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PII: S1385-8947(17)32181-2
DOI: https://doi.org/10.1016/j.cej.2017.12.060
Reference: CEJ 18221
Please cite this article as: R. Yin, C. Fan, J. Sun, C. Shang, Oxidation of iron sulfide and surface-bound iron to
regenerate granular ferric hydroxide for in-situ hydrogen sulfide control by persulfate, chlorine and peroxide,
Chemical Engineering Journal (2017), doi: https://doi.org/10.1016/j.cej.2017.12.060
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Oxidation of iron sulfide and surface-bound iron to regenerate granular
and peroxide
Submitted to:
University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
Control & Treatment of Heavy Metal Pollution, the Hong Kong University of
1
Abstract
estuaries and marine seafloor is a nuisance. The regeneration of the GFH for
hydrogen sulfide. This paper investigated the oxidation of iron sulfide and
peroxide for the in-situ control of hydrogen sulfide. The hydrogen sulfide
GFH were 68.34, 77.49, 67.87 and 57.59 mg S/g, respectively. The recovery of
the capacities was mainly attributed to the oxidation of iron sulfide, surface-
bound Fe(II) and released Fe2+ to amorphous ferric hydroxides. Iron sulfide was
(S(0)) (5.8 and 25%), thiosulfate (S2O32-) (27.7 and 11.3%) and SO42- (66.5 and
persulfate, the reaction between persulfate and the surface Fe(II) compounds
also generated sulfate radicals and hydroxyl radicals, which enhanced the
oxidation of the iron sulfide and surface-bound iron compounds on the GFH
2
1. Introduction
applications prevent the concrete corrosion, but cannot prevent hydrogen sulfide
formation, causing the odor nuisance and toxic effects. Chemical treatment can
3
Among the often-applied chemical treatment technologies, addition of
hydrogen peroxide and chlorine, which oxidize hydrogen sulfide into benign
forms of S(0) and SO 42-, have been applied to preventing the emissions of
sedimentary hydrogen sulfide in wells and swamps [6]. Addition of iron salt
(e.g., ferrous sulfate, ferric chloride and potassium ferrate) in the liquid form is
soluble chemicals at high concentration can result in the release of the excessive
to ensure the treatment efficiency for hydrogen sulfide control, which increases
and relatively long-lasting approach. Unlike soluble chemicals such as iron salts
that are easily released into the water phase, granular iron oxides in the solid
Fe(II) compounds, iron sulfide (FeS(s)) and S(0) under the given conditions [10–
12]. The used iron granules can be recovered by aerobic oxidation through
4
dissolved oxygen (DO) enhancement for an extended time period (e.g., more
than 6 h), in which process the hydrogen sulfide removing capacity is restored
FeS(s)) back to ferric (hydr)oxides [13]. However, S(0) generated from the
oxygen [14,15].
for in-situ regeneration of iron granules in storm drainage network and marine
been widely used in the subsurface systems (e.g., groundwater, soil, estuary and
chemical oxidants is not practically feasible to control the slowly generated and
accumulated hydrogen sulfide, due to high operational costs [13]. Also, these
oxidants are found capable of oxidizing Fe(II) compounds such as pyrite (FeS2)
control [18,19]. Under such a circumstance, the used iron granules can be
5
regenerated, thus restoring their ability for continuous use for hydrogen sulfide
control. In this manner, the iron granules (e.g., GFH) are the primary reagent
applied to controlling hydrogen sulfide and the oxidants are dosed periodically
for the regeneration of iron granules. It is anticipated that the integrated use of
GFH and chemical oxidants will significantly reduce the overall oxidant
consumption and operational costs that are encountered when the oxidant is
solid Fe(II) compounds with applied oxidants. The hydrogen peroxide was
found to oxidize FeS(s), resulting in the formation of ferric hydroxides and S(0)
coverage on the surface [20]. The hydrogen peroxide was also found to oxidize
FeS2 to form surface-bound Fe(III) and SO 42- that dissolved in water [21].
Chlorine and persulfate were also reported to oxidize FeS(s) but the reaction
by strong oxidants were conducted in pure water, and the complex compositions
such as persulfate and hydrogen peroxide, have their specific properties (e.g.,
sulfide and amorphous surface-bound Fe(II) compounds has not been reported
6
in the literature. 3) The interactions of Fe(II) compounds (e.g., Fe2+, FeS2 and
radicals (SO 4-•) and chlorine radicals (Cl•) under certain experimental
subsurface systems and how they contribute to the oxidation of surface Fe(II)
oxidation of iron- and sulfur- containing products during the regeneration by the
GmbH & Co. KG (Germany) and used without further purification. The
measured physical and chemical characteristics of GFH are listed in Table S1.
7
sodium sulfide crystals (Na2S·9H2O) in nitrogen-purged water. A free chlorine
stored at 4°C in the dark. The chlorine concentration was measured before each
test. Hydrogen peroxide (30%) was diluted with deionized water. A persulfate
deionized water and stirring overnight. The seawater was obtained from the
odorous box culvert in Jordan Valley of Hong Kong, was prepared by spiking
other components) into seawater. The composition of the nutrient stock solution
is adopted from the study by Wang et al. and listed in Table S2 [27]. Sediment
samples used in this study were collected from the odorous box culvert in Hong
Kong. Chemical and physical properties of the sediment samples are shown in
Table S3.
an anaerobic glove box chamber (855, Plas Labs Inc., USA) to avoid the
8
interference from oxygen. All experiments were conducted in duplicate at room
temperature of 22 ± 1°C.
conditions. A flow-over reactor system was set up to simulate the box culverts
in Hong Kong, where the saline sewage flowed over the sediments and
the reactor (10 cm in length, 4 cm in width and 45 cm in height) was filled with
the sediment samples (35 cm in height), and continuously supplied with the
synthetic substrate containing sulfate (300 mg S/L) and organic carbon (100 ±
5.0 mg C/L), which flowed over the sediment surface at a flow rate of 20 mL/h
sulfide measurement. After the hydrogen sulfide generation became stable, the
GFH was operationally considered being used up. The hydrogen sulfide
removal capacity of the virgin GFH was calculated from the cumulative
amounts of sulfide that were removed before the GFH exhaustion (Eq. 1) [13].
9
∑ Mass of sulfide removed
Sulfide removal capacity =
Mass of GFH
Eq. 1
(0.5 M) was injected into the sediment layer (2.5 cm beneath the sediment
surface), using a 10-mL syringe with a long and fine needle at eight evenly
substrate was resumed, and the hydrogen sulfide control capacity of the
investigate the interactions between the GFH and the oxidants. Tests were
conducted in 310 mL glass bottles with Teflon lined caps (Wheaton, USA), to
[13]. The used GFH was thoroughly mixed with oxidant solutions using an end-
over-end rotator at predetermined dosages (1, 5, 10, 15 and 20 mM) and the
initial pH of 8.0. The pH value was chosen to simulate the slightly alkaline
[13]. No pH buffer was used during the oxidation of the GFH. After 3-h
reaction time and 15-min standing, the settled solids were collected to measure
the surface S(0), surface acid volatile sulfide (AVS) and surface Fe(II). The
10
thiosulfate (S2O 32-), SO42-, suspended S(0), suspended AVS and
dissolved/suspended Fe(II). The oxidation of the used GFH was calculated from
the decreases in the quantities of total Fe(II) before and after regeneration.
Parallel tests were conducted in the same manner, and surface characterization
of the used and regenerated GFH was done using X-ray photoelectron
for 24 h.
species in the oxidation of the used GFH using phenol (20 µM) as a probe
initial pH of 8.0. Samples were withdrawn at fixed time intervals and the phenol
method [31]. The concentrations of dissolved Fe(II) and Fe(III) were measured
USA) with a cuvette providing a light path of 1 cm. The concentrations of SO42-
11
and S2O32- were determined using an ion chromatograph (100, Dionex, USA)
2 mM NaHCO3 and the injection volume was 20 µL. Analyses of AVS and
using the method developed by Allen et al. [32]. The detailed method is
described in Text S1. S(0) was measured using the method proposed by
detector. Phenol was detected at 268 nm, and the mixture of deionized water
and methanol (55:45, v/v%) at a flow rate of 0.8 mL/min was used as eluents
for the analysis [34]. XPS analysis was performed to identify the changes in
elemental compositions of the GFH surface, and XRD analysis was conducted
detailed description of XRD and XPS analyses are presented in Text S2.
12
on Origin 8.0 software. The results of the significance evaluation reported from
regeneration
regeneration was investigated and the results are shown in Figure 1. As shown
in Figure 1a, addition of GFH in the upper layer of sediment decreased the
dissolved sulfide concentrations in the effluents to the level less than 1 mg/L,
and the sulfide concentration increased markedly after the capacity of GFH was
used up. The sulfide removal capacity of the virgin GFH was calculated as
68.34 mg S/g (Figure 1b), which was a little bit higher than the observation of
our previous study [11]. After the addition of the three investigated oxidant
were 77.49, 67.87 and 57.59 mg S/g, respectively (Figure 1b). The recovery of
the sulfide removal capacity was likely due to the oxidation of Fe(II) products
(e.g., surface-bound Fe(II) and FeS(s)) on the GFH. Sun et al. also found that the
13
oxidation of the Fe(II) products on the used GFH by DO led to the formation of
ferric hydroxides and thus the recovery of the sulfide removal capacities [13].
regeneration. Compared to the virgin GFH, the sulfide removal capacity of the
persulfate regenerated GFH was 13.4% (p < 0.05) higher, and that regenerated
peroxide was 15.7% (p < 0.05) lower (Figure 1b). The superior performance of
persulfate was because more Fe(II) products were oxidized by persulfate than
by chlorine and hydrogen peroxide under the tested conditions and the
formation of ferric hydroxides with more reactive surface sites after the
regenerated GFH in three reuse cycles. Less than 10% in the decrease of the
sulfide removal capacity was found for all the regenerated GFH in each cycle,
suggesting the successful regeneration and the durability of the GFH. The slight
decrease in the capacity of the regenerated GFH was likely due to the
Our results demonstrate that the integrated use of GFH and chemical
14
when GFH dosage is increased. Taking using GFH with hydrogen peroxide and
comparison of chemical costs are shown in Text S3. The chemical cost of using
hydrogen peroxide alone was at least 1.79 times as high as that for the process
using GFH with hydrogen peroxide. Compared to dosing oxidants alone, this
integrated process will significantly lower the overall treatment costs, because
previous study has shown the operational costs of oxidant dosing for the soil
and sediment remediation are much higher than the chemical costs [17].
oxidants
suspended Fe(II) and the leached Fe2+, before and after the reactions of the GFH
with oxidants. The decrease in the amounts of total Fe(II) can represent the
amounts of Fe(III) formed during thee oxidation of the exhausted GFH, which
was supported by the literature [35]. The extent of the GFH oxidation was
calculated from the decreases in the percentage of total Fe(II) before and after
regeneration in Eq. 2:
Eq. 2
15
The percentages increased with increasing oxidant dosages from 0 to 20 mM.
The oxidized Fe(II) ratios were similar (around 10%, p > 0.05) at a dosage of 1
mM for the three investigated oxidants. When the oxidant dosage increased
from 5 to 10 mM, the oxidized Fe(II) ratio by persulfate increased from 43.3 to
78.2% (p < 0.05), which was higher than those by chlorine (31.1–67.5%) (p <
0.05) and hydrogen peroxide (22.6–58.8%) (p < 0.05). This finding supports the
To investigate the oxidation of iron and sulfur species during the GFH
regeneration, the surface variation from the used to regenerated GFH were
characterized by XPS and XRD analyses. FeS(s) (162.7 eV) and S(0) (164 eV),
previously identified in the literature, were also found as major sulfur products
accumulated on the GFH surface during sulfide removal in the present study
(Figure 3a) [13]. Figure 3a also shows that the peaks of S2O32- and SO42- were
identified at 167.8 and 168.8 eV after the oxidation by 10-mM chlorine and
S2O32- and SO42- by both chlorine and hydrogen peroxide. FeS(s) was not
detected during the regeneration by persulfate, implying that FeS(s) was oxidized
by persulfate. The identified peak of SO42- could result from the FeS(s) oxidation
16
Fe (2p) orbital XPS spectra of the used and regenerated GFH are shown in
Figure 3b. After the exhaustion of GFH, FeS(s) precipitates (refer to XRD data
in Figure S3) and amorphous surface-bound Fe(II) [13] were observed at 710.6
eV. After GFH regeneration by persulfate, chlorine and hydrogen peroxide, the
peak shifted from 710.6 eV to 712 eV, indicating that the surface Fe(II)
crystal was identified in the XRD patterns of the regenerated GFH (Figure S3).
containing compounds (mg as Fe) during the oxidation of the used GFH by the
tested oxidants (Detailed data are shown in Table S14). After the exhaustion of
GFH, 22.3 mg S(0) and 14.94 mg AVS (FeS(s)) were accumulated on the
peroxide, 87.2% (13.03 mg) of the AVS was oxidized. The total mass of S(0),
including the suspended and surface S(0), increased to 25 mg after the oxidation
by hydrogen peroxide. The mass of the formed S2O 32- and SO 42- were 1.2 and
6.8 mg, respectively, which were all dissolved in the solution phase. The total
22.3 S(0)) to 35.37 (i.e., 1.91 AVS + 25 S(0) + 1.2 S2O 32- + 6.8 SO42-) mg. A
good recovery (about 94%) for mass balance of the sulfur atom was obtained. A
17
supplementary test demonstrated that S(0) was rather stable and scarcely
persulfate within 24 hours (Figure S4). Thus, the increase in S(0) and newly
formed S2O32- and SO42- were mainly ascribed to the oxidation of AVS by
hydrogen peroxide, and S(0), S2O 32- and SO42- were composed 75.8%, 3.6%,
regeneration by chlorine, 90.3% (13.49 mg) of the AVS was oxidized. The total
mass of S(0) increased to 23.02 mg, along with the formation of 3.4 mg S2O32-
and 8.0 mg SO42-. The total mass of sulfur-containing compounds was 36.33
(i.e., 1.45 AVS + 23.02 S(0) + 3.4 S2O 32- + 8.0 SO42-) mg. A good recovery
(about 96%) for mass balance of the sulfur atom was also obtained. S(0), S2O32-
and SO 42- were composed 33.9%, 9.9% and 23.2% of the oxidation products,
respectively. When persulfate was used, AVS (14.94 mg) was completely
oxidized and the increases in the quantities of S(0) and S2O 32- were 0.08 mg and
SO 42- was produced from the oxidation of AVS, which accounted for 97.8% of
the sulfur-containing products from AVS oxidation. Since the measured total
SO 42- quantity was 229.8 mg from both AVS oxidation and persulfate
persulfate decomposition. The results demonstrate that the oxidant with higher
oxidation potential (i.e., 2.5–3.1, 1.8 and 1.5 V for persulfate, chlorine and
18
generates more sulfur-containing products of higher valence state (i.e., S2O 32-
and SO 42-) [37,38]. Since the gradual accumulation of S(0) on the GFH surface
during regeneration may lead to the loss of reactive surface sites and sulfide
enhance the renewability of GFH due to less S(0) formation. The accumulation
of S(0) on the GFH surface after several use cycles may reduce the
The mass/phase transfer of the surface Fe(II) compounds during the GFH
and 84.1% of FeS(s) (p < 0.05), and 54.8%, 45.5% and 40.7% (p < 0.05) of the
1.
reactive species
19
Based on the findings above, the main reactions involved in the hydrogen
sulfide control by GFH and the regeneration of GFH by the three oxidants are
S +≡ Fe
III →≡ Fe
II + FeS + S(0)
Eq. 3
/ /
≡ Fe
II Fe
OH
Eq. 4
/
FeS Fe
OH + S
0 + S O + SO
Eq. 5
FeS Fe
OH + SO
Eq. 6
/ /
Fe Fe
OH
Eq. 7
The reactions of hydrogen sulfide with GFH (≡Fe(III)) generates S(0), surface-
bound Fe(II) and FeS(s) (Eq. 3), which are accumulated on the GFH surface and
lead to the exhaustion of GFH. During the regeneration, the surface Fe(II)
(Eqs. 4–6). FeS(s) is oxidized to S(0), S2O 32- and SO 42- by chlorine or hydrogen
peroxide (Eq. 5), and to SO42- only by persulfate (Eq. 6). Fe2+ ions are released
during the GFH regeneration (Figure S5), and the released Fe2+ ions are
20
oxidized to Fe3+ by the applied oxidants and subsequently precipitates in the
species, because phenol is highly reactive towards OH• (1.4 × 1010 M-1 s-1), SO4-
• (8.8 × 109 M-1 s-1) and chloride radical (2.5 × 108 M-1 s-1) [39–41], and it was
hardly degraded (p > 0.05) in the presence of persulfate, hydrogen peroxide and
phenol was not degraded by the used GFH alone within 3 hours. The
peroxide were insignificant (less than 10%, p > 0.05), indicating limited
was 8, and the pH values of the solutions at the end of the reactions were 7.15
directly from the interaction of persulfate with Fe2+ ions and surface-bound
subsequently formed from the oxidation of water and hydroxide (6.5 × 107 M-1
21
s-1) by SO 4-• (Eqs. 10 and 11) [25, 42, 43]. The lower solution pH (4.82) in the
Eq. 8
≡ Fe
II + SO ∙
! → Fe
OH + SO + SO
Eq. 9
SO∙ ∙
+ HO → OH + SO
Eq. 10
SO∙ ∙
+ HO → OH + SO
Eq. 11
persulfate is used, the degradation of phenol in the presence of MeOH and TBA
reactive towards OH• (9.7 × 108 M-1 s-1) and SO 4-• (1.1 × 107 M-1 s-1), was used
to scavenge both radicals. TBA, having a large reaction rate constant towards
OH• (6.0 × 108 M-1 s-1) as compared to that towards SO4-• (4.0 × 105 M-1 s-1),
was used to scavenge OH• alone [44]. As shown in Figure 6, the phenol
degradation in the presence of TBA was reduced to ~50%. The results suggest
persulfate. Since the reaction rates of the reactive species with Fe(II)
compounds (e.g., Fe2+) (4.6 × 109 M-1 s-1) are much faster than those with
22
persulfate alone (27 M-1 s-1), the generated SO4-• and OH•, in addition to
persulfate itself, enhanced the consumed GFH oxidation and the regenerated
The significant formation of reactive species from the oxidation of the used
already abundant (up to 2,700 ppm in seawater) in these systems [48]. Instead,
the availability of bio-degradable organics (e.g., volatile fatty acids) and the
redox potential limit the formation of hydrogen sulfide [49]. Therefore, sulfate
from the decomposition of persulfate (e.g., 1–20 mM) is expected to not affect
23
persulfate may not have a significant influence on the hydrogen sulfide
introduction) is expected to be very low and the produced sulfate can be flushed
away.
4. Conclusions
This study was undertaken to investigate the use of common oxidants as the
hydrogen sulfide control. GFH that was dosed in the sediment phase effectively
chlorine and hydrogen peroxide, into the sediments. Persulfate was the best
compounds on the GFH surface into amorphous ferric hydroxides. FeS(s) was
oxidized to S(0), S2O32- and SO 42- by both chlorine and hydrogen peroxide, and
homogeneous oxidation of the Fe2+ ions released from the surface of the GFH.
Both SO4-• and OH• were generated during the oxidation of the surface Fe(II)
24
dosing (e.g., nitrate, persulfate and hydrogen peroxide) for hydrogen sulfide
control in the sediment systems, such as box culverts, marine and aquatic ponds.
The integrated technology can prevent the frequent oxidant dosing, which is
hydrogen sulfide.
Acknowledgements
This study was supported by the Hong Kong Innovation and Technology Fund
GFH.
Supplementary data associated with this article are available in the online
version.
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List of figures:
Figure 2. Effects of oxidant dosages on the oxidation of the GFH. [GFH]0 = 5.0
g/L, temperature = 22 ± 1 and reaction time = 3 h. ......................................... 35
Figure 3. (a) S(2p) orbital and (b) Fe(2p) orbital XPS spectra of the used and
regenerated GFH by persulfate, chlorine and hydrogen peroxide. [GFH]0 = 5
g/L, [S2O 82-]0 = [OCl-]0 = [H2O2]0 = 10 mM, temperature = 22 ±1 and
regeneration duration = 3 h. ............................................................................. 36
33
50
(a) Control Na2S2O8 NaClO H2O2
30
20
10
0
0 5 10 15 20 25 30 35
Time (d)
(b) 80
Sulfide removal capacity (mg S/g)
60
40
20
0
Virgin GFH Na2S2O8 reg NaOCl reg H2O2 reg
34
22 ±1‐, [S2O 82-]0 = [OCl-]0 = [H2O 2]0 = 0.5 M, injection volume = 10 mL, and
regeneration duration = 12 h.
100
Percentage of Fe(II) oxidized (%)
80
60
40
Na2S2O8 reg
20 NaOCl reg
H2O2 reg
0
0 5 10 15 20
Dosage of oxidants ( mM)
Figure 2. Effects of oxidant dosages on the oxidation of the GFH. [GFH]0 = 5.0
35
FeSx
(a) S(0) Used GFH
2-
SO4 Na2S2O8 regenerated
S(0)
2-
NaOCl regenerated
2- S2O3 S(0)
SO4 FeSx
S2O3
2- H2O2 regenerated
2- S(0) FeSx
SO4
NaOCl regenerated
Fe(III) Fe(II)
H2O2 regenerated
Fe(III)
Fe(II)
Figure 3. (a) S(2p) orbital and (b) Fe(2p) orbital XPS spectra of the used and
regeneration duration = 3 h.
36
(a) 270 2-
265
SO4 -S
2-
Sulfur mass (mg as S) 260 S2O3 -S
255 Suspended S(0)
250 Surface S(0)
Suspended AVS
245
Surface AVS
240
30
20
10
0
Used GFH H2O2 reg NaOCl reg Na2S2O8 reg
(b) 100
Suspended Fe(II)-Fe
FeS-Fe
80 Surface-Bound Fe(II)-Fe
Fe(II) mass (mg)
60
40
20
0
Used GFH H2O2 reg NaOCl reg Na2S2O8 reg
37
1.0
0.8
0.6
C/C0
Used GFH
0.4 Used GFH+Na2S2O8
Used GFH +H2O2
0.2 Used GFH + NaOCl
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Time (h)
g/L, [S2O 82-]0 = [OCl-]0 = [H2O2]0 = 1 mM, initial pH = 8.0, and temperature =
22 ± 1‐ .
38
1.0
0.8
0.6
Used GFH
C/C0
Na2S2O8
0.4 Used GFH+Na2S2O8
Used GFH+Na2S2O8+MeOH
0.2
Used GFH+Na2S2O8+TBA
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Time (h)
39
Highlights
peroxide.
GFH recovery.
FeS was oxidized to SO42- by persulfate and to S(0), S2O32- and SO42- by
40