediment in-
terface. J. Clean. Prod. 295, 126148. https://doi.org/10.1016/J.JCLEPRO.2021.126148.
Koopmans, G.F., Hiemstra, T., Vaseur, C., Chardon, W.J., Voegelin, A., Groenenberg, J.E.,
2020. Use of iron oxide nanoparticles for immobilizing phosphorus in-situ: increase in
soil reactive surface area and effect on soluble phosphorus. Sci. Total Environ. 711.
https://doi.org/10.1016/J.SCITOTENV.2019.135220.
Kwon, M.J., Boyanov, M.I., Antonopoulos, D.A., Brulc, J.M., Johnston, E.R., Skinner, K.A.,
Kemner, K.M., O’Loughlin, E.J., 2014. Effects of dissimilatory sulfate reduction on FeIII
(hydr)oxide reduction and microbial community development. Geochim. Cosmochim.
Acta 129, 177–190. https://doi.org/10.1016/J.GCA.2013.09.037.
Lambert, N., Van Aken, P., Van den Broeck, R., Dewil, R., 2021. Adsorption of phosphate
on iron-coated sand granules as a robust end-of-pipe purification strategy in the hor-
ticulture sector. Chemosphere 267. https://doi.org/10.1016/j.chemosphere.2020.
129276.
Li, Y., Fan, Y., Li, X., Wu, D., 2017. Evaluation of zeolite/hydrous aluminum oxide as a sedi-
ment capping agent to reduce nutrients level in a pond. Ecol. Eng. 101, 170–178. https://
doi.org/10.1016/J.ECOLENG.2017.02.011.
Li, X., Xie, Q., Chen, S., Xing, M., Guan, T., Wu, D., 2019. Inactivation of phosphorus in the
sediment of the Lake taihu by lanthanum modified zeolite using laboratory studies. Envi-
ron. Pollut. 247, 9–17. https://doi.org/10.1016/j.envpol.2019.01.008.
Ma, W.W., Zhu, M.X., Yang, G.P., Li, T., 2017. In situ, high-resolution DGT measurements of
dissolved sulfide, iron and phosphorus in sediments of the East China Sea: insights into
L. Xia et al.
phosphorus mobilization and microbial iron reduction. Mar. Pollut. Bull. 124, 400–410.
https://doi.org/10.1016/J.MARPOLBUL.2017.07.056.
Maranguit, D., Guillaume, T., Kuzyakov, Y., 2017. Effects of flooding on phosphorus and iron
mobilization in highly weathered soils under different land-use types: short-term effects
and mechanisms. Catena 158, 161–170. https://doi.org/10.1016/J.CATENA.2017.06.023.
Maynard, J.J., O’Geen, A.T., Dahlgren, R.A., 2011. Sulfide induced mobilization of wetland
phosphorus depends strongly on redox and iron geochemistry. Soil Sci. Soc. Am. J. 75,
1986–1999. https://doi.org/10.2136/SSSAJ2011.0031.
Murphy, J., Riley, J.P., 1962. A modified single solution method for the determination of
phosphate in natural waters. Anal. Chim. Acta 27, 31–36. https://doi.org/10.1016/
S0003-2670(00)88444-5.
Peiffer, S., Behrends, T., Hellige, K., Larese-Casanova, P., Wan, M., Pollok, K., 2015. Pyrite for-
mation and mineral transformation pathways upon sulfidation of ferric hydroxides de-
pend on mineral type and sulfide concentration. Chem. Geol. 400, 44–55. https://doi.
org/10.1016/j.chemgeo.2015.01.023.
Peter, M.K., Markus, S.N., Fendorf, K.S., Keiluweit, M., Nico, P.S., Kleber, M., 2016. Are Oxy-
gen Limitations Under Recognized Regulators of Organic Carbon Turnover in Upland
Soils?. 127, pp. 157–171. https://doi.org/10.1007/s10533-015-0180-6
Randall, S., Harper, D., Brierley, B., 1999. Ecological and ecophysiological impacts of ferric
dosing in reservoirs. Hydrobiologia 395, 355–364.
Saxton, M.A., Samarkin, V.A., Madigan, M.T., Bowles, M.W., Sattley, W.M., Schutte, C.A.,
Joye, S.B., 2021. Sulfate reduction and methanogenesis in the hypersaline deep waters
and sediments of a perennially ice-covered lake. Limnol. Oceanogr. 66, 1804–1818.
https://doi.org/10.1002/LNO.11723.
Schoumans, O.F., Chardon, W.J., Bechmann, M.E., Gascuel-Odoux, C., Hofman, G., Kronvang,
B., Rubæk, G.H., Ulén, B., Dorioz, J.M., 2014. Mitigation options to reduce phosphorus
losses from the agricultural sector and improve surface water quality: a review. Sci.
Total Environ. 468–469, 1255–1266. https://doi.org/10.1016/j.scitotenv.2013.08.061.
Schwertmann, U., 1991. Solubility and dissolution of iron oxides. Plant Soil 130, 1–25.
https://doi.org/10.1007/BF00011851.
Smolders, E., Baetens, E., Verbeeck, M., Nawara, S., Diels, J., Verdievel, M., Peeters, B., De
Cooman, W., Baken, S., 2017. Internal loading and redox cycling of sediment iron explain
reactive phosphorus concentrations in lowland Rivers. Environ. Sci. Technol. 51,
2584–2592. https://doi.org/10.1021/acs.est.6b04337.
Tang, X., Li, R., Han, D., Wu, X., 2020. Impacts of electrokinetic isolation of phosphorus
through pore water drainage on sediment phosphorus storage dynamics. Environ. Pollut.
266, 115210. https://doi.org/10.1016/j.envpol.2020.115210.
Van Dael, T., De Cooman, T., Verbeeck, M., Smolders, E., 2020. Sediment respiration contrib-
utes to phosphate release in lowland surface waters. Water Res. 168, 115168. https://doi.
org/10.1016/j.watres.2019.115168.
Van Der Grift, B., Rozemeijer, J.C., Griffioen, J., Van Der Velde, Y., 2014. Iron oxidation kinetics
and phosphate immobilization along the flow-path from groundwater into surface water.
Hydrol. Earth Syst. Sci. 18, 4687–4702. https://doi.org/10.5194/hess-18-4687-2014.
Vandermoere, S., Ralaizafisoloarivony, N.A., Van Ranst, E., De Neve, S., 2018. Reducing phos-
phorus (P) losses from drained agricultural fields with iron coated sand (- glauconite) fil-
ters. Water Res. 141, 329–339. https://doi.org/10.1016/j.watres.2018.05.022.
Wang, C., Bai, L., Pei, Y., 2013a. Assessing the stability of phosphorus in lake sediments
amended with water treatment residuals. J. Environ. Manag. 122, 31–36. https://doi.
org/10.1016/j.jenvman.2013.03.007.
Wang, C., Liu, J., Pei, Y., 2013b. Effect of hydrogen sulfide on phosphorus lability in lake sed-
iments amended with drinking water treatment residuals. Chemosphere 91, 1344–1348.
https://doi.org/10.1016/j.chemosphere.2013.02.003.
10
Science of the Total Environment 864 (2023) 160820
Wang, C., Jiang, H.-L, Jiang, H.-L., 2016. Chemicals used for in situ immobilization to reduce
the internal phosphorus loading from lake sediments for eutrophication control. Crit.
Rev. Environ. Sci. Technol. https://doi.org/10.1080/10643389.2016.1200330.
Wang, C., He, R., Wu, Y., Lürling, M., Cai, H., Jiang, H.L., Liu, X., 2017. Bioavailable phospho-
rus (P) reduction is less than mobile P immobilization in lake sediment for eutrophication
control by inactivating agents. Water Res. 109, 196–206. https://doi.org/10.1016/j.
watres.2016.11.045.
Wang, X.N., Sun, G.X., Li, X.M., Clarke, T.A., Zhu, Y.G., 2018. Electron shuttle-mediated mi-
crobial Fe(III) reduction under alkaline conditions. J. Soils Sediments 18, 159–168.
https://doi.org/10.1007/s11368-017-1736-y.
Wang, Q., Liao, Z., Yao, D., Yang, Z., Wu, Y., Tang, C., 2021. Phosphorus immobilization in
water and sediment using iron-based materials: a review. Sci. Total Environ. 767,
144246. https://doi.org/10.1016/j.scitotenv.2020.144246.
Wu, Yunhai, Wen, Y., Zhou, J., Wu, Yunying, 2014. Phosphorus release from lake sediments:
effects of pH, temperature and dissolved oxygen. KSCE J. Civ. Eng. 18, 323–329. https://
doi.org/10.1007/s12205-014-0192-0.
Wu, S., Zhao, Y., Chen, Y., Dong, X., Wang, M., Wang, G., 2019. Sulfur cycling in freshwater
sediments: a cryptic driving force of iron deposition and phosphorus mobilization. Sci.
Total Environ. 657, 1294–1303. https://doi.org/10.1016/j.scitotenv.2018.12.161.
Xia, L., 2022. The Application of Iron-rich Sorbents to Mitigate Phosphorus Release From Sed-
iments in Lowland Rivers.
Xia, D., Yi, X., Lu, Y., Huang, W., Xie, Y., Ye, H., Dang, Z., Tao, X., Li, L., Lu, G., 2019. Dissim-
ilatory iron and sulfate reduction by native microbial communities using lactate and cit-
rate as carbon sources and electron donors. Ecotoxicol. Environ. Saf. 174, 524–531.
https://doi.org/10.1016/J.ECOENV.2019.03.005.
Xia, L., David, T., Verbeeck, M., Bruneel, Y., Smolders, E., 2021. Iron rich glauconite sand as
an efficient phosphate immobilising agent in river sediments. Sci. Total Environ. 811,
152483. https://doi.org/10.1016/j.scitotenv.2021.152483.
Yang, Y., Zhao, Y.Q., Babatunde, A.O., Wang, L., Ren, Y.X., Han, Y., 2006. Characteristics and
mechanisms of phosphate adsorption on dewatered alum sludge. Sep. Purif. Technol. 51,
193–200. https://doi.org/10.1016/J.SEPPUR.2006.01.013.
Yao, Y., Wang, P., Wang, C., Hou, J., Miao, L., Yuan, Y., Wang, T., Liu, C., 2016. Assessment of
mobilization of labile phosphorus and iron across sediment-water interface in a shallow
lake (Hongze) based on in situ high-resolution measurement. Environ. Pollut. 219,
873–882. https://doi.org/10.1016/j.envpol.2016.08.054.
Zak, D., Kleeberg, A., Hupfer, M., 2006. Sulphate-mediated Phosphorus Mobilization in River-
ine Sediments at Increasing Sulphate Concentration, River Spree, NE Germany. 80,
pp. 109–119. https://doi.org/10.1007/s10533-006-0003-x.
Zhang, S., Yang, X., Hsu, L.C., Liu, Y.T., Wang, S.L., White, J.R., Shaheen, S.M., Chen, Q.,
Rinklebe, J., 2021. Soil acidification enhances the mobilization of phosphorus under an-
oxic conditions in an agricultural soil: investigating the potential for loss of phosphorus to
water and the associated environmental risk. Sci. Total Environ. 793, 148531. https://
doi.org/10.1016/j.scitotenv.2021.148531.
Zhang, S., Peiffer, S., Liao, X., Yang, Z., Ma, X., He, D., 2022. Sulfidation of ferric (hydr)oxides
and its implication on contaminants transformation: a review. Sci. Total Environ. 816.
https://doi.org/10.1016/J.SCITOTENV.2021.151574.
Zhou, C., Peng, Y., Deng, Y., Yu, M., Chen, L., Zhang, L., Xu, X., Zhao, F., Yan, Y., Wang, G.,
2022. Increasing sulfate concentration and sedimentary decaying cyanobacteria co-
affect organic carbon mineralization in eutrophic lake sediments. Sci. Total Environ.
806, 151260. https://doi.org/10.1016/J.SCITOTENV.2021.151260.
Zhu, C., Schwartz, F.W., 2011. Hydrogeochemical processes and controls on water quality and
water management. Elements 7, 169–174. https://doi.org/10.2113/gselements.7.3.169.