Effect of Temperature on Air-Water Transfer of

Hydrogen Sulfide
Chaturong Yongsiri, S.M.ASCE1; Jes Vollertsen2; and Thorkild Hvitved-Jacobsen3

Abstract: The extent of hydrogen sulfide transfer across the air-water interface plays a major role for odor and corrosion problems in
sewer networks. One significant physical factor affecting the air-water transfer process is temperature. This study describes the tempera-
ture dependence of air-water transfer of hydrogen sulfide in terms of a temperature correction factor 共temperature coefficient兲. The
air-water transfer rate was found to increase with increasing temperature at a constant turbulence level. A mathematical expression for the
transfer rate versus temperature was addressed following the Arrhenius equation. The temperature coefficient for air-water transfer of
hydrogen sulfide was observed under acidic and neutral conditions 共pH 4.5, 6.5, and 7.0兲, i.e., under conditions where only the molecular
form of hydrogen sulfide was present 共pH 4.5兲 and under conditions where both the molecular form and the ionized form existed 共pH 6.5
and 7.0兲. The effect of temperature on air-water transfer of hydrogen sulfide decreased with increasing pH. The temperature coefficients
found in this study were within the range reported in the literature for other substances transferring across the air-water interface such as
oxygen, ozone, and krypton-85.
DOI: 10.1061/共ASCE兲0733-9372共2004兲130:1共104兲
CE Database subject headings: Hydrogen sulfide; Sewers; Temperature effects; Air-water interactions; Hydraulic networks.

Introduction such adverse consequences is associated with sulfide formation

Transfer of substances across the air-water interface is of environ-
mental concern in a number of cases. Important examples are
release of odors, emission of substances that affect human health
and cause corrosion, and in case of reaeration and aeration. Pre-
diction of air-water transfer of transferable substances is, there-
fore, important and should be taken into consideration together
with sources and sinks for such substances that exist in both the
water phase and the air phase. Numerous studies have focused on
the transfer of oxygen (O2 ), resulting in a better understanding of
the reaeration process for self-purification in receiving waters or
sewer networks as well as the aeration process in wastewater
treatment plants. Another vital study refers to the exchange of
carbon dioxide (CO2 ) between the ocean and the atmosphere as a
central component for global climate dynamics. Other transfer-
able substances that are usually absent in the atmosphere—e.g.,
hydrogen sulfide (H2 S), ammonia (NH3 ), and volatile organic
compounds 共VOCs兲—also gain more attention because of their
adverse consequences to the environment. An obvious case of
1 temperature on the H2 S-transfer process has, however, not been
PhD Student, Dept. of Environmental Engineering, Aalborg Univ.,
Sohngaardsholmsvej 57, DK-9000 Aalborg, Denmark. E-mail:
cy@bio.auc.dk
2
Associate Professor, Dept. of Environmental Engineering, Aalborg
Univ., Sohngaardsholmsvej 57, DK-9000 Aalborg, Denmark. E-mail:
jv@bio.auc.dk
3
Professor, Dept. of Environmental Engineering, Aalborg Univ.,
Sohngaardsholmsvej 57, DK-9000 Aalborg, Denmark. E-mail:
thj@bio.auc.dk
Note. Associate Editor: George A. Sorial. Discussion open until June
1, 2004. Separate discussions must be submitted for individual papers. To
extend the closing date by one month, a written request must be filed with
the ASCE Managing Editor. The manuscript for this technical note was
submitted for review and possible publication on May 22, 2002; approved
on February 20, 2003. This technical note is part of the Journal of En-
vironmental Engineering, Vol. 130, No. 1, January 1, 2004. ©ASCE,
ISSN 0733-9372/2004/1-104 –109/$18.00.
and its subsequent emission in sewer networks, leading to odor,
health, and corrosion problems. In addition to the sources and
sinks that determine the total level of concentrations for sulfide,
the H2 S/HS⫺ equilibrium 共dissociation兲 and the emission process
共air-water transfer兲 are thereby related and influenced by the fol-
lowing environmental factors: pH, temperature, and conductivity
共U.S. EPA 1974; Hvitved-Jacobsen 2002兲. The combined effect of
these factors—not including the turbulence effect—on the emis-
sion process is depicted in Fig. 1.
Study on sulfide formation and its corresponding modeling in
sewers has been performed for many years 共Pomeroy and Bowlus
1946; Thistlethwayte 1972; Boon and Lister 1975; Nielsen and
Hvitved-Jacobsen 1988兲. Recently, Yongsiri et al. 共2002兲 have ex-
perimentally quantified the transfer of H2 S across the air-water
interface focusing on the importance of pH that is directly related
to the presence of the exchangeable molecular form of H2 S. This
knowledge can be employed as a tool in evaluating odor and
corrosion problems when integrated with modeling of sulfide for-
mation in the water phase. To the writers’ knowledge, the effect of
investigated and quantified.
It is the objective of the current study to describe the effect of
temperature on the air-water transfer process of H2 S including
those temperature-related factors that affect the relative amount of
the volatile molecular form of H2 S. This study also determines
the temperature correction factor 共temperature coefficient兲 of H2 S
transfer across the air-water interface.
Theoretical Background
Fundamentals of Air-Water Transfer of Hydrogen
Sulfide in Sewer Networks
The physicochemical process of hydrogen sulfide (H2 S) transfer
across the air-water interface 共i.e., the emission process兲 in sewer

104 / JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / JANUARY 2004


Fig. 1. Overview of combined effect of pH, temperature, and con-
ductivity on dissociation and emission of hydrogen sulfide in sewers
networks is basically expressed by the transfer of the molecular
共aqueous兲 form (H2 S共aq兲) into the gaseous form (H2 S(g) ) as fol-
lows:
H2 S共aq) →H2 S共 g兲 (1)
It is important to notice that only the H2 S共aq) fraction—not the
ionized form (HS⫺ )—can be transferred across the air-water in-
terface 共Thistlethwayte 1972; U.S. EPA 1974; Matos and de
Sousa 1992; Gostelow et al. 2001; Hvitved-Jacobsen 2002兲.
Owing to the existence of the acid-base equilibrium of H2 S/HS⫺ ,
the air-water transfer process is, thus, largely dependent on the
dissociation process 共Fig. 1兲. The sulfide ion (S2⫺ ) is practically
negligible since it exists in insignificant amounts in typical do-
mestic wastewater 共Thistlethwayte 1972; U.S. EPA 1974; Steudel
2000兲. The dissociation process of H2 S is described to be a func-
tion of pH and K a1 共equilibrium constant兲 where K a1 is a function
of temperature and conductivity 共Fig. 1兲. Conductivity 共at 25°C兲
is recommended to be a substitute for ionic strength by U.S. EPA
共1974兲 and APHA et al. 共1995兲. For a practical convenience,
pK a1 , the negative logarithm of K a1 , is preferably used when
calculating the proportions of H2 S共aq) and HS⫺ .
Dissociation of H2 S共aq) and HS⫺ can be expressed by Eq. 共2兲
关 HS⫺ 兴
log ⫽pH⫺pK a1 (2)
关 H2 S共aq兲 ]
Figs. 2 and 3 show the dissociation of H2 S on the basis of H2 S共aq)
relative to total sulfide (H2 S(aq) plus HS⫺ ), caused by the effects
of pH, temperature, and conductivity in reference to pK a1 values
suggested by U.S. EPA 共1974兲 and APHA et al. 共1995兲. Taking
into account the relevant variations of these parameters 共pH, tem-
perature, and conductivity兲 in typical wastewater, pH is consid-
ered to be the most dominating factor for the amount of H2 S共aq)
being present and hence the most important factor determining
air-water transfer of H2 S. Therefore, it can be noted that the air-
water transfer rate of H2 S for this practical application is propor-
tional to the concentration of H2 S共aq) . It is clear from Fig. 2 that
acidic conditions favor the amount of H2 S共aq) being present. As an
example stated by U.S. EPA 共1974兲, at 25°C, conductivity of 0.2
mS cm⫺1, and pH 7.0, ‘‘H 2 S will escape about half as fast as
JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / JANUARY 2004 / 105
Fig. 2. Dissociation of hydrogen sulfide 共H2 S/HS⫺ equilibrium兲 at
different pH and temperatures. Values of pK a1 共at a conductivity
value of 0.2 mS cm⫺1 at 25°C兲 are obtained from U.S. EPA 共1974兲
and APHA et al. 共1995兲.
from a strongly acid solution having the same dissolved sulfide
content. At pH 9.0, it will escape only 1% as fast as from an acid
solution.’’ This is also the case for air-water transfer of other
dissociable substances such as ammonia (NH3 ) through its
NH3 /NH⫹ 4 equilibrium 共Stratton 1968, 1969; Pano and Middle-
brooks 1982兲.
Because of the small variation of conductivity in typical do-
mestic wastewater 共about 0.7–1.2 mS cm⫺1 at 25°C兲, the effect of
conductivity on pK a1 and thereby on the amount of the H2 S共aq)
fraction is of minor significance 共Fig. 3兲. For instance, when com-
paring the effect of conductivity between 0.4 and 2.0 mS cm⫺1,
the difference in H2 S共aq) present—at pH 7.0 and 20°C—is only
1.7%. Temperature, on the other hand, plays a more significant
role for the pK a1 value. Its effect 共10– 40°C兲 on the pK a1 value is
described as a linear function 共U.S. EPA 1974; APHA et al.
1995兲. For example, at a conductivity value of 0.7 mS cm⫺1, pK a1
decreases from 7.12 to 6.84 when temperature increases from 15
to 35°C. As a result, the amount of H2 S共aq) at pH 7 decreases with
increasing temperature from 40.9 to 56.7% of the total sulfide
concentration. In conclusion, it is crucial to understand that—
when determining the effect of temperature on emission of
H2 S—taking into consideration the effect of temperature on the
air-water transfer process itself as well as that on the dissociation
process of H2 S is needed 共Fig. 1兲.
Model Formulation
To account for the effect of temperature on process kinetics in
many chemical and microbial contexts, the temperature coeffi-
cient 共␪兲 based on the Arrhenius equation 共i.e., the logarithmic
Fig. 3. Dissociation of hydrogen sulfide 共H2 S/HS⫺ equilibrium兲 at
different conductivity and pH. Values of pK a1 共at 20°C兲 are obtained
from U.S. EPA 共1974兲 and APHA et al. 共1995兲.
temperature effect兲 is generally used. The Arrhenius equation, Eq.
共3兲, quantifies the temperature dependence of chemical reactions.
Looking at the diffusion coefficient in water as a factor that leads
to gas transfer across the air-water interface, its dependence on
temperature has—for many years—experimentally been shown to
follow the Arrhenius equation for a number of gases such as O2
共Davidson and Cullen 1957; Wise and Houghton 1966; Ferrell
and Himmelblau 1967兲. Considering the gas-transfer rate across
the air-water interface, several investigators such as Streeter
共1926兲, Elmore and West 共1961兲, and Bewtra et al. 共1970兲 used
the Arrhenius equation to describe the temperature dependence of
O2 transfer. Jensen 共1991兲 and Wu and Masten 共2001兲 also ap-
plied the Arrhenius equation for the temperature dependence of
krypton-85 ( 85Kr) transfer and ozone (O3 ) transfer, respectively.
Following the results from these investigations, the Arrhenius
equation is selected for the empirical description of the tempera-
ture dependence of H2 S transfer across the air-water interface
d ln k Ea
⫽ (3)
dT RT 2
where k⫽rate constant 共h⫺1兲; T⫽temperature 共K兲; E a ⫽activation
energy of the reaction 共J mol⫺1兲; R⫽universal gas constant 共8.314
J mol⫺1 K⫺1兲. Integrating Eq. 共3兲 between temperatures T 1 and T 2
yields
k 2 E a 共 T 2 ⫺T 1 兲
ln ⫽ (4)
k1 RT 2 T 1
in which k 1 and k 2 correspond to the rate constants at tempera-
tures T 1 and T 2 , respectively.
Temperature in sewer networks typically varies within a nar-
row range. As such, T 1 T 2 does not change considerably in prac-
tice, allowing the term E a (RT 2 T 1 ) ⫺1 to be considered constant.
Introducing ␪⫽exp关Ea(RT2T1)⫺1兴, the temperature dependence of
the rate constants can then be reduced to the following relation-
ship as first used by Streeter 共1926兲 for O2 transfer in the reaera-
tion process:
k 2 ⫽k 1 ␪ 共 T 2 ⫺T 1 兲 (5)
In general, T 1 is at 20°C. Thereupon, Eq. 共5兲 can be rewritten
as follows:
k T ⫽k 20␪ 共 T⫺20兲 (6)
where k T ⫽rate constant at temperature T 共°C兲 and k 20⫽rate con-
stant at 20°C. It is noted that ␪ for a specific process, in practice,
must be determined experimentally.
For weak acids such as H2 S, it must be recognized that the
transfer rate for the emission process is related to the molecular
form alone as the ionized form cannot be transferred across the
air-water interface 关Eq. 共1兲 and Fig. 1兴. Consequently, when using
total sulfide as the reference for H2 S emission, the effect of tem-
perature on the dissociation process must also be considered to-
gether with that on the emission process. Based on the emission
and dissociation processes of H2 S, the mass balance for H2 S共aq) is
described as
d 关 H2 S共 aq兲 兴
⫽Rate of H2 S共aq兲 transferred from HS⫺
dt
⫺Rate of H2 S共aq兲 emitted (7)
By modifying Eqs. 共2兲 and 共7兲 as well as taking into account the
characteristics of air-water transfer of H2 S as described earlier,
Eq. 共6兲 can be reformulated as
106 / JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / JANUARY 2004
k H2S 共 T 兲 共 1⫹10pH⫺pKa1 共 T 兲 兲 ⫽k H2S 共 20兲 共 1⫹10pH⫺pKa1 共 20兲 兲 ␪ 共 T⫺20兲
(8)
where k H2S(T) ⫽air-water transfer rate of H2 S 共h⫺1 ) at temperature
T in °C; k H2S(20) ⫽air-water transfer rate of H2 S 共h⫺1 ) at 20°C.
Eq. 共8兲 can be rearranged as follows:
1⫹10pH⫺pKa1 共 20兲
k H2S 共 T 兲 ⫽k H2S 共 20兲 ␪ 共 T⫺20兲 (9)
1⫹10pH⫺pKa1 共 T 兲
Within the temperature range of interest for in-sewer pro-
cesses, Eq. 共9兲 can—with good accuracy—be approximated by
k H2S 共 T 兲 ⫽k H2S 共 20兲 ␪ 共cT⫺20兲 (10)
where ␪ c ⫽temperature coefficient due to the lumped effect 共com-
bined兲 of temperature on the dissociation and emission processes.
Materials and Methods
Experimental Setup and Procedures
The experimental setup and procedures used in this study were
similar to those applied by Yongsiri et al. 共2002兲. All experiments
for the determination of the H2 S-transfer rates were conducted in
closed vessels at constant pH and varying temperature. The vol-
umes of the water phase and the air phase of the closed vessels
were 2,500 and 870 mL, respectively. The hydraulic conditions of
the water phase defined as the Reynolds number of
the magnetic stirrer 共Ljubisavljevic 1984兲 were—for all
experiments—held constant at a Reynolds number of about
38,200. The air phase was continuously flushed with water-
saturated nitrogen gas during the emission process. Constant tem-
peratures in the water phase as well as in the air phase ranging
from 5 to 40°C 共⫾0.3°C兲 were obtained by placing the closed
vessels in a water bath.
Deionized water was used as a medium. An acetate buffer
system was employed to obtain pH at 4.5 共corresponding to a
conductivity value of 4.8 mS cm⫺1 at 25°C兲 whereas phosphate
buffer systems were used to obtain pH at 6.5 and 7.0 共correspond-
ing to conductivity values of 13.2 and 15.3 mS cm⫺1 at 25°C,
respectively兲. To avoid loss of sulfide from chemical oxidation,
the medium was deoxygenated with nitrogen gas prior to conduct-
ing the experiments. Sodium sulfide nonahydrate (Na2 S•9H2 O)
was added to the medium as the source of total sulfide. The initial
concentration of total sulfide for all experiments was 7–12
gS m⫺3. Using a syringe, samples for sulfide analysis were peri-
odically drawn through a stainless steel tube 共0.8-mm diameter兲.
Sulfide was measured by the methylene blue method as described
by Cline 共1969兲.
Since only the H2 S共aq) fraction is active in the air-water trans-
fer process of H2 S, it was assumed that the effect of different
conductivity values originating from the buffer systems on the
transfer rate was negligible. The assumption on the negligible
effect of conductivity on pK a1 within a practical range of conduc-
tivity was based on U.S. EPA 共1974兲 and APHA et al. 共1995兲 as
shown in Fig. 3. The independence of the transfer rate on con-
ductivity was confirmed by an experiment carried out at pH 4.5
and 20°C under the conductivity range of 4.8 –20.0 mS cm⫺1
共25°C兲. Under these conditions, almost all sulfide was present as
H2 S共aq) 共Fig. 3兲. The result 共Fig. 4兲 shows a slight tendency to-
ward decreasing transfer rates with increasing conductivity; how-
ever, the tendency is not statistically significant with a P value of
0.18 共at the 0.05 level of significance兲. Thus, it can be concluded

Fig. 4. Effect of conductivity on transfer rate of hydrogen sulfide at
20°C and pH 4.5. Number of measurements is 17. Level of signifi-
cance applied is 0.05.
that conductivity 共an estimate for ionic strength兲 plays no signifi-
cant role on the transfer rate of H2 S within the range of conduc-
tivity relevant in this study.
Determination of Temperature Coefficients
Air-water transfer rates of H2 S were determined at varying tem-
perature and constant pH values of 4.5, 6.5, and 7.0. The transfer
rates were calculated based on the measured sulfide loss 共due to
emission兲 in the water phase with time. The temperature coeffi-
cient due to the lumped effect of temperature on dissociation and
emission (␪ c ) was determined by relating the transfer rates to Eq.
共10兲. By applying a natural logarithmic function, a linear relation-
ship can be obtained with ln ␪c being the slope of the linear equa-
tion.
Results and Discussion
Effect of Temperature
The logarithmic plots of the transfer rates and temperature 共as T
⫺20) with reference to Eq. 共10兲 are shown in Fig. 5 for pH 4.5,
6.5, and 7.0. Increases in the transfer rate with temperature were
observed for all pH values investigated. At pH 4.5 where almost
all sulfide is present in the form of H2 S共aq) , there is no significant
effect of temperature on the amount of the H2 S共aq) fraction being
present 共Fig. 2兲. The amount of the H2 S共aq) fraction at pH 4.5 was
calculated to be 99.8 and 99.6% at 10 and 25°C, respectively
共shown in the brackets in Fig. 5兲. Therefore, it can be considered
Fig. 5. Effect of temperature on air-water transfer of hydrogen sul-
fide at different pH. Numbers in brackets are calculated amounts of
molecular hydrogen sulfide in percent.
JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / JANUARY 2004 / 107
Table 1. Linear Regression Statistics for Temperature Dependence of
Air-Water Transfer of Hydrogen Sulfide
Correlation
Study condition ln ␪c⫾SE coefficient 共r兲
pH 4.5 (n⫽21) 0.0334⫾0.0027 ( P⬍0.001) 0.94
pH 6.5 (n⫽16) 0.0282⫾0.0026 ( P⬍0.001) 0.95
pH 7.0 (n⫽27) 0.0210⫾0.0013 ( P⬍0.001) 0.96
Note: n⫽number of data; SE⫽standard error; P⫽P value from linear
regression analysis.
that what is seen here is the effect of temperature on the transfer
rate 共emission process兲 alone owing to the insignificant effect of
temperature on the amount of the H2 S共aq) fraction 共dissociation
process兲 that is present at pH 4.5. In contrast, the effect of in-
creasing temperature on the dissociation process 共i.e., a linear
decrease in pK a1 with increasing temperature兲 becomes larger at
pH 6.5 and 7.0 caused by decreasing amount of the H2 S共aq) frac-
tion. Decreases in sulfide present as H2 S共aq) in percent were esti-
mated to be 77.6 –71.5% 共15–25°C兲 at pH 6.5 and 56.3–32.9%
共10– 40°C兲 at pH 7.0 共Fig. 5兲. This exemplifies the fact that the
effect of temperature on H2 S transfer at conditions where both
H2 S共aq) and HS⫺ coexist 共e.g., pH 7.0兲 is the lumped effect on
both increased air-water transfer 共emission兲 and decreased
amounts of H2 S共aq) 共dissociation兲.
According to the collision theory and kinetic theory of gases,
the molecular fraction of collisions that has a minimum energy of
E a increases with increasing temperature as the molecular speed
becomes greater. As proposed by Krenkel and Orlob 共1962兲, the
gas-transfer process of O2 is dependent upon E a necessary for
reacting molecules to pass through the interface. A similar inter-
pretation must be true for H2 S, i.e., an increase in the transfer rate
with temperature is theoretically expected within practical ranges
as the number of H2 S共aq) possessing a minimum energy of E a
increases. Despite the fact that increasing temperature will de-
crease the amount of the H2 S共aq) fraction and hence reducing
transfer rates, a net increase in the transfer rates with temperature
within the range investigated 共5– 40°C兲 is observed. This refers to
the two processes 共dissociation and emission兲 working in the op-
posite direction. The effect of increasing temperature plays a
more influential role in air-water transfer of H2 S than in de-
creased amounts of H2 S共aq) , which implies that the number of
H2 S共aq) possessing a minimum energy of E a still increases within
this temperature range.
A linear regression analysis was used to fit the data for each
pH investigated. Table 1 summarizes regression statistics of the
results shown in Fig. 5. Using t-tests, each of the three slopes
(ln ␪c) is linear at a P value ⬍0.001 共statistically significant兲. It is,
therefore, concluded that there exists a linear relationship between
the natural logarithm of the transfer rate and temperature. This
indicates that the Arrhenius equation describing the temperature
dependence of chemical reactions can be applied for the air-water
transfer process of H2 S even though the effect of the dissociation
process is lumped into the description. From the slopes given in
Table 1, the temperature coefficient (␪ c ) for air-water transfer of
H2 S was calculated to be—with its 95% confidence interval—
1.0340⫾0.0057 共at pH 4.5兲. It must be recognized that this is
under the conditions where almost all sulfide is present in form of
H2 S共aq) , i.e., there are no significant effects of temperature and
conductivity on the amount of the H2 S共aq) fraction 共99.6 –99.8%兲.
As a result, ␪ is approximately equal to ␪ c . However, when pH
was raised to 6.5 and 7.0, the ␪ c values due to the lumped effect
of the transfer rate and the dissociation process, as expressed by

Fig. 6. Comparison of temperature coefficient for air-water transfer
of hydrogen sulfide observed at pH 4.5 as well as temperature coef-
ficients due to lumped effect observed at pH 6.5 and 7.0 and literature
values for other transferable substances 共cf. text兲. Error bars represent
95% confidence intervals.
Eq. 共10兲, were found to be—with their 95% confidence
intervals—1.0286⫾0.0057 and 1.0212⫾0.0027, respectively, i.e.,
lower than that of pH 4.5.
Using Eqs. 共9兲 and 共10兲 together with the ␪ c values obtained at
pH 6.5 and 7.0, the ␪ values for the air-water transfer process of
H2 S were calculated to compare with the directly observed value
of 1.034 共at pH 4.5兲. The calculated ␪ values were 1.036 and
1.037 corresponding to the observed ␪ c values at pH 6.5 and 7.0,
respectively. Both of the calculated ␪ values were well within the
error range found for ␪ at pH 4.5. It indicates that Eqs. 共9兲 and
共10兲 can be applied to describe the measured value well. When
using total sulfide as the reference for H2 S emission, it is obvious
that the effect of increasing temperature toward decreasing
H2 S共aq) concentrations and thereby decreasing transfer rates plays
a significant role for the effect of temperature on air-water trans-
fer of H2 S. For example, applying Eqs. 共9兲 and 共10兲 on pH 8.0
will lead to the lumped effect on the transfer rate with ␪ c equal to
1.005, i.e., a remarkable decrease in the observed temperature
dependence compared to what would be seen under more acidic
conditions. In consequence, it is strongly suggested that this effect
is taken into account when applying the temperature dependence
of H2 S emission.
Comparison with Other Transferable Substances
Fig. 6 illustrates a comparison of the ␪ 共at pH 4.5兲 and ␪ c 共at pH
6.5 and 7.0兲 values obtained in this study for air-water transfer of
H2 S and those for other transferable substances from the litera-
ture. Literature values of ␪ for O2 transfer vary from 1.006 to
1.047 共Streeter 1926; Streeter et al. 1936; Downing and Truesdale
1955; Truesdale and Vandyke 1958; Elmore and West 1961;
Metzger and Dobbins 1967; Metzger 1968; Barnhart 1969; Be-
wtra et al. 1970; Parkhurst and Pomeroy 1972; Matsuo and
Hirayama 1982; Jensen 1991兲. Wu and Masten 共2001兲 and Jensen
共1991兲 found the ␪ values of 1.031 and 1.0352 for air-water trans-
fer of O3 and 85Kr, respectively.
It can be seen that the ␪ value for air-water transfer of H2 S is
in a similar range to those for transfer of O2 , O3 , and 85Kr 共Fig.
6兲. In spite of some reports on gradual changes in ␪ as a function
of turbulence for O2 transfer 共Elmore and West 1961; Metzger
108 / JOURNAL OF ENVIRONMENTAL ENGINEERING © ASCE / JANUARY 2004
and Dobbins 1967; Metzger 1968; Matsuo and Hirayama 1982兲,
the turbulence level in this study was kept constant as its extent
from an application point of view in sewer networks is expected
to be of minor importance for air-water transfer of H2 S.
From Eq. 共4兲, the E a value of the air-water transfer process of
H2 S was calculated to be 23,198 J mol⫺1 based on the observed ␪
at pH 4.5. In comparison with air-water transfer of O2 , a value of
16,719 J mol⫺1 was calculated based on data presented by Elmore
and West 共1961兲 whereas Krenkel and Orlob 共1962兲 estimated the
E a value to be 20,938 J mol⫺1 as the same order of magnitude for
water vaporization.
Conclusions and Perspectives
The effect of temperature on air-water transfer of hydrogen sul-
fide was studied. Increases in the air-water transfer rates of hy-
drogen sulfide with increasing temperature were observed for all
pH values investigated 共pH 4.5, 6.5, and 7.0兲. The Arrhenius
equation can be employed to express the increase in the air-water
transfer rate with temperature, resulting in a temperature coeffi-
cient ␪⫽1.034 for the transfer process of molecular hydrogen
sulfide at pH 4.5. The effect of temperature on air-water transfer
of hydrogen sulfide as referred to total sulfide was smaller when
both species of hydrogen sulfide, i.e., the molecular and ionized
forms, are present. The observed temperature dependence de-
creased significantly with increasing pH as satisfactorily ex-
plained by the importance of temperature on the dissociation pro-
cess of hydrogen sulfide, i.e., ␪ c ⫽1.029 at pH 6.5 and ␪ c
⫽1.021 at pH 7.0. The temperature coefficient for air-water trans-
fer of hydrogen sulfide is in a similar range to those reported for
transfer of oxygen, ozone, and krypton-85.
It is strongly suggested that the effect of pH on the emission
process of hydrogen sulfide and the effect of pH on the tempera-
ture dependence of the same process are taken into account when
concerned with odor and corrosion problems in sewer networks.
The information obtained in the present study should be applied
when modeling the emission process of hydrogen sulfide for man-
aging anaerobic sewer networks.
Notation
The following symbols are used in this paper:
E a ⫽ activation energy of reaction 共J mol⫺1兲;
K a1 ⫽ equilibrium constant 共⫺兲;
k ⫽ rate constant 共h⫺1兲;
k H2S(T) ⫽ transfer rate of H2 S at temperature T (h⫺1 );
k H2S(20) ⫽ transfer rate of H2 S at 20°C 共h⫺1兲;
k T ⫽ rate constant at temperature T (h⫺1 );
k 1 , k 2 ⫽ rate constants at temperatures T 1 and T 2 (h⫺1 ),
respectively;
k 20 ⫽ rate constant at 20°C 共h⫺1兲;
pK a1 ⫽ negative logarithm of equilibrium constant 共⫺兲;
R ⫽ universal gas constant 共8.314 J mol⫺1 K⫺1兲;
T ⫽ temperature 共K or °C兲;
T 1 , T 2 ⫽ temperatures 1 and 2 共K or °C兲, respectively;
␪ ⫽ temperature coefficient 共⫺兲; and
␪ c ⫽ temperature coefficient due to lumped effect 共⫺兲.
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