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Accepted Manuscript

Oxidation of iron sulfide and surface-bound iron to regenerate granular ferric


hydroxide for in-situ hydrogen sulfide control by persulfate, chlorine and per-
oxide

Ran Yin, Chihhao Fan, Jianliang Sun, Chii Shang

PII: S1385-8947(17)32181-2
DOI: https://doi.org/10.1016/j.cej.2017.12.060
Reference: CEJ 18221

To appear in: Chemical Engineering Journal

Received Date: 19 June 2017


Revised Date: 11 December 2017
Accepted Date: 12 December 2017

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

ferric hydroxide for in-situ hydrogen sulfide control by persulfate, chlorine

and peroxide

Submitted to:

Chemical Engineering Journal

Ran YINa, Chihhao FAN b, Jianliang SUN*, a, Chii SHANG*, a, c

a. Department of Civil and Environmental Engineering, the Hong Kong

University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong

b. Department of Bioenvironmental Systems Engineering, National Taiwan

University, Taipei, Taiwan

c. Hong Kong Branch of Chinese National Engineering Research Center for

Control & Treatment of Heavy Metal Pollution, the Hong Kong University of

Science and Technology, Clear Water Bay, Kowloon, Hong Kong

* Corresponding authors: Tel: +86-13533626596, Email: jlsun@connect.ust.hk

(Sun, J.); Tel: +852-23587885, Email: cechii@ust.hk (Shang, C.).

1
Abstract

Hydrogen sulfide emission from sediments in storm drainage networks,

estuaries and marine seafloor is a nuisance. The regeneration of the GFH for

reuse is crucial to make dosing granular ferric hydroxide (GFH) an effective,

long-lasting solution than doing liquid oxidants to the control of sedimentary

hydrogen sulfide. This paper investigated the oxidation of iron sulfide and

surface-bound iron compounds to regenerate GHF using persulfate, chlorine and

peroxide for the in-situ control of hydrogen sulfide. The hydrogen sulfide

removal capacities of virgin, persulfate-, chlorine- and peroxide-regenerated

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

mainly oxidized to sulfate (SO42-) (97.8%) by persulfate, and to elemental sulfur

(S(0)) (5.8 and 25%), thiosulfate (S2O32-) (27.7 and 11.3%) and SO42- (66.5 and

63.7%) by chlorine and peroxide, respectively. In addition to the oxidation by

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

surface and regenerated GFH more completely.

Keywords: Hydrogen sulfide; Granular ferric hydroxide; Regeneration; Iron

sulfide oxidation; Surface-bound Fe(II) oxidation

2
1. Introduction

Hydrogen sulfide, formed by sulfate-reducing bacteria (SRB) under

anaerobic conditions, is a noxious and toxic substance occurring in sewers, and

sedimentary deposits of estuaries, storm drainage networks and marine seafloor

[1,2]. It is associated with several safety, maintenance and environmental

problems including concrete corrosion, toxicity to aquatic organisms and odor

nuisance [3–5]. Several preventive measures such as enhanced ventilation and

chemical treatment have been developed to mitigate the damage by hydrogen

sulfide. However, the ventilation measure often requires installation of localized

equipment, resulting in high cost of capital investments [5]. Protective coating

applications prevent the concrete corrosion, but cannot prevent hydrogen sulfide

formation, causing the odor nuisance and toxic effects. Chemical treatment can

effectively eliminate hydrogen sulfide, and therefore, becomes an attractive

technology for hydrogen sulfide control in many systems because of the

advantages of simple operation and low investments [4–6].

3
Among the often-applied chemical treatment technologies, addition of

chemical oxidants gains a great deal of popularity because it is a quick and

effective approach in hydrogen sulfide control [5]. Soluble oxidants, such as

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

another popular chemical treatment technology, which has been proved

effective in hydrogen sulfide removal in sanitary sewers [7,8]. However, in

drainage systems where hydrogen sulfide is often slowly produced, dosing

soluble chemicals at high concentration can result in the release of the excessive

soluble chemical to the surrounding environment, resulting in a significant

reduction of hydrogen sulfide control. Besides, frequent dosing is often required

to ensure the treatment efficiency for hydrogen sulfide control, which increases

the operational costs.

Granular iron-based technology has been demonstrated to be an effective,

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

form persistently remove hydrogen sulfide through ferric reduction in

aqueous/sediment systems, resulting in forming amorphous surface-bound

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

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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

through oxidation of surface Fe(II) products (i.e., surface-bound Fe(II) and

FeS(s)) back to ferric (hydr)oxides [13]. However, S(0) generated from the

oxidation of FeS(s) may gradually accumulate on the surface of iron granules,

leading to the reduction of reactive sites, thus diminishing their restored

capacity after repetitive use. In addition, the provision of DO via prolonged

mechanical mixing or aeration for iron regeneration in the sediment systems

may be difficult and energy-intensive due to the low aqueous solubility of

oxygen [14,15].

Use of chemical oxidants other than DO is proposed here as an alternative

for in-situ regeneration of iron granules in storm drainage network and marine

sediments. Oxidants such as hydrogen peroxide, chlorine and persulfate have

been widely used in the subsurface systems (e.g., groundwater, soil, estuary and

marine sediments) for the remediation of heavy metals, petroleum

hydrocarbons, pesticides, etc. [16,17]. However, continuous supply of the

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)

and siderite (FeCO3) to form ferric (hydr)oxides, suggesting their possible

application to oxidizing Fe(II) products generated during hydrogen sulfide

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

much frequently used to control hydrogen sulfide directly.

Regeneration of the used iron granules involves complex interactions of

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

mechanisms remain unclear [22,23]. However, further investigation is needed to

address the following aspects: 1) The feasibility of oxidizing a mixture of iron

sulfide and amorphous surface-bound Fe(II) compounds under realistic

conditions is uncertain. The previous studies regarding hydrogen sulfide control

by strong oxidants were conducted in pure water, and the complex compositions

of sediments may affect the effectiveness of oxidants. 2) The applied oxidants,

such as persulfate and hydrogen peroxide, have their specific properties (e.g.,

oxidation potential), and the side-by-side comparison in the oxidation of iron

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

FeCO 3) with often-used oxidants (e.g., hydrogen peroxide, persulfate and

chlorine) produce reactive species, such as hydroxyl radicals (OH•), sulfate

radicals (SO 4-•) and chlorine radicals (Cl•) under certain experimental

conditions [24–26]. Whether these reactive species can be formed in the

subsurface systems and how they contribute to the oxidation of surface Fe(II)

products during the regeneration remain unclear.

In this study, the regeneration of GFH by persulfate, hydrogen peroxide and

chlorine in the process of hydrogen sulfide control was investigated. The

oxidation of iron- and sulfur- containing products during the regeneration by the

three oxidants were evaluated. In addition, the contributions of reactive species

to the oxidation of GFH were explored.

2. Materials and methods

2.1 Chemicals and materials

Granular ferric hydroxide (GFH) was obtained from GEH Wasserchemie

GmbH & Co. KG (Germany) and used without further purification. The

measured physical and chemical characteristics of GFH are listed in Table S1.

Unless otherwise specified, all solutions were prepared by dissolving reagent-

grade chemicals purchased from Sigma-Aldrich in deionized water (18.2

MΩ·cm) prepared from a water purification system (Cascada, PALL

Corporation). A sodium sulfide stock solution was prepared by dissolving

7
sodium sulfide crystals (Na2S·9H2O) in nitrogen-purged water. A free chlorine

stock solution (2 g/L as Cl2) was prepared weekly by diluting a sodium

hypochlorite (NaOCl) solution (4.00–4.99%) with deionized water and then

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

stock solution was prepared by dissolving sodium persulfate (Na2S2O8) in

deionized water and stirring overnight. The seawater was obtained from the

Coastal Marine Laboratory at the Hong Kong University of Science and

Technology and filtered through a 0.45-µm membrane filter before use. A

synthetic substrate, which simulated the characteristics of the sewage in an

odorous box culvert in Jordan Valley of Hong Kong, was prepared by spiking

an aliquot of a nutrient stock solution (containing organic carbon sources and

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.

2.2 Experimental procedures

Unless otherwise specified, all experimental operations including sulfide

solution preparation, reagent addition, and sample collection were conducted in

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.

Experiments were performed to study the feasibility of controlling

sedimentary hydrogen sulfide by virgin and regenerated GFH under realistic

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

hydrogen sulfide is generated in the sediment phase. As illustrated in Figure S1,

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

to allow the production of hydrogen sulfide by SRB in the sediment. Effluent

samples were collected on daily basis and immediately subjected to dissolved

sulfide measurement. After the hydrogen sulfide generation became stable, the

upper sediment layer (5 cm in depth) was blended with an aliquot of GFH at a

predetermined dosage of 1 g GFH per liter of total sediment. When the

dissolved sulfide concentrations exceeded 1 mg/L, sulfide removal capacity of

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

To regenerate GFH by persulfate, hydrogen peroxide and chlorine, the

supply of the synthetic substrate was terminated and 10 mL of oxidant solutions

(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

distributed locations [28–30]. After 12 h of contact, the supply of the synthetic

substrate was resumed, and the hydrogen sulfide control capacity of the

regenerated GFH was evaluated in the same manner as described previously.

Batch experiments under well-controlled conditions were performed to

investigate the interactions between the GFH and the oxidants. Tests were

conducted in 310 mL glass bottles with Teflon lined caps (Wheaton, USA), to

use up the sulfide removal capacity of GFH (5 g/L) as previously mentioned

[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

condition of the seawater-impacted storm drainage system in in Hong Kong

[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

supernatant was collected for the measurement of dissolved sulfide (S2-),

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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

spectroscope (XPS) and X-ray diffraction (XRD) after vacuum-freeze drying

for 24 h.

Supplementary tests were performed to understand the role of the reactive

species in the oxidation of the used GFH using phenol (20 µM) as a probe

compound at a GFH dosage of 0.5 g/L, an oxidant dosage of 1 mM, and an

initial pH of 8.0. Samples were withdrawn at fixed time intervals and the phenol

concentrations were measured. The phenol degradation was also evaluated in

the presence of methanol (MeOH) and tert-butanol (TBA) at 5 mM as radical

scavengers for comparison.

2.3 Analytical methods

The dissolved sulfide concentrations were measured by the methylene blue

method [31]. The concentrations of dissolved Fe(II) and Fe(III) were measured

by the phenanthroline colorimetric method [31]. The absorbance of the

methylene blue at 664 nm and the Fe(II)-phenanthroline complex at 510 nm was

measured using an UV–Vis spectrophotometer (Lambda 25, Perkin Elmer Inc.,

USA) with a cuvette providing a light path of 1 cm. The concentrations of SO42-

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and S2O32- were determined using an ion chromatograph (100, Dionex, USA)

equipped with a conductivity detector and an IonPac AS9-HC analytical

column. The eluent for ion chromatograph determination was 2 mM Na2CO 3 +

2 mM NaHCO3 and the injection volume was 20 µL. Analyses of AVS and

extraction of solid-phase Fe(II) and Fe(III) were simultaneously performed

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

Edwards et al. [33]. Phenol was determined using an ultra-performance liquid

chromatography (VP series, Shimadzu) equipped with a Waters symmetry C18

column (4.6 mm × 150 mm, 5 µm particle size) and a SPD-10A UV–Vis

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

to characterize the crystal structure of substances on the GFH surface. The

detailed description of XRD and XPS analyses are presented in Text S2.

2.4 Statistical analysis

All experiments were conducted in duplicate. The data were expressed as

mean ± standard deviation of the two parallel experiments. Statistical

significance (p < 0.05) was evaluated by one-way analysis of variance (ANOVA)

12
on Origin 8.0 software. The results of the significance evaluation reported from

the software are listed in the Supplementary Materials (Table S5–14).

3. Results and discussion

3.1 Comparison of persulfate, hydrogen peroxide and chlorine for GFH

regeneration

The performance of persulfate, hydrogen peroxide and chlorine in GFH

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

solutions (i.e., persulfate, chlorine and hydrogen peroxide), the sulfide

concentrations in the effluents decreased significantly and remained below 1

mg/L until re-exhaustion after 8, 7, 6 d, respectively. The sulfide removal

capacities of GFH regenerated by persulfate, chlorine and hydrogen peroxide

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].

Interestingly, the three oxidants exhibited different capabilities for GFH

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

by chlorine was comparable (p > 0.05), while that regenerated by hydrogen

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

regeneration. Mechanistic exploration was thus conducted to reveal the

reactions of used GFH with the three investigated oxidants.

Figure S2 shows the sulfide removal capacities of the virgin and

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

accumulation of S(0) on the GFH surface after several use cycles.

Our results demonstrate that the integrated use of GFH and chemical

oxidants is a promising long-lasting approach to in-situ control hydrogen sulfide

in drainage sediment systems, where hydrogen sulfide is often slowly produced.

The frequency of dosing oxidants to regenerate GFH will be further reduced

14
when GFH dosage is increased. Taking using GFH with hydrogen peroxide and

using hydrogen peroxide alone as examples, the results of estimations 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].

3.2 Oxidation of Fe(II) and sulfide compounds on used GFH by common

oxidants

Figure 2 shows changes of total Fe(II), including the surface Fe(II),

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:

Change of Fe(II) mass


Percentage of Fe(II)oxidized =
Total iron mass

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

higher sulfide removal capacity of GFH regenerated by persulfate than those by

chlorine and hydrogen peroxide. At a high dosage of 20 mM, the percentages of

Fe(II) compounds being oxidized by all the investigated oxidants were

comparable (about 90%, p > 0.05).

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

hydrogen peroxide for 3 hours, respectively, suggesting the FeS(s) oxidation to

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

and decomposition of persulfate [33].

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)

products were oxidized to Fe(III) compounds. In addition, the Fe(III)

compounds formed were mainly in the amorphous form as no structured Fe(III)

crystal was identified in the XRD patterns of the regenerated GFH (Figure S3).

The formation of amorphous Fe(III) compounds also partially explains the

higher capacities of GFH regenerated by persulfate.

Figure 4 shows the mass changes of sulfur-containing (mg as S) and iron-

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

surface of the used GFH. After 3-hour regeneration by 10 mM hydrogen

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

mass of sulfur-containing compounds changed from 37.7 (i.e., 14.94 AVS +

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

oxidized (p > 0.05) to S2O32- or SO42- by hydrogen peroxide, chlorine and

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%,

and 20.6% of the sulfur-containing products, respectively. After the

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

0.25 mg, respectively. Based on mass balance, we estimated that 14.61 mg of

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

decomposition [36], it is estimated that 93.6% of SO42- was produced from

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

hydrogen peroxide, respectively) performs better in the AVS oxidation 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

removal capacity, the use of persulfate and chlorine is therefore expected to

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

effectiveness of GFH regeneration when H 2O2 is used.

The mass/phase transfer of the surface Fe(II) compounds during the GFH

regeneration by the investigated oxidants is shown in Figure 4b. After the

exhaustion, 87.9 mg surface-bound Fe(II) and 9.52 mg FeS(s) were formed.

After regeneration by persulfate, chlorine and hydrogen peroxide, 97.4%, 87.2%

and 84.1% of FeS(s) (p < 0.05), and 54.8%, 45.5% and 40.7% (p < 0.05) of the

surface-bound Fe(II) were respectively oxidized back into Fe(III). Apparently,

more FeS(s) and surface-bound Fe(II) were oxidized by persulfate, as compared

to those oxidized by chlorine and hydrogen peroxide. This trend further

supports the regeneration performance of the three oxidants observed in Figure

1.

3.3 Proposed mechanisms of the oxidation of GFH and contributions of

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

proposed as the following equations (Eqs. 3–7):

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)

products (surface-bound Fe(II) and FeS(s)) are oxidized to amorphous Fe(OH)3

(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

form of Fe(OH)3 (Eq. 7).

To quantify the contributions of reactive species to the regeneration of GFH

by the investigated oxidants, phenol was selected as a probe compound in the

competition degradation experiment to probe the formation of reactive radical

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

chlorine under the experimental conditions (Figure S6). As shown in Figure 5,

phenol was not degraded by the used GFH alone within 3 hours. The

degradation during the oxidation of used GFH by chlorine and hydrogen

peroxide were insignificant (less than 10%, p > 0.05), indicating limited

formation of reactive species under the experimental conditions. The initial pH

was 8, and the pH values of the solutions at the end of the reactions were 7.15

and 7.65, respectively, in the presence of chlorine and hydrogen peroxide.

Under such conditions, the radical generation by the conventional Fenton

reactions was negligible. By contrast, around 35% of phenol was degraded

during the oxidation of used GFH by persulfate, suggesting the significant

formation of reactive species. It has been reported that SO 4-• is produced

directly from the interaction of persulfate with Fe2+ ions and surface-bound

Fe(II) under acidic/neutral pH conditions (Eqs. 8 and 9), and OH• is

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

presence of persulfate also enhanced the radical formation.

Fe + S O!  → Fe + SO 


 ∙ +SO

Eq. 8

≡ Fe
II + SO ∙ 
! → Fe
OH  + SO + SO

Eq. 9

SO∙ ∙ 
 + HO → OH + SO

Eq. 10

SO∙  ∙ 
 + HO → OH + SO

Eq. 11

To differentiate the contribution of different radicals formed when

persulfate is used, the degradation of phenol in the presence of MeOH and TBA

(serving as the radical scavengers) was investigated. MeOH, which is highly

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 was completely inhibited in the presence of MeOH, and the

degradation in the presence of TBA was reduced to ~50%. The results suggest

that OH• and SO4-• contributed comparably to the regeneration of GFH by

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

GFH capacity [45].

The significant formation of reactive species from the oxidation of the used

GFH by persulfate suggests the possibility to simultaneously remove hydrogen

sulfide and persistent organic pollutants in subsurface/sediment systems by the

integrated use of iron granules and persulfate. Iron granules in water/sediments

can remove hydrogen sulfide and recalcitrant organic pollutants through

adsorption due to the excellent affinities of iron (hydr)oxides with many

recalcitrant organic pollutants (e.g., pesticides, industrial solvents and

pharmaceuticals) [46, 47]. During the subsequent in/ex-situ regeneration of iron

granules by the oxidants, the reactive species generated are expected to

concurrently degrade the adsorbed organic pollutants.

In the seawater-impacted sediment systems, such as the seawater-impacted

drainage systems in Hong Kong and marine sediments, because sulfate is

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

the hydrogen sulfide formation in these seawater-impacted drainage systems

significantly. On the other hand, in other fresh-water drainage systems where

the background sulfate concentration is not high, the occasional injection of

23
persulfate may not have a significant influence on the hydrogen sulfide

formation as well because the frequency of regeneration (by persulfate

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

alternatives to dissolved oxygen for the regeneration of GFH for sedimentary

hydrogen sulfide control. GFH that was dosed in the sediment phase effectively

removed hydrogen sulfide, and after the exhaustion, it was effectively

regenerated by periodically injecting common oxidants, including persulfate,

chlorine and hydrogen peroxide, into the sediments. Persulfate was the best

oxidant for GFH regeneration, followed by chlorine and hydrogen peroxide.

The regeneration of GFH was mainly attributed to the oxidation of Fe(II)

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

to SO42- alone by persulfate. The oxidation of the surface Fe(II) compounds

proceeded through heterogeneous oxidation of the surface-bound Fe(II) 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)

by persulfate, which enhanced the regeneration of GFH by persulfate. The

integrated process provides a superior alternative to the conventional oxidant

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

often required by the conventional methods to control the slowly-generated

hydrogen sulfide.

Acknowledgements

This study was supported by the Hong Kong Innovation and Technology Fund

(grant number ITS/182/11) and the Drainage Services Department of Hong

Kong (grant number LD 07/2014). We thank GEH Wasserchemie for providing

GFH.

Appendix A. Supplementary materials

Supplementary data associated with this article are available in the online

version.

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List of figures:

Figure 1. (a) Concentrations of dissolved sulfide in the effluents from the


reactors with/without embedded GFH in the sediment phase and regenerated by
persulfate, chlorine and hydrogen peroxide. (b) Sulfide removal capacities of
virgin and regenerated GFH. Conditions: [GFH]0 = 1 g /L of sediment, flow rate
= 20 mL/h, sulfate = 300 mg S/L, DOC = 100 mg C/L, pH = 7.1, temperature =
22 ±1 , [S2O82-]0 = [OCl-]0 = [H2O 2]0 = 0.5 M, injection volume = 10 mL, and
regeneration duration = 12 h. ........................................................................... 34

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

Figure 4. Mass/phase transfer of (a) sulfur-containing products and (b) iron-


containing products during the oxidation of the exhausted GFH by persulfate,
chlorine and hydrogen peroxide. [GFH]0 = 5 g/L, [S2O82-]0 = [OCl-]0 = [H2O2]0
= 10 mM, temperature = 22 ±1 and regeneration duration = 3 h..................... 37

Figure 5. Degradation of phenol during the oxidation of the used GFH by


persulfate, chlorine and hydrogen peroxide. [Phenol]0 = 20 µM, [GFH]0 = 0.5
g/L, [S2O 82-]0 = [OCl-]0 = [H2O2]0 = 1 mM, initial pH = 8.0, and temperature =
22 ± 1 . ........................................................................................................... 38

Figure 6. Effects of methanol (MeOH) and tert-butanol (TBA) on the


degradation of phenol during the oxidation of the used GFH by persulfate.
[Phenol]0 = 20 µM, [GFH]0 = 0.5 g/L, [S2O82-]0 = [OCl-]0 = [H2O2]0 = 1 mM,
[MeOH] = [TBA] = 5 mM, initial pH = 8.0, and temperature = 22 ± 1 . ......... 39

33
50
(a) Control Na2S2O8 NaClO H2O2

GFH addition Oxidants injection


40
on Day 7
Sulfide concentration (mg/L)
on Day 19

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

Figure 1. (a) Concentrations of dissolved sulfide in the effluents from the

reactors with/without embedded GFH in the sediment phase and regenerated by

persulfate, chlorine and hydrogen peroxide. (b) Sulfide removal capacities of

virgin and regenerated GFH. Conditions: [GFH]0 = 1 g /L of sediment, flow rate

= 20 mL/h, sulfate = 300 mg S/L, DOC = 100 mg C/L, pH = 7.1, temperature =

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

g/L, temperature = 22 ± 1‐ and reaction time = 3 h.

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

172 170 168 166 164 162 160


B.E.(eV)

(b) Used GFH


Fe(II)

Fe(III) Na2S2O8 regenerated


Fe(II)

NaOCl regenerated
Fe(III) Fe(II)

H2O2 regenerated
Fe(III)
Fe(II)

716 714 712 710 708 706


B.E.(eV)

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
(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

Figure 4. Mass/phase transfer of (a) sulfur-containing products and (b) iron-

containing products during the oxidation of the exhausted GFH by persulfate,

chlorine and hydrogen peroxide. [GFH]0 = 5 g/L, [S2O82-]0 = [OCl-]0 = [H2O2]0

= 10 mM, temperature = 22 ±1‐ and regeneration duration = 3 h.

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)

Figure 5. Degradation of phenol during the oxidation of the used GFH by

persulfate, chlorine and hydrogen peroxide. [Phenol]0 = 20 µM, [GFH]0 = 0.5

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)

Figure 6. Effects of methanol (MeOH) and tert-butanol (TBA) on the

degradation of phenol during the oxidation of the used GFH by persulfate.

[Phenol]0 = 20 µM, [GFH]0 = 0.5 g/L, [S2O82-]0 = [OCl-]0 = [H2O2]0 = 1 mM,

[MeOH] = [TBA] = 5 mM, initial pH = 8.0, and temperature = 22 ± 1‐.

39
Highlights

 Persulfate was more efficient in regenerating GFH than chlorine and

peroxide.

 The Fe(II) products were oxidized to amorphous ferric hydroxides for

GFH recovery.

 FeS was oxidized to SO42- by persulfate and to S(0), S2O32- and SO42- by

chlorine and peroxide.

 Radical-induced pathway enhanced the GFH regeneration by persulfate.

40