TREATMENT OF HYDROGEN SULFIDE

GAS GENERATED IN LANDFILL SITES

T. TAKESHITA*, S. HIGUCHI* AND M. HANASHIMA**

* Graduate School of Engineering, Fukuoka University

Koyomachi 10, Wakamatsu, Kitakyushu, Fukuoka, 808-0002, Japan
** Fukuoka Research Center for Recycling Systems
Hibikino 2-1, Wakamatsu, Kitakyushu, Fukuoka, 808-0135, Japan

SUMMARY: In order to tackle the problem of hydrogen sulfide, H2S, generation occurred in the
landfill sites where industrial waste was discarded, the use of oxidizing agents such as hydrogen
peroxide, H2O2, and bleaching powder was examined. Experiments for the degradation of
gaseous H2S were carried out in a 300 ml conical flask filled with H2S gas that was supplied
from H2S containing leachate. We concluded that the H2S gas could be effectively degraded by
the treatment of H2O2 or bleaching powder when appropriate amount of these chemicals were
exerted. Next, in order to find out the causal organic substances refer to the generation of H2S,
we selected the ingredients used in the materials that were discarded in the landfill sites. When
10 mg of the identified organic material that belongs to admixture for cement or mortar,
plasticizer and monomer for plastics and crude rubber was added in a conical flask containing
200 ml leachate and kept in an incubator at 35C, the generation of H2S in high concentration
was observed.

1. INTRODUCTION

The term of inert type landfill site stands for the landfill site where chemically and biologically
stable industrial waste materials such as concrete fragments, plastic waste, rubber waste, scrap
metal, glass and pottery waste are discarded in Japan. But recently, this type of landfill sites is
suffering from the problem of unexpected hydrogen sulfide, H2S, generation. The generated H2S
gas caused fatal accidents in the facilities of landfill site and gave the surrounding dwellers for
malodor problem. However, little information on the effective methods for dealing with this
problem has been well prevailed. Hence the development of technologies for controlling and the
identification of the causal substances for contributing the H2S gas generation in landfill sites are
urgently awaited.
On the other hand, the reaction of H2S and heavy metals produces sulfides that are usually
insoluble in water and form sediment. From this point of view, H2S plays an important role in
contributing to the stabilization of discarded waste in the landfill site. On H2S generation in the
landfill site, the sulfur reducing bacteria must metabolize some kinds of organic substances

Proceedings Sardinia 2003, Ninth International Waste Management and Landfill Symposium
S. Margherita di Pula, Cagliari, Italy; 6 - 10 October 2003
2003 by CISA, Environmental Sanitary Engineering Centre, Italy
found in discarded waste as carbon and energy sources and finally produce H2S gas by reducing
SO42-. But the organic substances feeding to the bacteria are hardly identified.
In this study, one of the objectives was to develop the method for controlling the generation
of H2S gas in the landfill site. In order to achieve this, the use of oxidizing agents such as H2O2
and bleaching powder, its principal ingredient was calcium hypochlorite, was proposed. This
method targeted the selective oxidation of H2S with the highly reactive radicals when the agents
were applied. Another objective was to elucidate the substances contributing to the generation of
H2S in landfill sites. On these five types of wastes as mentioned above, the ingredients that were
used in the materials were selected. Then the H2S gas generation was examined on the mixture of
leachate containing sulfuric ions plus selected chemical substances under anaerobic culture
condition.

2. EXPERIMENTAL METHODS AND ANALYSES

2.1 Experiment for the degradation of H2S

The following samples and equipment were used throughout the experiments. Leachate sample
containing H2S gas was obtained from an open-air landfill simulation facility (top;
10m(W)10m(D), bottom; 5m(W)5m(D), height; 2.5m) installed in our laboratory. Experiment
was conducted in a 300 ml conical flask containing 200ml of the leachate. Prior to the operation,
the headspace gas in the flask was replaced with purified nitrogen gas and sealed with a gastight
silicon rubber stopper. Prepared flask was statically stored in an incubator which temperature
was kept at 35C. When the temperature of the sample was achieved, an oxidizing agent and/or a
liquid solution containing metallic element were added. After this, the headspace gas in the flask
was taken off with a gastight syringe to analyze H2S concentration.

2.2 Identification of the substances that causes the generation of H2S

Almost the same experimental apparatus was used for the H2S generation experiment. But
aerated sample leachate was used in order to remove H2S. Two hundred milliliters of the leachate
was pored in a 300ml flask into which 10mg of an identified organic compound was added. After
nitrogen substitution, the flask was sealed with a silicon plug and stored at 35C without
agitation. After this, the headspace gas was sampled periodically and the concentration of H2S in
the headspace was measured. About 30 organic chemicals were selected as the substrate and
subjected to the test for H2S generation.

2.3 Analyses
In the analysis of H2S concentration, a packed glass column (column length 3 meters, liquid
phase: 1.2.3- 1 cis- (2-cyanoethoxy) propane 25%, support Chromosorb W 60/80 mesh, column
temperature 70 C isotherm) was attached to a gas chromatograph (G6800 with FPD). Moreover,
in order to confirm the generation of halogenated organic compounds, a wide bore capillary
column (length 25 m, fixed phase: 100% methyl silicone, membrane thickness: 1m, I.D. 530m
column, temperature constant at 50 C) was attached to a gas chromatograph (G2800, ECD).
3. CHEMICAL OXIDATION PROCESSES

3.1 Degradation of H2S by H2O2

The use of H2O2 for the degradation of H2S is first examined. In this treatment H2S can be
selectively oxidized with H2O2 and form sulfur (S) according to the reaction (1) because H2S is a
well-known reducing reagent.
H2S + H2O2 S + 2H2O (1)
However, excess amount of H2O2 is subjected to the degradation reaction, the generated sulfur is
further oxidized by H2O2 to form sulfuric acid as reaction (2) or self decomposition of H2O2 is
taken place to form oxygen gas as reaction (3).
S + 3H2O2 H2SO4 + 2H2O (2)
2H2O2 2H2O + O 2 (3)
When H2O2 is coexisted with ferrous ions, highly reactive hydroxyl radical (OH ) can be
generated as depicted in reaction (4). So the catalytic effect of the addition of ferrous may be
promoted the effect on H2S degradation. This estimation is based on the well-known Harbor-
Weiss/Fenton reaction (4).
H2O2 + Fe(II) OH + OH- + Fe(III) (4)
Commercially available hydrogen peroxide solution which concentration was certified up to 31%
(W/W) was used for this experiment.

3.2 Degradation of H2S by bleaching powder

The use of bleaching powder is next investigated to degrade H2S. When the calcium
hypochlorite, Ca(ClO)2, contained bleaching powder is dissolved in water, highly reactive
oxygen called oxygen radical (O ) is generated as shown in reactions (5) and (6).
Ca(ClO)2 Ca2+ + 2ClO- (5)
2ClO- 2Cl- + 2O (6)
The generated oxygen radical is then selectively reacted with H2S and produces sulfur or further
oxidized sulfuric ion (SO4 2-) as shown in reactions (7) and (8).
H2S + O H2O + S (7)
4O + S SO42- (8)
Here, the sulfuric ion generated in reaction (8) makes insoluble calcium sulfate as shown in
reaction (9).
Ca2+ + SO42- CaSO4 (9)
Finally, the whole reaction of H2S degradation by bleaching powder is summarized as reaction
(10)
2Ca(ClO)2 + H2S CaCl2 + CaSO4 + 2HCl (10)
Commercially available bleaching powder whose chlorine content was certified up to 60 % was
used in this experiment. As the reagent was in pellet form, the grains were grounded into powder
before use.
 4. RESULTS

4.1. Experiments for the degradation of H2S by oxidizing agents

4.1.1 Degradation of H2S by H2O2

The use of hydrogen peroxide, H2O2, for the degradation of hydrogen sulfide, H2S, was first
examined. Figure 1 shows the degradation profiles of H2S in headspace gas by exerting different
amount of 31%(W/W) H2O2 solution. When 0.2 ml of H2O2 was added into the 300 ml flask
containing 200 ml of H2S dissolved leachate, the concentration of H2S in the headspace
decreased to undetectable level in 17 min. Moreover, when the amount of H2O2 was changed to
5-fold (1.0 ml) and 1/5-fold (0.04 ml) of 0.2 ml, the disappearance time required for the
degradation of H2S in the headspace took about 10 min. and 65 min., respectively.

4.1.2 Effect of the addition of metal solution on the degradation of H2S byH2O2
In order to improve the degradation of H2S, the effect of the addition of metal solution on the
degradation of H2S by H2O2 was next investigated. Four metallic elements such as Cu, Fe, Mn
and Zn were selected and the solutions containing 1.0g/l of each metallic element were prepared
by dissolving the salts (CuSO4 5H2O, FeSO4 7H20, MnSO4 5H2O and ZnSO4 7H2O) into ion-
exchanged water. After 0.2 ml of 31%H2O2 and 0.2 ml of the metal solution were simultaneously
added into the flask containing 200 ml of H2S dissolved leachate, the concentration of H2S in the
headspace was measured. As shown in Figure 2, the most effective element tested in this
experiment was Fe and the time for H2S degradation was shorten by 10 min. at least as compared
to the result obtained without use the Fe solution.
200 200

H2 S
ppm j

ppm j

H2 S
Concentr 150 Concen 150
ation Control
i

Cont rol
i

tration
(ppm) Control (ppm)
Control 00
H 2 S concentration

H 2 S concentration

l
40
40 l Cu 200
Cu200 l
100 100
Fe 200
Fe200 l
200
200 l
Mn 200
M n200 l
1000
1000 l
50 50 Zn 200
Zn200 l

0 0
0 20 40 60 80 0 5 10 15 20
Tim e @
(m in) Tim e(min)
Time @
m in
Time (min)

Fig.1 Degradation profiles of hydrogen Fig. 2 2.

Figure Degradation
Degradationprofiles of of H S
profiles
Figure 1. Degradation
sulfide in the headspaceprofile of H2S in the
gas by exerting hydrogen sulfide in the headspace 2
headspace gas by exerting
hydrogen peroxide. H O
2 2 . ingas
thebyheadspace gas by exerting
exerting hydrogen H2O2
peroxide
and
andaametal
metalsolution
solutionsimultaneously.
simultaneously.

4.1.3 Effect of the addition of Fe solution on the Degradation of H2S by H2O2

The degradation of H2S in the headspace gas by exerting 0.2 ml of 31%H2O2 and various
amounts of the Fe solution was examined. As shown in Fig. 3, the time needed for H2S
degradation was shortened with increasing the addition of the Fe solution. But only Fe solution
was exerted, the degradation of H2S gas did not take place effectively. In this experiment Fe
 played a key role as catalyst and promoted the formation of hydroxyl radicals from H2O2.

4.1.4 Degradation of H2S by bleaching powder

Figure 4 shows the degradation profiles of H2S by exerting 4 to 100 mg of bleaching powder.
When 20 mg of bleaching powder was added, the concentration of the H2S in the headspace gas
was decreased to 51.3% of the initial concentration in 1 min. and disappeared in 4 min.
Moreover, when 100 mg of bleaching powder was added, the concentration of the H2S decreased
to 13.5% of the initial concentration in 1 min. and disappeared in 4 min. On the other hand, the
amount of bleaching powder was reduced to 10 or 4mg, the times needed to decrease the H2S
concentration in the headspace gas to undetectable level were 61 and 194 min., respectively.

4.1.5 Formation of chlorinated organic compounds as byproducts from the degradation of H2S
by using bleaching powder
The formation of chlorinated organic compounds in the treatment of H2S by bleaching powder
was examined. When the samples were treated with 20 mg or without bleaching powder, a single
peak was detected by GC-ECD. On the other hand, when the samples were treated with 100 mg
of bleaching powder, several peaks were detected. These peaks were believed to be volatile
chlorinated organic compounds produced by the reaction of excess calcium hypochlorite and
organic substances in the leachate. Identification of these chemicals is continued.

4.2. Experiments for identification of materials that cause generation of H2S

200
200

H2 S
ppm j
ppm j

H2 S
Concent Conce
150
ration ntrati 150
i

(ppm) on
Control 100m g
H 2 S concentration

H 2 S concentration

(ppm) 20mg
Fe0
100 10m g
Fe100
l 100
4m g
Fe200
l 0m g
50 Fe2000
l
50

0
0
0 5 10 15 20
0 50 100 150 200
TimeTime @
(min) m in
TimeTim e (m in)
(min)

FigureFig.
3. 3Degradation
Degradation profiles of hydrogen
profiles of H2S in Figure
Fig.44.Degradation
Degradation profiles
profiles ofof
sulfide in the headspace gas exerting
the headspade gas exerting
hydrogen peroxide H2O2ferrous
under different under H2S inhydrogen sulfide
the headspace gasinexerting
the
different ferrous concentration.
concentrations. headspace
bleaching powder. gas exerting
bl hi d
 100000

10000
H 2S concentration

1000

100

10

1
0 10 20 30 40 50
Tim e (day)

Figure 5 Generation of hydrogen sulfide gas

applying the identified organic additives to the
leachate and incubated at 35 C. (Symbols are as
follows; sodium carboxymethylcellulose (CMC)
xylose dibuthyl phthalate arabic gum powder
soluble starch sodium gluconate vinyl
acetate monomer.

Five types of waste materials that are brought to the inert type landfill sites are: concrete
fragments of constructions, waste plastic; waste rubber, waste metals and waste glass and
ceramics. Of the waste materials, the ingredients provably used in manufactures were purchased
as commercially available reagents and were subjected to the experiment for H2S generation.
Figure 5 shows the time course of H2S generated in the flask when the identified chemicals were
supplied to the leachate and the flask was kept in an incubator controlled at 35C under
anaerobic condition. The amount of each organic compound added was 10 mg. The H2S gas
generation was observed on all the chemicals listed in the legend of Fig.5 within 10 days and
about 10,000 ppm of H2S was produced by sodium gluconate and vinyl acetate monomer in
particular. These organic materials that H2S generation was observed were chemical admixture
for cement or mortar, plasticizer and monomer for plastics and crude rubber, etc.

5. DISCUSSION

As shown in the results, H2S gas could be immediately degraded by the use of oxidizing agents
such as H2O2 or bleaching powder. The same effect would be expected by the use of relating
oxidizing agents such as sodium percarbonate and ozone. The following effects were also
considered in this treatment; namely the level of the dissolved oxygen concentration in the
leachate was increased, the dissolved oxygen was gradually degraded dissolved H2S, and the
growth of the sulfur reducing bacteria was inhibited or ceased by using the oxidizing agents.
Also, the organic compounds that fed to the sulfur reducing bacteria were oxidized and degraded
by the oxidizing agents or the growth of aerobic bacteria.
The use of H2O2 with Fe solution could promote the effect of H2S degradation. On this
reaction, Harber-Weiss/Fenton reaction is known in the catalytic reaction of H2O2. But the
concentration of Fe2+ was very low in the H2S dissolved leachate because Fe2+ and H2S formed
insoluble sediment of FeS. Hence the use of Fe solution with H2O2 was needed for the effective
degradation of H2S.
In order to find out the chemical compounds that contribute to the H2S generation in landfill
sites, the ingredients in the waste material were next investigated The generation of H2S was
confirmed on the chemical substances as depicted in the legend of Fig. 5., but many other
substances were never identified. Moreover, the debris of photosynthetic or heterotrophic
bacteria could also feed nutrition to the sulfur reducing bacteria when the water in the landfill
sites was stagnated.
Hydrogen peroxide and bleaching powder are commercially available everywhere in Japan as
chemical products. Due to the convenience, we considered that the use of these chemicals would
be a practical method for controlling H2S in landfill sites. Further investigations on the H2S
control in landfill site have been continued.

6. CONCLUSIONS

The following facts were ascertained in this study.

The use of oxidizing agents such as hydrogen peroxide and bleaching powder was the
promising technique for the degradation of hydrogen sulfide.
The organic compounds depicted in the legend of Fig. 5 would contribute to the H2S
generation in landfill site when these compounds were supplied to the leachate under anaerobic
condition.