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Journal of Environmental Management 170 (2016) 186e206

Contents lists available at ScienceDirect

Journal of Environmental Management


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

Review

An overview of principles of odor production, emission, and control


methods in wastewater collection and treatment systems
Amirreza Talaiekhozani a, *, Marzieh Bagheri b, Amin Goli c,
Mohammad Reza Talaei Khoozani d
a
Jami Institute of Technology, Civil Engineering Department, Isfahan, Iran
b
Jami Institute of Technology, Chemical Engineering Department, Isfahan, Iran
c
Jami Institute of Technology, Mechanical Engineering Department, Isfahan, Iran
d
University of Isfahan, Faculty of Engineering, Chemical Engineering Department, Isfahan, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Odorous gases are the most important reason that people register complaints with organizations
Received 18 September 2015 responsible for wastewater collection and treatment systems (WCTS). Although several studies have
Received in revised form been conducted for prevention and control of odorous gases, no comprehensive research exists about
16 January 2016
recent achievements in this area. The aim of the present study is to collect and categorize the new
Accepted 19 January 2016
Available online 30 January 2016
achievements in preventing and controlling odorous gases in WCTS. Two strategies for controlling odor
emissions from WCTS are (1) prevention of odor production and (2) removal of odorous compounds from
emissions of WCTS. Between the two, priority goes to preventing odorous compounds' production.
Keywords:
Odorous gases
Several methods have been developed to prevent odor production, such as increasing oxidation reduc-
Wastewater collection tion potential; inhibiting the activity of sulfide reducing bacteria; chemical removal of hydrogen sulfide;
Wastewater treatment applying formaldehyde and paraformaldehyde to prevent hydrogen sulfide production; and using fuel
Odor removal cells in hydrogen sulfide inhibition and gradual release of oxygen in gas phase by using MgO2 or CaO2. In
addition to preventing odorous compounds in WCTS, many other methods have been introduced to
remove odorous compounds from emissions of WCTS, such as biofilters; bioscrubbers; biotrickling fil-
ters; suspended growth reactors; and membrane bioreactors and scrubbers. Through this review,
responsible organizations can find new, effective, and economical strategies to prevent and control
odorous gases in WCTS.
© 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
2. Odor and odorous compounds in wastewater facilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
3. A summary of odor control methods in wastewater facilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
4. Hydrogen sulfide production in wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
5. Increasing the oxidation reduction potential to control the level of hydrogen sulfide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
5.1. Air or pure oxygen injection into the wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
5.2. Inhibiting hydrogen sulfide by nitrate injection into wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
6. Inhibiting the activity of sulfide reducing bacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
7. Chemical removal of hydrogen sulfide from wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
7.1. Chemical decomposition of hydrogen sulfide by metal salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
7.1.1. Insoluble metal sulfides in wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
7.1.2. Hydrogen sulfide elimination by iron salt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
7.1.3. Operation conditions and removal costs of sulfide by metal salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196

* Corresponding author.
E-mail address: amirtkh@yahoo.com (A. Talaiekhozani).

http://dx.doi.org/10.1016/j.jenvman.2016.01.021
0301-4797/© 2016 Elsevier Ltd. All rights reserved.
A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206 187

7.2. Chemical decomposition of hydrogen sulfide by oxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196


7.2.1. Hydrogen peroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
7.2.2. Chlorine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
7.2.3. Potassium permanganate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
7.2.4. Advanced oxidation methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
8. Biological removal of hydrogen sulfide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
9. Prospects for hydrogen sulfide removal in the future . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
9.1. Application of formaldehyde and paraformaldehyde in elimination of hydrogen sulfide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
9.2. Gradual release of oxygen in gas phase (MgO2/CaO2) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
9.3. Fuel cell application in hydrogen sulfide inhibition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
10. Hydrogen sulfide polluted air treatment methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
10.1. Biological treatment methods of hydrogen sulfide polluted air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
10.1.1. Biofilters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
10.1.2. Bioscrubbers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
10.1.3. Biotrickling filter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
10.1.4. Suspended growth reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
10.1.5. Membrane bioreactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
10.2. Application of scrubbers in elimination of hydrogen sulfide and other odorous compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
11. A comparison of hydrogen sulfide removal methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
12. Methods of measuring the concentration of hydrogen sulfide in the air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
13. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204

1. Introduction contaminants through stimulation of their smell organs. Odors can


be pleasant (perfume, fresh food) or unpleasant (rotten egg,
Gases that primarily affect the sense of smell are known as the sewage). Individual reaction to smells differs with physiological
“odorous gases.” These gases usually convey a negative and un- and psychological aspects. Some people may perceive certain
pleasant sense. When asked to describe the odorous compounds, smells as pleasant, while others might perceive them as unpleasant.
most people refer to them as unpleasant odors. However, even During the wastewater collection and treatment operation, odor-
pleasant and desirable odors may become uncomfortable in high producing compounds are generated through the anaerobic
concentrations. In many cases, by cleaning wastewater treatment decomposition of organic matter containing sulfur and nitrogen
facilities, removing excess sand and sludge, and optimized opera- (Nielsen et al., 1998; Zhang et al., 2008; Hvitved-Jacobsen., 2002).
tion, odor generation in sewer installations can be dramatically These volatile compounds possess relatively low molecular weight.
reduced. In some cases, by bringing in clean outside air or by dis- Odorous compounds have an odor threshold value, the odor unit, in
charging polluted air in indoor facilities, odor-causing pollutants which the odor is not detectable below a given concentration. To
can be reduced. Sometimes discharging polluted gasses outside measure accurately the odor in water, at least five individuals are
facilities can lead to protests from local residents. In such circum- needed. Each individual attempts to smell the odor. If they detect
stances, pollutant control must be achieved through exhaust air the odor, the water is then diluted with distilled water and the
treatment (Nielsen et al., 1998; Zhang et al., 2008; Hvitved- process is repeated. The dilution is repeated until the odor is no
Jacobsen., 2002). longer detectable. Ultimately, the odor threshold value is calculated
Hydrogen sulfide is considered the most important reason for using Equation (1) (Tchobanoglous and Burton, 2003):
odor emission and corrosion in wastewater collection and treat-
ment facilities. In 1996, Sydney et al. investigated the corrosion of
TON ¼ ðA þ BÞ=A (1)
wastewater collection networks in the city of Los Angeles. They
confirmed hydrogen sulfide corrosion in 10% of the pipes. The Where A is the volume of odorous water, B is the volume of the
wastewater collection network estimated the loss at US$500 odorless distilled water used in the test, and TON is the threshold
million (Sydney et al., 1996). Kaempfer et al. conducted a similar odor number. Three is the maximum acceptable threshold value.
investigation in 1998 in Germany. They concluded that the damage The compound that produces the most odors usually possesses low
caused by the lack of hydrogen sulfide control in wastewater molecular weight. Gaseous compounds with molecular weight
collection networks amounted to US$125 million. Vincke (2002) higher than 300 g per mole are generally considered odorless.
revealed that the damage caused by the hydrogen sulfide corro- Hydrogen sulfide, one of the most important odor-causing com-
sion of Belgium's wastewater collection networks was US$2.6 pounds, possesses a molecular weight of 34 g per mole.
million per year, equivalent to 10% of the nation's wastewater Indoles, skatoles, mercaptans, various volatile organic com-
treatment and collection costs (Kaempfer and Berndt, 1998; pounds (VOCs), hydrogen sulfide, and ammonia are among the
Antonopoulou et al., 2014). odorous compounds that are capable of producing odor in waste-
Despite several studies on prevention and control of odorous water collection and treatment facilities. The main odor-producing
gases, no comprehensive paper exists about recent research compounds and their associated information are listed in Table 1.
achievements. The present study collects and categorizes new Odor-causing compounds presented in Table 1, rows 1e24, can
achievements in prevention and control of odorous gases in WCTS. naturally enter water supplies as the result of biochemical re-
actions. Compounds presented in rows 25e30 are produced in
2. Odor and odorous compounds in wastewater facilities microbial biofilm layers formed in drinking water distribution
networks, in which they are released into the water supply. Com-
Humans and animals recognize the presence of chemical pounds presented in rows 31e34 are produced during the
188 A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206

Table 1
List of common odorous compounds.

No. Compound Chemical formula Odor Odor threshold value (ppm) Molecular weight (g/mole)

1 2-propene 1 thiol CH2¼CHeH2eSH The smell of garlic, hot coffee 0.00005 47.15
2 1-thiol-pentane CH3e(CH2)3-CH2-SH Stench, goo 0.0003 104.22
3 Benzyl mercaptan C6H5CH2SH Leek- or garlic-like 0.00019 124.21
4 2-butene-1-thiol CH3eCH]CHeCH2-SH Odor similar to the smell of skunk 0.000029 90.19
5 Dimethyl sulfide (CH3)2S Cabbage, sulfurous 0.0001 62.13
6 Ethyl mercaptan C2H6S Rotten cabbage, flatulence, skunk-like 0.00019 62.10
7 Hydrogen sulfide H2S Rotten egg 0.00047 34.10
8 Methyl mercaptan CH4S Rotten cabbage, flatulence 0.0011 48.10
9 Propyl mercaptan C3H8S Cabbage-like 0.000015 76.16
10 Sulfur dioxide SO2 Pungent; similar to a just-struck match 0.009 64.07
11 tert-Butylthiol C4H10S The smell of skunk 0.00008 90.10
12 Thiocresol CH3eC6H4-SH The smell of rancidity 0.000062 124.21
13 Ammonia NH4 Strong pungent odor 1 18.014
14 Thiophenol C6H6S The smell of garlic, stench 0.000064 110.18
15 Geosmin C12H22O Earthy and musty odor 0.004 182.3
16 Methylisoborneol C11H20O Earthy and musty odor 0.015 162.28
17 2-Isopropyl-3-methoxypyrazine C8H12N2O Rotten vegetables, wet paper 0.0002 152.19
18 2-Isobutyl-3-methoxypyrazine C9H14N2O The smell of wood, decay, coal particles 0.001 122.66
19 b-Ionone C13H20O Smell of violets 0.007 192.3
20 b-Cyclocitral C10H16O The smell of fruit 19 152.23
21 cis-3-hexen-1-ol C6H12O The smell of grass 70 100.16
22 1-Penten-3-one C5H8O The smell of rotten fish 1.25 82.11
23 Dimethyl trisulfide C2H6S3 The smell of rotten vegetables 0.1 126.26
24 3-Methyl-1-butanal C5H12O The smell of oil 0.15 88.14
25 Trans,cis-2,6-nonadienal C9H14O The smell of cucumber 0.02 183.2
26 Trans-2,trans-4-decadienal C10H16O The smell of cucumber, fish, oil 3 152.23
27 Trans-2,trans-4-heptadienal C7H10O The smell of vegetables, fish 25 110.15
28 2,4,6-Trichloroanisole (TCA) C7H5Cl3O The smell of decay and mold 0.00003 211.47
29 2,4,6-Tribromoanisole (TBA) C7H5Br3O The smell of decay, rot, soil 0.00003 344.83
30 Benzothiazole C7H5NS The smell of chemicals 0.08 135.18
31 Aldehydes with Low molecular weight e The smell of fruit 30 > Less than heptanal
32 2-Chlorophenol C6H5ClO The smell and taste of medicine 0.36 128.56
33 2,6-Dibromophenol Br2C6H3OH The smell and taste of medicine 0.0005 521.9
34 Iodoform CHI3 Saffron-like 0.03 393.73
35 Acetic acid C2H4O2 Pungent/vinegar-like 0.0060 60.05
36 Propionic acid C3H6O2 Body odor 0.0057 74.078
37 Skatole C9H9N Strong fecal odor 0.0000056 131.174
38 Indole C8H7N Feces or jasmine-like 0.00030 117.15
39 Ethyl-o-toluidine CH3C6H4NHC2H5 Unpleasant 0.026 135.21
40 n-Butyric acid C4H8O2 Unpleasant and obnoxious 0.00019 88.11
41 Propane C3H8 Unpleasant 1500 88.11
42 Isobutyric acid C4H8O2 Rancid butter 0.0015 88.11
43 Isovaleric acid C5H10O2 Cheesy, sweaty 0.000078 102.1317
44 n-Pentane C5H12 Gasoline-like 1.4 72.15
45 n-Valeric acid C5H10O2 Very unpleasant 0.000037 102.13
46 n-Butane C4H10 Gasoline-like or natural gaselike 1200 58.12
47 Isohexanoic acid C6H12O2 Sweaty, fruity 0.00040 116.15
48 n -Hexane C6H14 Unpleasant 1.5 86.18
49 n-Hexanoic acid C6H12O2 Goat-like 0.00060 116.1583
50 Isopentane C₅H₁₂ Unpleasant 1.3 72.15
51 Methyl mercaptan CH4S Rotten cabbage, flatulence 0.000070 48.11
52 Propionaldehyde C3H6O Malty odor 0.0010 58.08
53 Sulfur dioxide SO2 Pungent; similar to a just-struck match 0.87 64.066
54 Carbonyl sulfide COS Sulfide-like 0.055 60.07
55 Acetaldehyde C2H4O Ethereal 0.0015 44.052
56 Formaldehyde CH2O Pungent and irritating 0.50 30.031
57 Methyl allyl sulfide CH₂ ¼ CHCH₂SCH₃ Garlic 0.00014 88.17
58 Dimethyl sulfide (CH₃)₂S Cabbage, sulfurous 0.0030 62.13
59 n-Nonyl Aldehyde CH3(CH2)7CHO Unpleasant 0.00034 142.24
60 Ethyl mercaptan C2H6S Rotten cabbage, flatulence, skunk-like 0.0000087 62.13404
61 n-decyl aldehyde CH3(CH2)8CHO Strong citrus peel 0.00040 156.27
62 n-Propyl mercaptan C3H8S Cabbage-like 0.000013 76.16
63 Acrolein C3H4O Irritating 0.0036 56.06
64 n-Hexyl mercaptan CH3(CH2)5SH Unpleasant 0.000015 118.24
65 n-Butanol C₄H₉OH Banana-like, harsh, alcoholic 0.038 74.12
66 Isoamyl mercaptan C5H12S Unpleasant 0.00000077 104.213
67 Isopropanol C3H8O Fruity odor 26 60.1
68 n-Amyl mercaptan C5H12S Unpleasant 0.00000078 104.2158
69 n-Propanol C3H8O Mild, alcohol-like 0.094 60.095
70 Tert-Butyl mercaptan (CH₃)₃CSH Natural gaselike 0.000029 90.2
71 Ethanol C2H6O Chemical odor 0.52 46.068
72 sec. Butyl mercaptan C4H10S Unpleasant 0.000030 90.18
73 Methanol CH4O Similar to ethanol 33 32.04
74 Isobutyl mercaptan C4H10S Unpleasant 0.0000068 90.187
A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206 189

Table 1 (continued )

No. Compound Chemical formula Odor Odor threshold value (ppm) Molecular weight (g/mole)

75 Crotonaldehyde CH₃CH]CHCHO Pungent, suffocating odor 0.023 70.09


76 n-Butyl mercaptan C4H10S Cabbage-like, skunk-like, garlic-like 0.0000028 90.18
77 Methacrolein C4H6O Unpleasant 0.0085 70.09
78 Isopropyl mercaptan C3H8S Skunk-like odor 0.0000060 76.16

wastewater treatment process at wastewater treatment plants, taste into the water (Peter and von Gunten, 2007). Some groups of
after which are released into the water. It should be noted that the odor-causing compounds could be released into the water through
odor-producing compounds would definitely release flavor into the the dissolution of small amounts of existing substances in waste-
water as well. However, the flavor-producing compounds will not water collection or through water distribution polyethylene pipes.
necessarily produce any odor. Thus, the list presented in Table 1 The most important compound of this group is 2,4,6-
could also be considered as both taste and odor-producing com- trichloroanisole (Khiari et al., 2002). The prevailing odor-causing
pounds. Trapped gases produced in wastewater collection pipes, compounds in drinking water are geosmin, methylisoborneol, and
which cause corrosion and unpleasant odors, should be collected hydrogen sulfide in wastewater, of which methylisoborneol is the
and then treated through air conditioning. The production of these main cause of odor in water. Hydrogen sulfide is a principal
odorous compounds could also be prevented using the methods component in odor production and corrosion in sewer in-
introduced in the following sections (Antonopoulou et al., 2014). stallments. Thus far, a large number of biochemical reactions that
One such substance that produces odor in wastewater collection can lead to the production of hydrogen sulfide have been identified.
networks' ducts is ammonia, caused by bacterial decomposition of Some of these chemical reactions are mentioned below (Chestnutt
urea produced in the networks. During the nitrogen cycle, nitrogen et al., 2007). According to Reaction (2), the sulfate ion can react with
fixing bacteria and plants absorb nitrogen from the air and convert organic carbon and water in the presence of appropriate microor-
it to ammonia, urea, nitrite, nitrate, and nitrogen-containing ganisms to produce bicarbonate ions and hydrogen sulfide. Ac-
organic compounds, which are stored by these organisms. The cording to Reaction (3), the sulfate ion can also produce hydrogen
fixated nitrogen is then cycled through the food chain after defe- sulfide in acidic conditions. Reaction (4) shows that elemental
cation, urination, or death, and ultimately converted back into sulfur can also be converted to hydrogen sulfide in biochemical
molecular nitrogen through various processes, such as ammonifi- reactions. Thus, the presence of adequate hydrogen and low pH is
cation, nitrification, and denitrification. Nitrogen organic com- crucial in this matter. Although Reaction (5) will not directly pro-
pounds and urea are converted into ammonia through the duce any hydrogen sulfide, it can lead to production of RSH sets or
ammonification aerobic process, but due to the absence of neces- mercaptans. Mercaptans are sulfur-containing compounds that
sary oxygen in the wastewater collection networks, the nitrogen possess not only intense and unpleasant odor, but can also cause
cycle cannot continue further into the nitrification process and serious problems such as tears, difficulty breathing, headache,
remain at the ammonification level. Ultimately, nitrite is converted abdominal pain, and nausea in humans.
into molecular nitrogen through anoxic denitrification process.
Early wastewater entry into the collection pipes carries small Microorganisms

SO2
4 þ 2C þ 2H2 O ƒƒƒƒƒƒƒ! 2HCO3 þ H2 S (2)
amounts of dissolved oxygen, which are completely depleted in the
first few kilometers, leading to the anaerobic condition in the pipe.
þ Microorganisms
In the first few kilometers, the existing urea in the wastewater, in S2
4 þ 10H ƒƒƒƒƒƒƒ! H2 S þ 4H2 O (3)
the presence of the remaining oxygen, is converted into ammonia
by the bacteria through ammonification process. Thus, the con- Microorganisms
version of nitrogen organic compounds to ammonia is halted. This S þ 2H þ ƒƒƒƒƒƒƒ! H2 S (4)
chemical process is then resumed in the wastewater treatment
plants. Ammonia possesses a low evaporation temperature, thus it Microorganisms
R ¼ S þ H þ ƒƒƒƒƒƒƒ! RSH (5)
is easily evaporated and leads to the release of wastewater odors in
the environment.
Other odor-causing compounds in wastewater collection net-
works and treatment plants are volatile organic compounds. These
compounds with low molecular weight (lower than 300 g per
mole) can ingress into the air through evaporation, which can be
inhaled by humans. Below are compounds that are among the most
important problematic volatile organic compounds in wastewater
collection and treatment plants. Ingression of taste and odor into
surface water can also occur during some human activities. The
most common cause of taste and odor ingress into surface waters is
water eutrophication caused by human activities such as agricul-
ture, and municipal and industrial waste disposal (Paerl et al., 2011;
Ptacnik et al., 2008). Ingression of nutrients into surface waters as a
result of aforementioned activities can increase the growth of mi-
croorganisms such as aqueous green algae (cyanobacteria) and
actinomycetes. These microorganisms are capable of releasing a
range of toxic (geosmin, methylisoborneol (Table 1)) and nontoxic
(cyanotoxin, microcystin) compounds into surface waters. The Fig. 1. Solubility of hydrogen sulfide in water at different temperatures (Nielsen et al.,
nontoxic compounds produced are capable of releasing odor and 1998).
190 A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206

3. A summary of odor control methods in wastewater between 650 and 815  C (Sun et al., 2008). Combustion of gasses
facilities and treatment plants' solid waste is achievable through incinerator
devices. Important factors in designing a thermal ablation system
Evaporation and degassing are the two primary methods for the include combustion temperature and air retention time. Their
emission of odor-causing agents from wastewater collection and importance stems from the fact that they determine volatile
treatment systems. In balanced conditions, the amount of evapo- organic compounds' subversion efficiency. As effective as it is, this
rated matter would be equal to the matter returned to the liquid method is very expensive and leads to the emission of secondary
level. However, in ventilated conditions or where the liquid is in pollutants such as carbon dioxide.
contact with the atmosphere, the evaporation rate would be higher The catalytic incineration process is another method of odor
than the returned gas into the liquid level. Primarily, odor-causing control. In this process, volatile organic compounds in the emitted
substances possess low molecular weight, which is detectable in gasses are oxidized in temperatures between 300 and 500  C in the
low concentrations. Thus, even smallest amounts of evaporation presence of a catalyst. The catalyst increases the rate of reaction at a
can lead to odor generation. Increments of the joint surface of the given temperature without significant changes during the reaction.
gas and liquid phases can also increase evaporation. In other words, Platinum and palladium are catalysts used in the incineration
as the contact surface of wastewater and air increases, the evapo- process of volatile organic compounds. This method is substantially
ration of odor-causing substances mutually increases. In the expensive.
degassing process, dissolved gases in water or wastewater transfer Another method in eliminating odor-causing compounds is
from liquid phase into the gas phase due to temperature increase or adsorption. In adsorption, the odorous gas is removed through
turbulence. In general, the emission control strategies of odor- passing the wastewater or the ventilated air of the wastewater
causing compounds include: (i) reducing the amount of odor- collection network through a bed of active carbon, silica gel, or
causing compounds produced at the source; (ii) eliminating tur- alumina. Activated carbon is among the most utilized adsorbents.
bulence in sewage; (iii) applying a prevention plan for wastewater Active carbon is much cheaper than other odor control methods. In
pre-treatment or the discharge of odor-causing compounds in certain circumstances, the amount of natural organic compounds is
municipal wastewater collection networks; (iv) establishing mean high. In this case, the adsorption of odor-causing compounds
intervals; (v) dilution of contaminated air through mixture with competes with adsorption of natural organic compounds,
clean air; (vi) combustion of odor-causing compounds in high decreasing the absorbents' removal efficiency (Chestnut et al.,
temperatures, known as the incineration process; (vii) catalytic 2007).
combustion of odor-causing compounds; (viii) adsorption of odor- Biological methods can also eliminate odor-causing compounds
causing compounds from wastewater and surrounding contami- in wastewater and surrounding air. Many microorganisms possess
nated air; (ix) biological decomposition of odor-causing com- the capability to absorb and decompose odorous compounds. These
pounds in wastewater and surrounding air; (x) utilizing overlying biological methods include biofilters, bioscrubbers, suspended
chemical compounds to reduce generated odor; (xi) improvement growth reactors, and biotrickling filters. All these methods are
of concrete resistance to sulfuric acid generated from biological inexpensive and effective despite their complex steering. The
decomposition of hydrogen sulfide; and (xii) establishing covered importance of applying biological methods in treating contami-
odor-management installations. Establishing covered installments nated air in wastewater collection networks and wastewater
possess two major problems: (1) the treatment necessity of treatment plants is all-encompassing, and discussed in the next
collected gases from installations and (2) corrosion of mechanical section.
equipment due to the increase of corrosive gases such as hydrogen Overlying chemical compounds are another way to control odor
sulfide. Preventing the discharge of odor-causing compounds into in the environment. Unpleasant odors near wastewater treatment
the wastewater collection networks is a difficult and, in some cases, plants are overlaid or overshadowed by aromatic odors dispersed in
financially impossible task. Airlocking the entrance to municipal ultrafine particles of liquid (mist), or evaporated state (steam). To
wastewater collection networks would reduce emission of odor- some individuals, however, the overlying odors are much more
causing compounds into the air, reducing the ventilation in unpleasant than the original odor, and occasionally the effective-
wastewater collection networks and aggravating the corrosion. ness of masking agents is limited. Among the many odor-causing
Turbulence could be greatly diminished through proper design of compounds, hydrogen sulfide is the most important odorous
wastewater collection network; however, turbulence is reestab- agent in wastewater collection networks. Therefore, more specific
lished in these wastewater collection networks and wastewater methods have been developed by researchers for its control (Zhang
treatment plants. The amount of dissolved hydrogen sulfide in et al., 2008). Sulfide occurs in microbial layers (biofilm) on the inner
water is highly dependent on temperature. Thus, with slight surface of the wastewater collection pipes. Its production rate de-
changes of temperature, hydrogen sulfide would transfer from pends on (i) the concentration of organic matter and nutrients; (ii)
liquid phase into gas phase. The solubility of hydrogen sulfide at the concentration of sulfur in the wastewater; (iii) the level of
various temperatures is presented in Fig. 1. dissolved oxygen; (iv) the pH of wastewater; (v) the temperature of
Establishing mean intervals is another method in odor control. wastewater and the internal environment of collection pipes; (vi)
An average distance of 70e500 m between the odor source and turbulence and flow speed of wastewater in the pipes; (vii)
residential areas can lead to the dilution of odor-causing gases. This wastewater retention time in wastewater collection pipes; and
interval is dependent on the odor source and climate conditions. (viii) the level of wastewater free surface in disposal for compound
Maintaining such a distance, however, especially in municipal areas exchange between wastewater and the contacting air (Nielsen
and wastewater collection systems in vicinity of residential areas, is et al., 1998). The presence of hydrogen sulfide is associated with
not always attainable. Dilution by odorless air is another strategy in pipe corrosion, unpleasant odor production, and wastewater
odor control. The odorous gases can be directed through long treatment plants' staff poisoning (Zhang et al., 2008). Slight prob-
funnels to be diluted by fresh air before reaching the surface. lems with corrosion in concrete pipes are initiated when the con-
Chimneys with an effective height of 35e45 m already exist to centration of sulfur in wastewater is between 0.1 and 0.5 mg/l in
dilute odorous gases. However, sometimes this method is very anaerobic conditions (Hvitved-Jacobsen et al., 2002). Intense pipe
expensive and not applicable to a given situation. corrosion problems are initiated when the concentration of sulfur
Odorous gasses can also be incinerated at temperatures rises above 2.0 mg/l in anaerobic conditions. Increasing the
A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206 191

Fig. 2. Classification of hydrogen sulfide prevention methods in wastewater collection networks.

oxidation and reduction potential is one effective way to prevent dissolved sulfur. Adding hydrogen peroxide, potassium perman-
the production of hydrogen sulfide (Hobson and Yang, 2000). ganate, or chlorine in wastewater can oxidize sulfur in insoluble
Increasing the oxidation and reduction potential means adding forms and consequently keep it out of reach of microorganisms.
electron acceptor compounds, such as oxygen, nitrate, and nitrite to Previous studies suggest that although the removal efficiency of
water. Adding nitrate and nitrite to wastewater can effectively hydrogen sulfide by oxidizing compounds is high, its removal ca-
reduce hydrogen sulfide production (Shelley et al., 2005). In the pacity for compounds such as geosmin and methylisoborneol
presence of nitrite and nitrate, the bacteria tend to reduce nitrite (Table 1) is very limited, mainly because of the resistance of tertiary
and nitrate and oxidize sulfide, which leads to the decline of alcohols (Qi et al., 2010; Korategere et al., 2004).
hydrogen sulfide production. Reducing the activity of sulfate- Physical methods, such as air ventilation of wastewater collec-
reducing bacteria (SRB) is another strategy to reduce the tion networks, can also have promising results in preventing the
hydrogen sulfide production (Jayaraman et al., 1999; Nemati et al., corrosion of pipes by hydrogen sulfide. However, releasing the
2001; Reinsel et al., 1996). To reduce the activity of SRB, increasing ventilated air into the environment can cause inconvenience for
the pH and using bactericidal compounds, molybdate ions, bacte- area residents. Therefore, treating the ventilated air prior to release
riophages are recommended (Nielsen et al., 2005). Utilizing into the environment is advisable (Rosenfeldt et al., 2005).
chemical compounds such as iron ions, hydrogen peroxide, and The advanced oxidation processes have also proved effective in
chlorine are among other methods to control hydrogen sulfide in eliminating odor and taste from water and wastewater. Some of the
wastewater collection networks. most common advance oxidation processes include: (i) application
Iron ions can react with sulfur ions to produce ferrous sulfide of ozone; (ii) simultaneous use of ozone and hydrogen peroxide in
(FeS), which possesses low solubility in water and places sulfur out combination with UV light; (ii) Fenton method; (iv) photo-Fenton
of reach of bacteria. In this situation, hydrogen sulfur production method; (v) semiconductor photocatalysis; (vi) electrolysis; (viii)
will be reduced due to depriving the bacteria of the required ultrasound irradiation; and (viii) wet air oxidation (Comninellis
192 A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206

et al., 2008). The oxidation and advanced oxidation processes are to odor production (Table 1) and corrosion in wastewater in-
classified under the same family for taking advantage of oxidizing stallments. Fungus can grow on various surfaces and objects,
compounds such as hydroxide (OH). The advantages of the causing serious problems. In tropical regions, corrosion by fungi
advanced oxidation process are its speed and the possibility of (white mold) is very common. Fungi can corrode rubber and steel
simultaneous oxidation of a wide range of contaminates (Chestnutt (coated or uncoated). In most cases, fungi do not inflict much
et al., 2007). However, each advanced oxidation method has its own mechanical damage but can harm the appearance and color of
specific way to produce hydroxide, making each suitable for use in objects. In addition to organic acids production, fungi can also cause
specific conditions (Chiron et al., 2000). Despite the efficiency of crevice corrosion on metal surfaces. The following measures can be
advanced oxidation methods in eliminating odor, thus far no carried out to prevent corrosion by fungi: (i) periodic cleaning of
practical application has been found due to the complexity of the metallic and nonmetallic surfaces to prevent the growth of mold;
operation. It is clear that the best option for odor control is pre- (ii) where possible, reducing relative humidity; and (iii) using toxic
vention of odorous compounds' production and not their removal organic substances such as Gentian violet to prevent fungi growth.
from air. Restricting hydrogen sulfide production can hamper the Gentian violet is an antimicrobial, antifungal and anti-worm dye
corrosion of wastewater collection networks and treatment used for coloring purposes in biology and microbiology. This
equipment. Fig. 2 presents the known hydrogen sulfide prevention compound can reduce the growth of mold and fungi on metallic
or elimination methods in wastewater or contacting air. surfaces. One way to prevent corrosion in metal pipes is cathodic
Some fungi can occasionally produce odor and corrosion in protection.
wastewater and water networks. Fungi are heterotrophic organ-
isms that have no roots, stems, or leaves. Lacking chlorophyll, these 4. Hydrogen sulfide production in wastewater
organisms are unable to synthesize organic materials and thus are
compelled to live on organic matter, such as dead animals and Lens and Kuenen (2001) concluded that the sulfur cycle is highly
plants, or as parasites on or inside living cells. These organisms use complex and associated with many factors such as wastewater
organic materials and produce considerable amounts of organic volume, the concentration of microorganisms in wastewater, the
acids such as oxalic acid, acetic acid, and citric acid, which can lead amount of sediments in wastewater collection pipes, and

Fig. 3. Different outcomes of sulfur after entering into wastewater collection network.
A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206 193

Fig. 4. Cycling of sulfur in a sulfuretum.

wastewater contact area with air. Despite the complexity of the hydrogen sulfide into sulfuric acid. The main source of carbon for
cycle, some researchers, such as Lahav et al. (2004), have success- chemoautotrophic bacteria is carbon dioxide and their main source
fully provided mathematical models to predict the amount of sulfur of energy is chemical compounds. By absorbing carbon dioxide as a
produced in the cycle. Sulfur cycle includes processes such as the source of carbon and hydrogen sulfide as its main source of energy,
production of sulfide, sulfide transition from the liquid phase into this bacterium can properly grow and reproduce. The produced
the gas phase, chemical and biological oxidation of sulfur, and, ul- sulfuric acid can attack concrete constituents and cause intense
timately, the reactions of sulfide ion-containing compounds with corrosion in metals.
iron and chemical sequestration (Zhang et al., 2008). The sulfate ion In different depths of a pond or in wastewater collection pipes,
is the most common type of sulfur, observed in concentrations diverse species of sulfur are converted into each other (Fig. 4). In
between 20 and 400 mg/l (Paing et al., 2000), and is converted into surface water, which contain the highest amount of oxygen,
sulfide by sulfate regenerative bacteria. This conversion takes place elemental sulfur and hydrogen sulfide are biologically converted to
essentially in anaerobic conditions by microorganisms present in CH2O and SO2 4 . In the middle depth of water, where the concen-
sediment-inhabited regions of the wastewater collection networks tration of oxygen is lower than at the surface, only facultative
(Parande et al., 2006). The activity of sulfate-reducing bacteria is bacteria can grow. In this facultative area, hydrogen sulfide is
mostly observed in areas where the wastewater flow moves slowly, converted to CH2O and elemental sulfur. Finally, the deepest part of
is poorly aerated, and retains high temperature (Hvitved-Jacobsen the water is where anaerobic conditions prevail. In this anaerobic
et al., 2000). At a pH of about 7, sulfur is observed in two forms: area, organic sulfur, CH2O, and SO2 4 are converted to hydrogen
H2S and HS¡ (Yang et al., 2005). At a pH of more than 7, the sulfide by anaerobic bacteria. This situation often occurs in natural
dominant form of sulfur is S¡ (Fu and Shen, 1990). Various forms of lakes or facultative ponds and is called a sulfuretum. Fig. 4 shows
sulfur are converted into one another (Reactions 6 and 7): cycling of sulfur in a sulfuretum. Different bacteria tend to live in
those areas of the pond where their particular capabilities provide
H2 S4Hþ þ HS (6) them with an ecological niche. Near the pond's surface, chemo-
trophic bacteria dominate; here they can obtain their energy from
the aerobic oxidation of H2S and elemental sulfur to form SO2 4 .
HS 4Hþ þ S2 (7) Therefore, chemotrophic bacteria are essential to prevent hydrogen
sulfide emission from lakes or wastewater treatment ponds.
In Reactions 5 and 6, only hydrogen sulfide can transfer from
Many researchers claim that biological degradation of proteins
liquid phase into gas phase and vice versa (Fu and Shen, 1990).
and particularly the biological degradation of the amino acid
Hydrogen sulfide transition from one phase to another depends on
methionine are the main reasons that volatile sulfur compounds
factors such as temperature, pH, the rate of wastewater flow tur-
are produced during anaerobic digestion. Volatile sulfur com-
bulence, and air conditioning in the wastewater collection network
pounds are a group of chemicals with sulfur in their chemical
(Yongsiri et al., 2004, 2005). In numerous studies, researchers have
structure. In addition, this group of chemicals has low molecular
demonstrated that the air in wastewater collection networks
weight, allowing them to evaporate easily. Some of the well-known
collected by the slope of the land contains about 300 mg/m3
volatile sulfur compounds are hydrogen sulfide, methanethiol,
hydrogen sulfide (Pomeroy and Bowlus, 1946; Thistlethwayte and
dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide. Amino
Goleb, 1972; Matos and Aires, 1995). In Fig. 3, various possible
acids are the building blocks of protein structure. The following
outcomes of sulfur in wastewater collection networks are pre-
pathway is suggested for production of methyl mercaptan (also
sented. Based on Fig. 3, the chief consequence of sulfur resources is
known as methanethiol) from proteins through methionine (see
chemical sequestration caused by hydrogen sulfide reaction with
Reaction 8).
metals such as zinc, lead, nickel, and iron. As mentioned earlier, the
metallic sulfides are poorly soluble in water, and so are quickly
sedimented. Oxidation of sulfur compounds in wastewater pro- Protease enzyme Peptidase enzyme
Proteins ƒƒƒƒƒƒƒ! Polypeptides ƒƒƒƒƒƒƒƒ! C4 H8 O2 N  S
ceeds both biologically and chemically; therefore, the process is
Methionine gammalyase
highly complex (Gadekar et al., 2006). Biological oxidation of  CH3 ƒƒƒƒƒƒƒƒƒƒƒ! H  S  CH3
hydrogen sulfide is normally carried out on the free wastewater
(8)
surface, where there is contact with air (Islander et al., 1991). Thi-
obacillus sp. is a chemoautotrophic aerobic bacterium, through Similarly, biological degradation of cysteine, which is a sulfur-
which a wet layer of pipe crown has the capability to oxidize containing amino acid, can form hydrogen sulfide. Cycling of
194 A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206

sulfur comprises two forward and reverse steps of sulfurication and


desulfurication. During sulfurication process all forms of sulfur Desulfovibrio desulfuricans
4H2 þ K2 SO4 ƒƒƒƒƒƒƒƒƒƒƒƒƒƒ! Ks S þ 4H2 O þ 850 KJ (15)
including hydrogen sulfide (H2S), sulfides (S2), sulfites (SO32),
thiosulfates (S2O32) and sulfates (SO42) are oxidized by
Desulfovibrio desulfuricans
different species of microorganisms. Features of bacteria suitable CaSO4 þ CH4 ƒƒƒƒƒƒƒƒƒƒƒƒƒƒ! CaCO3 þ H2 S þ H2 O (16)
for converting hydrogen sulfide to elemental sulfur are: (i) the
bacterium must have reliable capability of converting hydrogen Desulfovibrio desulfuricans
sulfide toS0; (ii) the bacterium should need minimal nutrient in- C6 H12 O6 þ 3K2 SO4 ƒƒƒƒƒƒƒƒƒƒƒƒƒƒ! 6KHCO3 þ 3H2 S þ 295KJ
puts; and (iii) the converted S0should be easily separated from the (17)
biomass. Many species of bacteria, such as Veillonella, Actinomyces,
Escherichia coli, Bacillus subtilis, Proteus vulgaris and Prevotella, are Desulfovibrio desulfuricans
able to produce H2S and can be the predominant H2S-producing 4CH3  CO  COOH þ H2 SO4 ƒƒƒƒƒƒƒƒƒƒƒƒƒƒ! 4CH3  COOH
bacteria in wastewater collection and treatment systems. On the þ 4CO2 þ H2 S
other hand, many species of bacteria such as Beggiatoa, Thiobacillus (18)
and Thiothrix are able to convert H2S to elemental sulfur (S0). In the
wastewater having a high concentration of oxygen, H2S is oxidized Desulfovibrio desulfuricans
þ
chemically or as a result of certain bacteria activities through the 4Fe2þ þ SO2þ
2 þ 2H2 O þ 2H ƒƒƒƒƒƒƒƒƒƒƒƒƒƒ! Fes þ 3FeðOHÞ2
Reaction (9). Based on this reaction the bacteria are able to gain (19)
494 KJ energy. Sulfur is collected as small particles by Beggiatoa and
Thiothrix while Thiobacillus releases all the small particles of sulfur The transferred hydrogen sulfide from liquid phase to gas phase
into wastewater. When H2S concentration of wastewater ap- is accumulated in the air above the wastewater in the collection
proaches nearly to zero, elemental sulfur oxidation is occurred network. The bacterial layer containing Thiobacillus sp. would then
according to Reaction (10). Thiobacillus are the most effective be able to absorb and oxidize hydrogen sulfide into sulfuric acid,
oxidizing species sulfur in wastewater. Reactions (9) and (10) based on Reaction (20).
demonstrates that oxygen is an integral part of oxidation process of
Bacteria
H2S and S0. Therefore, Beggiatoa, Thiobacillus and Thiothrix can only H2 S þ 2O2 ƒƒƒ
ƒ!H2 SO4 (20)
live in middle region where both H2S contained in settled sludge
The produced sulfuric acid would then gradually create a reac-
and oxygen contained in wastewater are accessible.
tion with the material incorporated with wastewater concrete
pipes, which leads to the amassment of a layer of plaster (CaSO4) in
2H2 S þ O2 /2S0 þ 2H2 O þ 494KJ (9)
the microbial activity region. As the production of sulfuric acid
increases, the thickness of the layer increases as well. In addition to
2S0 þ 3O2 þ 2H2 O/2H2 SO4 þ 598KJ (10) the production of sulfuric acid, a substance called ettringite
(CaAl2(SO4)3(OH)12.26H2O) is also produced, which causes cracks
Thiobacillus denitrificans is able to utilize oxygen elements in the
and holes in the concrete and increases depth of penetration for
molecules containing both nitrogen and oxygen. The activities of
sulfuric acid (Redner et al., 1994). Sulfuric acid production, reaction
this bacterium in sulfur oxidation are presented through Reactions
with concrete pipe wall, conversion to plaster, and production of
(11), (12) and (13).
ettringite, all contribute to the weakening of the pipe crown, which
ultimately collapses within a few years (US Environmental
5S0 þ 6KNO3 þ 2H2 O/3N2 þ 3K2 SO4 þ 2H2 SO4 þ 2584KJ Protection Agency (USEPA), 1991). According to the USEPA and
(11) based on the investigations carried out in 34 municipal wastewater
collection networks, the corrosion rate of wastewater concrete
pipes was estimated at 2.5e10 mm per year. Other researchers such
5S0 þ 6KNO3 þ 2CaCO3 /3K2 SO4 þ 2CaSO4 þ 2CO2 þ 3N2
as Davis et al. (1998) believe that the average corrosion rate in pipes
(12) is 3 mm per year, which grants a 50-year lifespan to standard
wastewater pipes. Based on another study conducted in Belgium,
5Na2 S2 O3 þ 8KNO3 þ 2NaHCO3 /6Na2 SO4 þ 4K2 SO4 the average corrosion rate of sewer pipes was reported at
(13) 1.1e1.8 mm per year. According to the study conducted by Davis
þ 2CO2 þ H2 O þ 4N2 þ 3739KJ
et al. (1998), the corrosion rate in Portland cement mixed with fly
Chromatiacea and Chlorbakteria species require light to survive. ash is lower than those of concrete pipes, with a corrosion rate of
As a result, they are able to oxidize H2S according to photosynthesis 1.0e1.3 mm per year, which grants a lifespan of 90e150 years to the
Reaction (14). pipes (Vincke, 2002). In order to calculate the corrosion rate in an
object, Equation (21) is adopted (Monteny et al., 2001):
6CO2 þ 3H2 S þ 6H2 O/C6 H12 O6 þ 3H2 SO4 (14)
mpy ¼ ð534  wÞ=ðD  A  TÞ (21)
During disulfurication process, specific species of bacteria are
capable of reducing þ8 valance sulfur to the 2 valance one Where mpy is the lost thickness of the object in thousandths of
appearing in molecules such as H2S or K2S. Some examples of an inch per year; w is the lost weight of the object in milligrams; D
disulfurication process reactions are shown in Reactions (15) is the density of the object in g/cm2; A is the body surface of the
through (18). Organic acids, alcohols, methane and various oils and object in square inches; and T is the test interval in hours. To utilize
fats are the most important electron donors in disulfurication this equation, the weight of the object must be determined and
process. Adenosine-5'-phosphosulfate reductase, Phosphoadenylyl then embedded in the specified environment for a fixed period of
sulfate reductase, Sulfite reductases and Desulfhydrase are the time. In the next stage, the object is weighed again and the corro-
most important enzymes involving in disulfurication process. As sion rate is calculated by the equation. Yamanaka et al. (2002) re-
shown in Reaction (19) Desulfovibrio desulfuricans are able to ported that the addition of formate, especially calcium formate, to
contribute to Iron corrosion as well. cement in concentrations of more than 50 mmol strongly inhibits
A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206 195

the growth of sulfate-oxidizing (such as Thiobacillus sp.) and 12.5e13 for 20e30 min. Such pH shocks can inhibit the activity of
acidophilic iron-oxidizing bacteria, which would control the sulfide reducing bacteria for as long as two weeks. While main-
corrosion rate in wastewater collection pipes. taining high levels of pH, the wastewater should not immediately
enter the treatment plant, lest it lead to the elimination of the
5. Increasing the oxidation reduction potential to control the microorganisms (USEPA, 1991).
level of hydrogen sulfide
7. Chemical removal of hydrogen sulfide from wastewater
5.1. Air or pure oxygen injection into the wastewater
7.1. Chemical decomposition of hydrogen sulfide by metal salts
Inadequate oxygen levels in wastewater cause hydrogen sulfide
production in sedimentations of wastewater collection networks 7.1.1. Insoluble metal sulfides in wastewater
with a depth of more than 1 mm (Yu et al., 1998). This occurs Sulfide reaction with metals such as iron, lead, nickel, manga-
because the maximum oxygen penetration into the sedimented nese, and zinc can convert sulfide into a poorly soluble form, which
layer in wastewater pipes is limited to 0.4 mm (Yu et al., 1998). In would eliminate it from wastewater and reduce hydrogen sulfide
aerated and aerobic conditions, the accumulated hydrogen sulfide production. In low and average concentrations of sulfide, there is a
in sedimented layers would be exposed to oxygen and immediately significant amount of insoluble metallic sulfides in wastewater
oxidized biologically or chemically (Zhang et al., 2008). If the (Nielsen et al., 2005). Studies conducted by the Brisbane City
wastewater contains no dissolved oxygen, the produced hydrogen Council, reported by ASCE (1989) reflect the importance of sulfide
sulfide can then easily take soluble form (USEPA, 1991). If waste- chemical decomposition by metal salts. Their study suggests that
water contains oxygen concentration of more than 0.5 mg/l, all with 0.12 mg/l sulfur in wastewater, no sulfide can be observed.
hydrogen sulfide is easily oxidized in sedimented layers with depth Chemical decomposition of sulfide by metal salts plays a crucial role
of 1 mm or more. The dissolved oxygen level can easily reach a in reducing hydrogen sulfide in wastewater.
concentration of 0.2 and 1 mg/l by injecting air into the wastewater
(Ochi et al., 1998). Doing so possesses advantages such as non- 7.1.2. Hydrogen sulfide elimination by iron salt
toxicity and lower levels of biological oxygen demand (BOD) in Iron is one of the most dominant metals in municipal waste-
wastewater (USEPA, 1992). The disadvantage of this method is the water. Generally, the concentration of iron in wastewater remains
limited solubility of oxygen in the wastewater. Since the concen- in the range of 0.4e1.5 mg/L, which plays an important role in
tration of pure oxygen is five times greater than in air, by injecting chemical decomposition of sulfide in wastewater throughout the
pure oxygen higher oxygen concentrations in wastewater can be sulfur cycle (Nielsen et al., 2005; Henze et al., 1997). The high
achieved, in the range of 5e7 mg/l (Chen and Leung, 2000). How- importance of iron in sulfide elimination signifies the important
ever, due to the presence of flammable gases, the risk of fire and role of iron salt in controlling hydrogen sulfide levels in wastewater
explosion would greatly increase (USEPA, 1992). Furthermore, us- (ASCE, 1989). In various studies, chloride salts of iron, iron sulfide,
ing pure oxygen can significantly increase total expense. and iron nitrite were utilized in both ferric and ferrous forms to
eliminate hydrogen sulfide. By decomposing ferrous sulfide, diva-
5.2. Inhibiting hydrogen sulfide by nitrate injection into wastewater lent iron can eliminate hydrogen sulfide from wastewater. Trivalent
iron can also bring about the elimination of hydrogen sulfide
Both long-term and short-term prevention of pipe corrosion by through the production of elemental sulfur and chemically
nitrate and nitrite has been reported by researchers (Zhang et al., oxidizing it into divalent iron (Reactions 22 and 23).
2008; Yang et al., 2005; Allen, 1949). Carpenter (1932) reported
that the production of odors in wastewater was greatly reduced by Fe2þ þ HS /FeS þ Hþ (22)
injecting sodium nitrate. This is due mainly to the fact that the
microorganisms are more able to reduce nitrate than sulfide; as a
2Fe3þ þ HS /2Fe2þ S0 þ Hþ (23)
result, less odor is produced (Allen, 1949). Allen concluded that by
adding 1 mg/l nitrate can halt hydrogen sulfide production for 29 Researchers believe that ferrous sulfate chemical decomposition
days. Nitrate injection can increase the oxidation and reduction of process is fast; however, some researchers including Nielsen et al.
wastewater, which would inhibit hydrogen sulfide. One study re- (2005) believe that chemical decomposition of hydrogen sulfide
ported that by increasing the potential oxidation and reduction rate by ferric chloride requires several hours of retention time before
to 500 mV, one can halt hydrogen sulfide production in wastewater. the process is complete. Furthermore, during the chemical
The production delay of hydrogen sulfide is highly dependent on decomposition of sulfur, some substances can interfere with the
the amount of initial injected nitrate (Poduska and Anderson, 1981). process by competing with the reaction of iron salts and sulfides.
This clash can lead to a decline in iron salts' level and consequently
6. Inhibiting the activity of sulfide reducing bacteria decreases removal efficiency. Iron phosphate and complex by li-
gands can appear as competitors in these reactions. There is no
In inhibiting the activity of sulfate-reducing bacteria, increasing specific agreement among researchers as to the superiority of ferric
the pH of the environment is the most effective way. However, iron over ferrous iron or vice versa in removal efficiency of
other methods like utilizing bactericides or molybdates has also hydrogen sulfide. Researchers have concluded that ferrous chloride
received much attention from researchers (Nemati et al., 2001; performed twice as efficiently as ferric chloride in sulfide removal
Reinsel et al., 1996; Poduska and Anderson, 1981). At a pH level of (Araújo et al., 2000; Jameel, 1989). On the other hand, Tomar and
9, the amount of hydrogen sulfide is insignificant and mostly ap- Abdullah (1994) reported that ferric chloride is somewhat more
pears in the form HS. It should be noted that increasing the pH to efficient in decomposition of sulfide. Based on their report, the
levels higher than 9 would reduce the efficiency of biological amount of required ferric iron is 20% lower than ferrous chloride
treatment of wastewater in treatment plants and considerably in- under the same conditions. Therefore, it is impossible to make a
crease total expense (Zhang et al., 2008). The best way to inhibit the sound judgment based on these contradictory results. However,
activity of sulfate-reducing bacteria is by using sodium hydroxide numerous studies conducted on the decomposition of sulfide in
to induce a pH shock, which increases the level of pH to a range of wastewater indicate that the ferrous and ferric iron salts are the
196 A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206

most effective chemical compounds in the decomposition of sulfur matter can produce trihalomethanes, which are proven to be car-
(Padival et al., 1995; USEPA, 1974). Despite the decomposition of a cinogens (Acero et al., 2005). Compounds such as bromine ions in
large portion of sulfide by iron salts, slight amounts of sulfur would water can also react with chlorine and produce bromophenols,
remain in soluble form, are very difficult to eliminate, and require which would limit applicability of wastewater chlorination. The
high amounts of iron salts to be removed (ASCE, 1989). application costs of chloride are estimated at US$26.50e38.20 per
kg of sulfur (Zhang et al., 2008).
7.1.3. Operation conditions and removal costs of sulfide by metal
salts
Zhang et al. (2008) reviewed the costs associated with chemical 7.2.3. Potassium permanganate
decomposition of sulfide by metal salts, and presented their results Potassium permanganate (KMNO4) is a strong oxidizing com-
in tabular form. This study is recommended to those interested in pound, capable of oxidizing sulfide into sulfate. Potassium per-
industrial applications of sulfide chemical decomposition. The manganate is typically a dry compound; therefore, it is kept in
application costs of sulfide chemical decomposition are reported in aqueous solution at 6% concentration before being applied in
the range of US$4.63e9.00 per kg of sulfur in wastewater (Zhang treatment (USEPA, 1991). One of the biggest disadvantages of po-
et al., 2008). The proper ratio of iron proportionate to sulfide is tassium permanganate is its high application cost, which amounts
recommended at 1e2.5 portions of iron to 1 portion of sulfide, to US$54.27e66.23/kg sulfur in wastewater.
which increases the sulfide removal efficiency to 88e100% (Nielsen
et al., 2005; Tomar and Abdullah, 1994; Padival et al., 1995).
7.2.4. Advanced oxidation methods
Advanced oxidation processes are among the methods for
7.2. Chemical decomposition of hydrogen sulfide by oxidants eliminating odor, taste, and other contaminants in water and
wastewater (Comninellis et al., 2008). Although oxidation and
7.2.1. Hydrogen peroxide advanced oxidation processes are classified in the same family of
Hydrogen peroxide (H2O2) can oxidize sulfide and produce oxidizing compounds, such as hydroxide (OH), they are investi-
water and oxygen. In addition, hydrogen peroxide can help create gated separately for more accurate classification (Chestnutt et al.,
an aerobic condition in the wastewater. The proper ratio of 2007). The advantages of the advanced oxidation process are its
hydrogen peroxide proportionate to sulfide is 1.3e4 mg/l per mg of speed and the possibility of simultaneous oxidation of a wide range
sulfur in wastewater, which achieves a removal efficiency of of contaminants. Various advanced oxidation methods and their
85e100%. Unfortunately, since the lifespan of hydrogen peroxide is corresponding oxidants are illustrated in Table 2. Advanced
about 90 min, in order to achieve the desired removal efficiency, oxidation processes can be applied simultaneously, resulting in
this compound should be injected in various regions of wastewater higher efficiencies (Comninellis et al., 2008). These methods can
networks (USEPA, 1991). The application cost of hydrogen peroxide also be combined with conventional physicochemical and biolog-
is estimated at US$2.38e5.26 per kg of sulfide (Zhang et al., 2008). ical processes of water treatment to achieve higher efficiencies in
odor elimination (Comninellis et al., 2008). In addition to odor-
7.2.2. Chlorine causing compounds, other organic compounds such as toxic sub-
Chlorine can reduce sulfur into sulfate oxide or elemental sulfur stances and biodegradation-resistant compounds will be removed
(USEPA, 1992). Chlorine's efficiency is limited due to its capacity to throughout the process. Four members of the mercaptans family
form reactions with organic and inorganic compounds. Chlorine include (Habibi et al., 2001): (1) mercaptobenzimidazole; (2)
can be injected into wastewater as a solution, such as a sodium mercaptobenzoxazole; (3) mercaptopyridine; and (4) para-
hypochlorite solution. Furthermore, if the concentration of sulfide tolylmercaptan, which were removed in a study conducted with
in wastewater is less than 1 mg/l, the oxidation reaction speed of photocatalytic decomposition process, with titanium dioxide (TiO2)
chlorine would be very low. In the case of chlorine in gas form, a as the catalyst. The study results suggest that removal efficiency is
ratio of 9e15 mg/l per mg/l of sulfide in wastewater is recom- directly associated with the amount of catalyst applied in a certain
mended (USEPA, 1991; Tomar and Abdullah, 1994). Where chlorine concentration level (3.33 mg/L). Among the aforementioned mer-
is injected in soluble forms such as NaClO or Ca(ClO)2, a ratio of captans, mercaptobenzimidazole and para-tolylmercaptan
1.8e0.2 mg/l per mg/l of sulfide is advised (ASCE, 1989). Chlorine possessed the lowest removal efficiency in photocatalytic decom-
can form reactions with a wide range of organic and inorganic position process due to their physicochemical properties. Many
substances. Therefore, in addition to eliminating portions of avail- studies conducted on odor- and taste-causing compounds suggest
able sulfide ions, it can also lead to the oxidation of organic matter that the majority of these substances can be eliminated easily by
in wastewater and reduction of the BOD of water (Bichsel and von advanced oxidation processes below the human olfactory
Gunten, 2000). The reaction between chlorine and some organic threshold.

Table 2
List of current advance oxidation methods and their produced oxidant (Chestnutt et al., 2007).

Method Produced oxidant

Ozone application OH, HO2, HO3, O 


2 , O3
Simultaneous application of ozone and hydrogen peroxide OH, O 
2 , O3
Fenton method (H2O2/Feþ 2) OH, HO2
Photo-Fenton OH
UV/O3, UV/H2O2, and UV/O3/H2O2 OH, HO2/O 2 , O3


Using ultraviolet beam in wavelength less than 190 nm OH, Hþ, eaq
Using ultrasonic irradiation OH, H
Photocatalytic process including ultraviolet/visible light and TiO2, ZnO, or any other catalyst OH, Hþ , O  -
2 , e , O2, HO2, HOO
g-Radiolysis OH, H, eaq
A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206 197

8. Biological removal of hydrogen sulfide US$41e88 for every kg of sulfur in wastewater (Yang et al., 2005).

According to studies of biological removal of hydrogen sulfide in


9. Prospects for hydrogen sulfide removal in the future
oil reservoirs and wastewater collection networks, nitrate-reducing
and sulfide-oxidizing bacteria (NR-SOB) can easily oxidize
9.1. Application of formaldehyde and paraformaldehyde in
hydrogen sulfide produced by sulfate-reducing bacteria (Nemati
elimination of hydrogen sulfide
et al., 2001a, 2001b). Results of the study on oil reservoirs illus-
trate the importance of nitrate-reducing and sulfide-oxidizing
Today, the application of formaldehyde in microbial growth,
bacteria (NR-SOB), followed by nitrate ions, in inhibiting the pro-
especially in food industries, is widely recognized (Kajitvichyanukul
duction of hydrogen sulfide (Æsoy et al., 2002; Okabe et al., 1999,
and Suntronvipart, 2006). Formaldehyde can suspend microbial
2003a, 2003b). Various forms of bacteria have been identified
growth and is ultimately fully eliminated in wastewater treatment
NR-SOB (Nemati et al., 2001a, 2001b). These bacteria include Thi-
plants (Kajitvichyanukul and Suntronvipart, 2006). Para-
omicrospira denitrificans, Proteobacteria, Thiobacillus denitrificans,
formaldehyde is an inexpensive compound and an excellent
and b-Proteobacterium, all of which are capable of oxidizing sulfide
replacement for formaldehyde. The transformation of para-
in the presence of nitrate (Kodama and Watanabe, 2003). Sulfide
formaldehyde to formaldehyde occurs in conditions where pH is
oxidation has also been observed in an anoxic condition in the
neutral, and the environment contains water and remains at room
presence of Beggiatoa bacteria. Sayama et al. (2005) reported that
temperature (McMurry, 2003). Studies suggest that by suspending
Beggiatoa is capable of oxidizing HS into S0, after which they are
bacterial activity, formaldehyde can inhibit the production of
stored and converted into SO4 2 intercellular globules (Æsoy et al., hydrogen sulfide (Zhang et al., 2008). Formaldehyde is water solu-
2002). Based on Reactions 24 and 25, conditions in which oxygen
ble, and upon entering water reversibly transforms into meth-
and nitrate are the final receptors, the final product of oxidation is
anediol (CH2(OH)2). Since wastewater collection networks are
generally elemental sulfur or S (Anja et al., 2006). According to
closed systems, ingress of formaldehyde into the atmosphere would
these reactions, HS- is converted into S in contact with nitrate,
not occur. Formaldehyde can be transferred to treatment plants for
which ultimately increases the pH of the environment. On the other
disposition. Formaldehyde is a toxic, mutagenic, teratogenic com-
hand, Reactions 26 and 27 illustrate the conversion of S into SO4
2 , pound, suspected of being carcinogenic. This can cause serious
leading to the decline of pH (Sayama et al., 2005; Buisman et al.,
problems for treatment plants' workers. Thus, it is essential to
1990; Gadekar et al., 2006).
ensure that formaldehyde is entirely eliminated through the treat-
ment process (Fulazzaki et al., 2013; Talaiekhozani et al., 2013). The
HS þ NO þ 0 
3 þ H /S þ NO2 þ H2 O (24)
application cost of formaldehyde is estimated in the range of
US$1.63e2.00/kg of sulfur in wastewater.
HS þ 0:4NO þ 0
3 þ 1:4H /S þ 0:2N2 þ 1:2H2 O (25)
9.2. Gradual release of oxygen in gas phase (MgO2/CaO2)
S0 þ 3NO þ 2
3 þ H2 O þ 3H /SO4 þ 3NO3 þ 5H
þ
(26)
Several methods have been applied in oil industries to inhibit
the production of hydrogen sulfide in oil reservoirs, which are
0
S þ 1:2NO
3 þ 0:4H2 O þ 1:2H þ
/SO2
4 þ 0:6N2 þ 2H þ
(27)
rarely used in wastewater (Lee et al., 2005). Solid compounds like
Although the amount of required nitrate depends on the type magnesium peroxide (MgO2) and calcium peroxide (CaO) can
and concentration of organic matter and the level of bacterial ac- gradually release their oxygen, which would in time transfer into
tivity, theoretically in wastewater this ratio falls in the range of magnesium hydroxide (Mg(OH)2) and calcium hydroxide
0.18e0.44 mg/l nitrate (in terms of nitrogen per 1 mg/l sulfur) (Luis (Ca(OH)2), respectively. By injecting these compounds into oil wells
et al., 2005). The application costs of this method are roughly and river bed sediments, their aerobic condition can be maintained

Fig. 5. Schematic of wastewater collection pipes protection against hydrogen sulfide by using microbial fuel cell.
198 A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206

Fig. 6. Schematic of a microbial layer on biofilter bed (Fulazaky et al., 2014).

for long periods of time. The inhibition of hydrogen sulfide by electrons are transferred to cathode electrodes by anode electrodes.
magnesium peroxide and calcium peroxide is mainly due to the The next stage involves the production of water through the reac-
chemical oxidation of hydrogen sulfide and toxicity to sulfate- tion of Hþ with 2 transferred electrons and 0.5 mol of oxygen in
reducing bacteria. Study results suggest that the presence of 4% wastewater. Taking advantage of this method, in addition to the
magnesium peroxide can inhibit the production of hydrogen sul- odor and corrosion control, electricity can be generated. The
fide for 40 days. The best option in inhibiting the production of generated electricity is very low; however, countless number of
hydrogen sulfide over time is through gradual release of oxygen in these electrodes throughout hundreds of kilometer of wastewater
solid phase (Chang et al., 2007). Although it is quite possible to collection networks would generate measureable amounts of
apply this method to sediments in wastewater collection pipes, it electricity. Note that the aforementioned method was entirely
still faces the issue of being washed off when applied in solid phase. theoretical at the publication of this article, and the author found
no relevant research that was directly conducted on wastewater
9.3. Fuel cell application in hydrogen sulfide inhibition networks (Zhang et al., 2008; McNerney, 1999; Randerson, 2003;
Redner et al., 1991; Verthe  and Verstraete, 2006; Verthe  et al.,
A fuel cell is an electrochemical device that converts chemical 2004).
energy into electrical energy. The conversion process continues
until the fuel and the oxidants are depleted. Many studies have 10. Hydrogen sulfide polluted air treatment methods
confirmed the applicability of hydrogen sulfide in fuel cells (Aguilar
et al., 2004; Kirk and Winnick, 1993; Peterson and Winnick, 1996). If the inhibition of hydrogen sulfide production in wastewater
Microbial fuel cells are devices capable of converting chemical collection networks or wastewater treatment plants is not possible,
energy into electrical energy directly through electrochemical re- the ventilation of surrounding air (in indoor facilities) would prove
actions associated with biological processes. Some researchers useful. The ventilated air must first be treated prior to being
report that hydrogen sulfide can be converted into elemental sulfur released into the atmosphere. Various physicochemical and bio-
in microbial fuel cells. Oxidation of hydrogen sulfide in the anodic logical methods of air purification have been developed, which are
region of microbial fuel cells can generate electrical energy equal to briefly mentioned in this section.
101 mW (Rabaey et al., 2006). Fuel cells made by upflow anaerobic
sludge blanket (UASB) reactors are capable of eliminating 98% of 10.1. Biological treatment methods of hydrogen sulfide polluted air
acetate and 46% of sulfate from wastewater. Applying this system in
hydrogen sulfide removal from wastewater is an interesting idea, Humanity's increasing demand for reliable sources of material
illustrated in Fig. 5 (Zhang et al., 2008). In addition to the elimi- and energy as a result of industrial and technological advancements
nation of hydrogen sulfide, odor, and corrosion, this application can in the present century has led to the contamination of essential,
also generate some electricity. Hydrogen sulfide elimination in fuel nonrenewable sources of water, air, and soil. Consequently, exten-
cells occurs while transferring electrons from bacteria to the elec- sive research has been carried out in the past half century to control
tron receptor. the emission of such contaminants (Chow, 2007). The main source
As mentioned earlier, the penetration capacity of dissolved ox- of these environmental contaminants is fossil fuels, which pose
ygen into the sediments on a pipe bed is only 0.4 mm above this immediate threat to human health, climate quality, agriculture, and
depth (especially above 1 mm), the condition is entirely anaerobic. the global economy. Hydrogen sulfide is a toxic, flammable, and
At this point, the sulfate-reducing bacteria would convert toSO2 4 , colorless gas with an unpleasant smell, similar to that of rotten egg.
and organic carbon in the sediments into carbon dioxide and Hydrogen sulfide can be produced and released naturally or as the
hydrogen sulfide. At the next stage, due to the existence of anode result of human activities. Hydrogen sulfide production sources
electrodes, hydrogen sulfide would transform into 2 electrons, Hþ include volcanoes, swamps, hot springs containing sulfate, volcanic
and elemental sulfur. Since elemental sulfur is not soluble in water, underwater vents, oil and gas reservoirs embedded in the earth,
it would be decomposed and would remain out of reach for sulfate- and anaerobic biodegradation of organic compounds (Lomans et al.,
reducing bacteria. Electricity is generated when the produced 2002). In addition to the aforementioned sources, significant
A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206 199

Fig. 7. Schematic of a simple biofilter for removal of odorous compounds from air.

amounts of hydrogen sulfide are released by industries, including Hence, nutrients do not need to be added to the biofilter. The rate of
oil refineries, pulp and paper factories, wastewater treatment biodegradation in biofiltration processes is determined by mass
plants, food industries, livestock farms, the gas industry, and transfer mechanisms (Lebrero et al., 2012). Based on the present
especially wastewater collection and treatment facilities. The con- research, the solubility of hydrophobic substances in water con-
centration of hydrogen sulfide by these industries are very low, but taining microorganisms is higher than solubility in water with no
even a slight amount can cause significant corrosion and odor, microorganism, which is caused by several enzymes secreted by
which necessitates the elimination of this gas. Based on the Euro- microorganisms. The biofilm layer, containing millions of micro-
pean, American, and Chinese standards, the maximum permissible organisms, is responsible for the decomposition and removal of
hydrogen sulfide emission through a chimney is 5e10 ppm (Lenior, contaminants in every biofiltration process. Biofilm is a thin layer of
2009). Studies suggest that the biological method would be an microorganisms that stick together on a surface. The thickness of
efficient and inexpensive way to remove hydrogen sulfide. The the biofilm and the efficiency of biofiltration processes are directly
advantage of the biological method is that no chemical compound proportional. In other words, by increasing the thickness of biofilm
that is harmful for the environment is used. Therefore, the waste and the microbial concentration, the capacity for removal will also
and sludge produced by these processes has fewer adverse effects increase (Kennes and Veiga, 2013). On the other hand, increasing
in comparison with other chemical processes. A wide range of the thickness can limit the penetration of nutrients and oxygen into
microorganisms is capable of removing hydrogen sulfide. Aroca the biofilm (Schifftner, 2013). The region of biofilm that receives
et al. (2007) and Sercu et al. (2005) reported that two groups of appropriate amounts of nutrients and oxygen is called the active
microorganisms belonging to the Acidithiobacillus and Thiobacillus layer, while the deprived regions are called the passive layer. The
families are capable of removing hydrogen sulfide from the air. Cho passive layer is typically the deeper part of the biofilm (Fig. 6). This
et al. (1991) introduced neutrophilic bacteria and Thiobacillus region is responsible for keeping the wall of the bed attached to the
novellus as capable of hydrogen sulfide removal. Many researchers, biofilm. Microorganisms in the active layer would consume the
including Chung et al. (2000), consider Thiobacillus thioparus to be nutrients and oxygen and would leave nothing for the passive re-
hydrogen-removing bacteria. Thiobacillus denitrificans, Pseudo- gions. With the decline of oxygen and nutrients in passive layer, the
monas putida CH11, Hyphomicrobium sp., and Haloalkaliphilic microorganisms would start feeding off their own cytoplasm and
groups have also been considered to be proper hydrogen sulfide one another. Consequently, they would lose touch with the bed
removers (Gonzalez-Sanchez et al., 2008; Sercu et al., 2005). Some surface and become detached. These regions would continually
hydrogen-removing bacteria are categorized under the chemoau- detach from the biofiltration system and be replaced by a new
totrophic group, which are capable of decomposing chemical biofilm (Devinny et al., 1999).
compounds as their energy source and carbon dioxide as their With a large volume of air passing through the biofilter, water
carbon source. Chemoautotrophic bacteria can be used for simul- would start to evaporate from the bed, leading to the filter drying
taneous removal of various contaminants mixed with carbon di- out and a decline in microbial activity. Therefore, necessary mea-
oxide. For example, a combination of hydrogen sulfide (as energy sures should be taken. For example, some researchers have
source) and carbon dioxide (as carbon source) can lead to the attempted to cool the exhaust gas from the biofilter; therefore, the
simultaneous elimination of both compounds. Most applicable evaporated water would return to the biofilm as liquid. Some other
bioreactors used for treatment purposes include biofilters, bio- researchers propose injection of water vapor or moist air in asso-
trickling filter reactors, suspended growth reactors, membrane ciation with contaminated air into the biofilter. Others have
bioreactors, and bioscrubbers (Fulazzaky et al., 2014). attempted to spray water directly onto the biofilter bed to
compensate for water shortages. Note that excess water would fill
10.1.1. Biofilters the porous structure of the biofilm bed, namely soil, compost, and
Biofilters are containers filled with a bed of natural materials garden waste, leading to a pressure drop in the biofilter, channeli-
such as soil, compost, and agricultural waste, through which zation of inlet polluted air, and consequently a decline in the
contaminated air passes. With proper environmental humidity, the removal efficiency of the odor-causing compound. In channelized
hydrogen sulfide would transfer from gas phase into liquid phase in conditions, the air passes only from portions that are not filled with
the surface bed, which would ultimately be decomposed by mi- water and experience a slight pressure drop. Channelization of
croorganisms naturally supplied on the beds. Microorganisms airflow would decrease the retention time of air in the biofilter,
require organic nutrients such as phosphorus, nitrogen, calcium, thus rendering certain parts inactive. When the airflow declines on
potassium, sodium, and manganese in order to grow, which are the water-filled parts, an anaerobic condition is dominant, leading
naturally provided in the biofilter, through compost, soil, etc. to odor production. A biofilter can be established by spreading the
200 A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206

Fig. 8. Suspended growth reactor containing phototrophic microorganisms.

odorous gas on less than 1e3 m depth of compost or soil layer issues.
(Fig. 7).
As mentioned in previous sections, a smell is a mixture of many
10.1.3. Biotrickling filter
odorous compounds. In some cases, removing hydrogen sulfide
Synthetic beds are used in order to fill the void in biotrickling
would not completely eliminate the odor. Thus, the removal of
filters and establish a broad surface for bacterial growth. Although
volatile organic compounds or mercaptans should also be under-
these beds lack the nutrients and bacteria to operate the bio-
taken. Elimination of acidic contaminants like hydrogen sulfide is
trickling filter, they establish a much broader range than the
followed by accumulation of sulfuric acid, which causes acidic pH.
components of a natural bed, such as compost or soil. In order to
The removal capability of microorganisms for the elimination of
provide the microorganisms with the required water and nutrients,
other contaminants plummets, except for hydrogen sulfide.
a solution of chemical compounds containing substances such as
Hydrogen sulfideeremoving microorganisms can easily resist
phosphorus, nitrogen, calcium, potassium, sodium, and iron is
acidic environments with pH of 1 or less while others require
circulated around the bed by a pump (Fulazzaki et al., 2013a, 2013b,
neutral pH. The only way to control pH in biofilters is by replacing
2014). This explains why even in high debits of contaminated air,
the bed. Continuous replacement of the bed to control pH would
the possibility of drying out and evaporation is nonexistent.
increase the removal efficiency of other contaminants, but limits
Furthermore, since the pH of the bed is easily adjustable by altering
the removal of hydrogen sulfide. The pH of the environment can
the pH of the circulating nutrient solution, the elimination of
increase up to a level of 2 pH, which is not optimal for the removal
hydrogen sulfide produces no sulfuric acid on the microbial layer,
of other contaminants (Fulazzaky et al., 2014). This is one of the
so removal efficiency would easily be maintained. The absence of
weaknesses of biofilters. Some researchers address this issue by
microorganisms on the initial bed provides the possibility of
serial use of scrubbers and biofilters in which hydrogen sulfide is
breeding special microorganism strains on the bed (Ramíreza et al.,
first removed by the scrubbers, and biofilters are used to eliminate
2009). Wani et al. (1999) and Ma et al. (2006) reported that active
other contaminants. In various research studies, bioscrubber tech-
carbon can be utilized as the bed in a biotrickling filter. Active
nologies were developed to address the issue of constant biofilter
carbon can easily absorb a wide range of contaminants, such as
bed replacement to adjust steering parameters such as pH (Gabriel
carbon dioxide, hydrogen sulfide, and mercaptans. The adsorbed
and Deshusses, 2003b).
contaminants are also immediately consumed by microorganisms,
so there is no need to replace or reactivate the active carbon. Other
10.1.2. Bioscrubbers beds, such as plastic beds, volcanic beds, and ceramic beds have
Bioscrubbers are scrubber devices that facilitate the trans- been successfully applied in various studies (Fulazzaky et al., 2014a;
ference of contaminants from gas phase into the liquid phase by Ma et al., 2006). In a study conducted by Kennes and Veiga (2013),
establishing contact between the solvent (usually water) and the the ratio of mass transfer from gas phase into the liquid phase in
contaminated air. In this method, the contaminant is effectively biotrickling filter depends on the flow rate of both the nutrient
transformed from gas phase; however, further treatment is solution and the contaminated air. They believe that the appro-
required while in liquid phase. Thus, by incorporating biological priate range of volumetric flow rate of gas to liquid (G/L) is between
methods with scrubbers, the treatment of the liquid phase is 100 and 300. High G/L rates are associated with low retention times
handled in a separate system, which increases the initial costs of and vice versa. High retention times above 1 min are needed in
establishing such air treatment systems. Bioscrubbers also possess certain circumstances where contaminants are resistant to the
low capacity for treatment in the removal of poorly soluble con- biological degradation or are poorly soluble in water. Kennes and
taminants, such as hydrogen sulfide (Fulazzaky et al., 2014). How- Veiga demonstrated (2013) that for hydrophobic compounds, a
ever, adding chemical compounds such as sodium hydroxide or relatively low liquid flow rates results in higher removal efficiency.
lime water to the circulating liquid provides higher removal rates For example, carbon monoxide and carbon dioxide are better
for compounds such as hydrogen sulfide. Since these compounds treated in biofilters (which are fluid in the liquid phase) and bio-
would cause great interference with biological treatment of the trickling filters are the appropriate choice with low nutrient liquid
liquid phase, biotrickling filters are recommended to address these circulation rate (Kennes and Viega, 2013). It should be noted that
A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206 201

Fig. 9. Schematic of different methods for treatment of contaminated air including (a) biofilter; (b) biotrickling filter reactor; (c) suspended growth reactor, and (d) bioscrubber
(Fulazaky et al., 2014).

the impact of flow rates is relatively variable depending on various the gas phase (contaminated air) into the liquid phase (water
factors such as the properties of contaminants and the bed type. containing suspended microorganisms). In the liquid phase, sus-
However, the effect of the G/L ratio of remains controversial. pended microorganisms can absorb and decompose the contami-
nants (Fulazzaky et al., 2014). It should be noted that hydrogen
10.1.4. Suspended growth reactors sulfide can act as an energy source for microorganisms, so the
Studies conducted on finding a method providing simultaneous carbon sources can be provided by compounds such as glucose,
treatment of air and wastewater led to the introduction of sus- methanol or untreated domestic sewage. Solubility of hydrogen
pended growth reactors. In this type of bioreactor, air is released by sulfide in water with pH of 7 and temperature of 19  C is 4 g/l
diffusers into the depth of the reactor, which contains a high con- (www.engineeringtoolbox.com, 2014). Considering the average
centration of suspended microorganisms in the form of small solubility of hydrogen sulfide in water, suspended growth reactors
bubbles. These small bubbles provide a broad surface for the ex- are recommended in treatment of this contaminant. One limitation
change of contaminants (such as hydrogen sulfide) between gas for these reactors in removing hydrogen sulfide is the time the
and liquid phases. Contaminants in trapped air would transfer from injected air is retained. Suspended growth reactors are considered

Fig. 10. Schematic of membrane bioreactor operation for removal of odorous compounds from air.
202 A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206

displays the various biological air treatment methods. Although


biological methods are highly effective in odor elimination, there
are several reports of failure in eliminating some odor-causing
compounds such as benzothiazole. Benzothiazole can be naturally
produced in surface waters and odorizes the water. In addition,
benzothiazole can be released in surface water through industrial
wastes (Andreozzi et al., 2001).

10.1.5. Membrane bioreactors


A membrane bioreactor is a chamber divided into two parts by a
membrane. The contaminated air is injected and passed through
the membrane. While air can easily pass through the membrane,
odorous compounds cannot. Therefore, these compounds would
remain in one side of the chamber, which would be consumed by
microorganisms. A presentation of a membrane bioreactor is pro-
vided in Fig. 10.
Fig. 11. Schematic of a scrubber.

10.2. Application of scrubbers in elimination of hydrogen sulfide


Table 3 and other odorous compounds
Samples for removal efficiency of odorous compounds by using chemical scrubbers
containing sodium hypochlorite.
Scrubbers or gas scrubber towers can be employed in hydrogen
Gases Removal efficiency (%) sulfide elimination from a gas stream. Among all physical-chemical
Hydrogen sulfide 98 methods for air pollution control, scrubbers are basically one of the
Ammonia 98 most appropriate instruments to collect both gaseous pollutant and
Carbon dioxide 95 particular matter from an air stream simultaneously (Talaie et al.,
Mercaptan 90
Other oxidizable odorous compounds 70e90
2009). Scrubbers can also be used to cool hot gases (Fig. 11).
Although scrubbers possess suitable removal efficiency, the sig-
nificant amounts of liquid waste are produced, requiring further
treatment. In scrubbers, the contaminated air and the solvent
to be the same as the tanks used in the aeration of activated sludge (typically water) are come into contact. Plastic packing are some-
systems. Therefore, hydrogen sulfide contaminated air can be times used in scrubbers to increase the contact area. While main-
replaced by air and injected into the tank as the oxygen source for taining the contact between the gas and liquid, the contaminants
bacteria. Photosynthetic bacteria such as Chlorobium can be used in would transfer from the gas phase to the liquid phase, which tends
hydrogen sulfide elimination in the presence of light (Poramini to producing pollution-free air.
et al., 2006). These bacteria in suspended growth reactors can be To increase the solubility of poorly soluble contaminants, certain
used to demonstrate suspended growth reactors containing pho- chemical compounds (chemical scrubbers) can be utilized. Using
totrophs aerobic bacteria or photosynthetic bioreactor (Fig. 8). Note alkaline materials can increase the removal efficiency for some
that the phototrophic bacteria supply their energy from sunlight. contaminants. Revisions made in the chemical scrubbers have
Membrane bioreactors are another air treatment method that increased the removal efficiency of hydrogen sulfide and other
demonstrates a capacity to eliminate hydrogen sulfide. Fig. 9 odor-causing compounds. Various types of scrubbers include the

Fig. 12. Schematic of a Venturi scrubber.


A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206 203

Table 4
Advantages and disadvantages of various methods for air treatment.

Technology Advantages Disadvantages Sources

Adsorption High odor removal efficiency; Short life span; air humidity and small molecule size; Goli et al., 2014;
by active carbon simplicity of mechanism high reduction costs; efficient only in small Morales et al., 2008;
concentrations of contaminant Kaye and Jiang, 2000
Utilized to Low costs; appropriate to overshadow Method does not lead to decomposition or elimination of Iranpour et al., 2005;
overlaying alternative odors odorous compounds; although unpleasant smells are Zarra et al., 2008
odors covered, odor concentration rises overtime; neglects
volatile organic matter
harmful for human health; inability to control air pollutants
Heat oxidation High efficiency; capable of removing a wide High energy requirements and expenses; economically Kaye and Jiang, 2000
range of gaseous pollutants efficient only for incompliant compound; causes the
production of alternative pollutants such as CO2
Chemical scrubber Simple; effective; efficient; reliable; proper utilization; More expensive than biological treatment; secondary Kaye and Jiang, 2000
low maintenance costs treatment of leftover sludge Revah and
Morgan-Sagastume, 2005
Bioscrubber Stability of operation; proper biological parameters Low efficiency in case of poorly soluble substances; Stuetz et al., 2001;
control, including pH, temperature, nutrients, etc.; high treatment efficiency is reduced by special Easter et al., 2008
pressure drop; harmful environmental compounds contact area of gas/liquid
are easily eliminated; avoids inhibitory effects
Suspended growth Utilization of available equipment (lower costs); easy Complex steering by experts; tower efficiency due Kaye and Jiang, 2000
reactor operation; higher management capability for larger to the limits of gaseliquid transference; possibility
loadings; simultaneous treatment of air and wastewater of corrosion in equipment
Biofilter Simple and flexible design; appropriate for poorly Pilot design requires additional studies; higher retention Kaye and Jiang, 2000;
soluble compounds with Henry coefficient of less times due to the limits of gas/liquid transference; high Stuetz et al., 2001
than 1 (in absence of dynamic phase); lower costs. volumes of reactors is needed; inability to eliminate acidic
gasses like hydrogen sulfide; possibility of accumulation of
additional biomass which increases the pressure drop;
establishment of aerobic regions and odor production.
Biotrickling filter Easy control of operation parameters including: pH, Solubility limits for VOCs; only effective where Henry Kaye and Jiang, 2000
reactor nutrients, etc.; easy removal of by-products; capability coefficient is less than 0.1; possibility of accumulation of Stuetz et al., 2001;
to remove acidic gasses; higher control over the additional biomass which increases the pressure drop; Easter et al., 2008
biofilm growth; less bed congestion Establishment of aerobic regions and odor production;
high operational costs, especially in spinning types

counter-current scrubber, cross-flow scrubber, and venturi (vi) the ability to remove particles and gases simultaneously. All of
scrubber. The main objective in all scrubber types is to provide these factors have contributed to the popularity of Venturi scrub-
maximum contact surface among air, water, and chemical sub- bers (Fig. 12).
stances to oxidize or absorb contaminants. Fluids used as oxidants In general, Venturi scrubbers can be distinguished from other
are chlorine solution (especially sodium hypochlorite) and potas- biological methods such as biofilters:
sium permanganate. In systems that are designed for high con-
centrations of hydrogen sulfide, sodium hydroxide is also used. i. Venturi scrubbers can treat larger volumes of air in com-
Typical rates of odorous substances removal by scrubbers con- parison with biofilters. To achieve the highest possible
taining sodium hypochlorite are presented in Table 3. removal efficiency by a biofilter, retention of time of 15e150 s
In cases where the scrubber outlet gas cannot properly deo- is considered based on the bed type. Therefore, under the
dorized, a multi-stage scrubber is often used. Designing a scrubber best circumstances, a biofilter with a volume of 1 m3 is
system includes: (i) determining the characteristics and volume of capable of treating only 250 m3/hr (Fulazzaky et al., 2014). On
the gas applied for treatment; (ii) defining necessary conditions for the other hand, a Venturi scrubber with a volume of only
the exhaust gas from the scrubber; (iii) selection of scrubber liquid 0.0078 m3 is capable of treating 1000 m3/hr.
based on the chemical nature and concentration of the malodorous ii. Like other biological treatment devices, biofilters require
substance; and (iv) pilot scale tests to determine design criteria and long periods of time to achieve maximum efficiency after
system performance. Venturi scrubbers possess high particle and starting up, since the microbial layer must reach a desirable
gas removal efficiency (Talaie et al., 2009; Fathikalajahi, et at., 1996; thickness. The smallest environmental shocks can decrease
Talaie et al., 1997). In this system, the transformation from liquid the removal efficiency, which takes time to recover. Thus far,
solvent into small droplets provides a high absorption surface area. a biological treatment system requires extensive specialized
After transferring pollutants from the gas phase to the liquid phase maintenance. On the other hand, Venturi scrubbers quickly
(solvent droplets), the treated air contains a large number of reach their maximum efficiency and require little
droplets containing contaminants. In order to separate these maintenance.
droplets, a cyclone can be used as shown in Fig. 12. As opposed to iii. Hydrogen sulfide removal in a biofilter requires a liquid
conventional scrubbers, this system possesses higher removal ef- phase to be established on the biofilm. This is handled by
ficiency, especially in large volume of polluted air. For the ventila- pumping water from the reservoir onto the bed. Biofilm is a
tion of wastewater networks, Venturi scrubbers can be a highly biomass requiring all of the macro nutrients (calcium, mag-
cost-efficient candidate. In many industries, the application of nesium, sodium, nitrogen, phosphorus, etc.) as well as the
Venturi scrubbers to treat contaminated gases has become very micro nutrients (vanadium, cobalt, zinc, copper, etc.) for
popular, due to (i) their simplicity of construction, (ii) ease of use, growth. These are not efficiently supplied in drinking water.
(iii) low operational difficulties, (iv) very high efficiency in In order to address this deficiency, these supplies must be
removing contaminants, (v) the ability to purify large volume of air added to water manually, which would increase operating
in a short time considering the small size of the device, as well as expenses. One can also use waste liquid instead of fresh
204 A. Talaiekhozani et al. / Journal of Environmental Management 170 (2016) 186e206

water to feed the biofilter. In addition, the presence of sub- digital measurement devices can provide direct hydrogen sulfide
stances such as lactate and pyruvate causes Reaction (28), measurement directly from air. UV spectrophotometry is the
which would convert the accumulated sulfuric acid back into proper method in measuring hydrogen sulfide. Hydrogen sulfide
hydrogen sulfide. strongly absorbs ultraviolet wavelengths. A wavelength of 228 nm
is proposed to avoid any interference from other compounds, such
4CH4  CO  COOH þ H2 SO4 /4CH4  COOH þ 4CO2 þ H2 S as hydrocarbons (Lenior, 2009). The UV wavelengths absorbed by
(28) hydrogen sulfide are very low; therefore, in low hydrogen sulfide
concentrations (0e5 ppm) ultraviolet spectrophotometry cannot
The end result of this reaction is that the absorption rate of
be applied. In this case, the hydrogen sulfide contaminated air is
hydrogen sulfide on the biofilm would decline, leading to a dra-
blown into a solution containing water and ammonia, which would
matic fall in removal efficiency. In Venturi scrubbers, alkaline
produce ammonium sulfide. Ammonium sulfide acts much more
substances such as limewater can convert sulfur into calcium sul-
strongly than hydrogen sulfide in absorbing UV wavelengths.
fide and inhibit the reproduction of hydrogen sulfide.
Therefore, despite the low concentration, it can be easily measured
at a wavelength of 228 nm. Other measurement methods include X-
iv. As shown in Table 1, the smell threshold for most odor-
Ray spectroscopy, tunable diode laser absorption spectroscopy, and
causing substances is very low. In other words, these sub-
diode array spectroscopy (Lenior, 2009).
stances have a recognizable smell in small concentrations.
Removal efficiency of the scrubbers would focus on low
concentrations of odorous substances, in which case, the 13. Conclusion
biological methods would operate with higher efficiencies.
This manuscript discussed the causes of odor production and its
11. A comparison of hydrogen sulfide removal methods emission into the atmosphere in wastewater collection and treat-
ment facilities. In addition, the manuscript introduced several
In comparison with other biofiltration processes, biotrickling methods to prevent or control odorous compound emissions with
filters are considered an optimum option in elimination of con- emphasize on hydrogen sulfide. In general, the emissions control
taminants with average solubility in water. They are mainly sug- strategies of odor-causing compounds, especially hydrogen sulfide,
gested for contaminants in which the Henry coefficient is less than include: (i) prevention of hydrogen sulfide production, and (ii)
0.1. On the other hand, popular biofilters can be applied to most elimination of produced hydrogen sulfide. The strategic priority is
hydrophobic substances with a Henry coefficient greater than 1. prevention of hydrogen sulfide production. Prevention of sulfur-
Other biofiltration processes such as bioscrubbers and suspended reducing bacteria growth is accomplished by adding electron do-
growth reactors are suitable only for highly water soluble sub- nors such as nitrite and nitrate or by adding germicides or
stances with Henry coefficient of less than 0.01 (Kennes and Viega, increasing wastewater pH. These are the most important methods
2013). Several studies have been conducted on the removal of to prevent hydrogen sulfide production. There are also many
volatile organic substances with a variety of different biofiltration methods to eliminate produced odor-causing compounds, such as
methods (Aldy et al., 2003; Stern, 2007; Mohajan, 2011). It is worth combustion in high temperatures; catalytic combustion; adsorp-
mentioning that the Henry coefficient of hydrogen sulfide is 0.098, tion, and biological decomposition of odor-causing compounds in
and several studies have demonstrated the applicability of most wastewater and surrounding air. Some novel approaches for pre-
treatment method, including biofilters. The advantages and dis- vention of hydrogen sulfide have been developed by the oil and gas
advantages of various air treatment methods are compared in industries, such as application of fuel cells or gradual release of
Table 4. It should be noted that the Henry's law is one of the gas oxygen in gas phase by using MgO2 or CaO2 which have never
laws formulated by William Henry in 1803. It states, “At a constant before been used for removal of odor in wastewater collection and
temperature, the amount of a given gas that dissolves in a given treatment facilities. The present study is a complete review on
type and volume of liquid is directly proportional to the partial different aspects of odor control strategies, useful for all persons or
pressure of that gas in equilibrium with that liquid.” Henry's companies that collect and treat water and wastewater.
equation is written as p ¼ kHc, where p is the partial pressure of the
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