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Overview of different solutions to mitigate odour and H 2 S from municipal

emission sources

Conference Paper · September 2017

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Overview of different solutions to mitigate odour and H2S from

municipal emission sources

W. Franke*, M. Ettl**, G. Doppelbauer**, J. Hilmers** and M. Allerborg***

*
Yara International ASA, Hydrovegen 67, 3936 Porsgrunn, Norway
(E-mail: wolfram.franke@yara.com)
**
Yara Industrial GmbH, Sprudelstraße 3, 53557 Bad Hönningen, Germany
***
Yara Sweden AB, Varuvägen 9, 125 30 Älvsjö, Sweden

Abstract
Sewage systems often demand a treatment against odour emissions. There are several options
available how to perform the approach. However there is no “one size solution” that fits all,
instead a choice is required based on the individual case. Typically a process of chemical treatment
of the water/sludge or a vapour phase treatment is in favour. In order to prevent emissions and to
minimize the necessary costs is appears useful to combine different methods. Within this paper
three measures will be discussed especially with focus on the individual efficiency range: 1) The
optimization of nitrate dosage for bio-chemical prevention of odour emission. 2) A novel oxidizer
solution based on chlorite for sludge treatment for selective oxidation of sulphide. 3) A photo-
ionization technology in combination with activated carbon filter as enhanced air treatment
process to handle the remaining emissions.

Keywords
Odour emissions, mitigation strategies, nitrate, oxidizer, photo-ionization

INTRODUCTION
Transport and treatment of waste water is a challenging task from a technical point of view, not
only with respect to carbon and nutrient removal. There is a significant potential for hydrogen
sulphide (H2S) formation and odour emissions from waste water and sludge - and this causes
problems regarding emission, safety and life span of sewer systems. An overview of the odour
subject can be found at STUETZ and FRECHEN (2001) as well as at FRECHEN (2009).

In many cases the environment needs to be protected against odorous contaminants, in particular as
environmental protection regulations are more stringent than before, like for instance the Odour
Immission Guideline (LAI, 2009). Accordingly, the impact of odour for the area around an
emission source needs to be restricted depending on the actual use of the area. As a consequence the
impact of odour emissions needs to be evaluated based on the surrounding area and not only by the
emission level itself.

Regulations for working areas have become stricter over the years (EC, 2009). This affects in
particular pumping stations as well as the inflow area of waste water treatment plants (WWTP), as
they are frequently used working areas . Consequently a short term exposure limit (STEL) of 10
ppm H2S and the time-weighted average (TWA) of 5 ppm H2S must not be exceeded in such areas.
Workers protection requires a selection of feasible odour and H2S removal methods besides the
prevention of emission to the environment.

First of all the leading question at municipal sites should be whether a formation of odorous
substances has to be prevented or if contaminated air streams might be treated. This is valid for
sludge and waste water works as well as for sewers. A preventive measure allows controlling the air
quality directly by limiting the emission potential from the sewage for instance, whereas an air
treatment system can only work via dilution of the contaminants prior the treatment by applying a
7th IWA Odour 2017, Warsaw, Poland 1
specific air exchange rate.

Moreover, contaminants like H2S are highly corrosive and will damage the sewer system over time.
Also in this respect control of the emission potential can be more efficient than air movement, in
particular within a sewer. Corrosion, affecting primarily manholes or WWTPs inflow, needs to be
reduced in order to minimize re-investment costs. More details can be found in DWA-M 168
(2010).

A chemical treatment focuses on the reduction of the emission potential and therefore an emission
problem is solved closer to its roots. Chemical treatment to meet regulations (dedicated to
prevention of odour and/or H2S formation) is recommended by the guideline ATV-DVWK-M 154
(2003) and literature like FRECHEN and FRANKE (2009).

Cost-efficient chemical solution may lead to remaining emissions, as the chemicals shall not be
overdosed. On the other hand the entire water body containing potential odorous compounds needs
to be treated. Therefore remaining emissions (on a selected level) might occur on a level that can
still be noticed. Those emissions might require an additional vapour phase treatment.

The vapour phase treatment can be performed by various methods, and the best applicative method
needs to be selected based on the local situation. Most common are bio-filters, activated carbon
filters and chemical scrubbers. Odour mitigation strategies can be achieved by combining several
methods to reduce all contaminates of a gas stream.

A combination of chemical and vapour phase treatment allows using a solution in a cost efficient
range and avoids stretching into costly overdosing or oversizing the vapour phase treatment
respectively. In order to prevent emissions and to minimize the required costs chemical measure
and air treatment technology need to be adjusted in order to match best.

Within this paper three measures will be discussed especially with focus on the individual
efficiency:
1. The optimization of nitrate dosage for bio-chemical prevention of odour emission
2. A novel oxidizer solution based on chlorite for sludge treatment for selective oxidation of
sulphide
3. A photo-ionization technology in combination with activated carbon filter as a simple and
effective air treatment process to handle remaining emissions
4.

OVERVIEW OF THE METHODS

Nitrate dosage is an established method to prevent odour formation.
The basic concept to apply a nitrate solution for this purpose was described by BENTZEN et al.
(1995) for instance for pressure mains. A detailed study on several gravity sewage systems can be
found at FREY (2008). FELDHAUS et al. (2006) compare chemical treatments with calcium
nitrate, ferric chloride and hydrogen peroxide (H2O2), and conclude that for the specific case the
calcium nitrate dosage is the most beneficial choice.

Calcium nitrate solution is added to maintain anoxic conditions in the sewage and to prevent the
development of anaerobic zones. Anoxic conditions prevent the formation of sulphide and
eventually H2S, which is one of the most common odorous compounds linked to sewage systems. In
the course of the triggered denitrification process bacteria consume carbon compounds, leading to
the degradation of some of the volatile organic carbon (VOC) in addition. As a conclusion nitrate

7th IWA Odour 2017, Warsaw, Poland 2

dosage is a well-established, preventive measure to avoid odour and H2S emissions. Additionally,
the nitrate dosage stimulates a biological community, thus it is a natural process to provide odour
and H2S free conditions in a sewage network. The application of a nitrate solution is required prior
to the formation of odorous compounds. The challenge is to apply the correct amount of nitrate to
not over-dose (and waste product) or to under-dose (and allow emissions). Therefore different
levels of sophisticated dosage technologies are available. An overview of different dosage strategies
and systems is given by FRANKE et al. (2011). The described systems are useful especially if the
emissions are re-occurring and following some statistically detectable pattern. This is valid for
municipal waste water systems with pumping stations and a certain degree of turbulence.

Nitrate dosage has been established for a large range of odour and H2S prevention measures. To
avoid over-dosage it is often desired to allow a remaining emission, in particular at industrial
installations with high contamination levels. In such cases the remaining emission will not be
hazardous but still might be unpleasant.

The nitrate dosage is most suitable if the expected potential of sulphide concentrations in the waste
water is << 100 mg/L or the H2S concentration in air is << 1,000 ppm. In such cases a dosage of
0.1-1.0 L/m3 of a 45-50% calcium nitrate solution is suitable to prevent sulphide formation and H2S
emissions in average below 1 ppm H2S.

Oxidizer for rapid sulphide neutralization

An oxidizer typically oxidizes organic or inorganic substances. This implies that oxidizers are a
suitable measure to instantaneously treat sulphide or odour problems in the liquid phase. Especially
sludge and slurry with an increased viscosity and reduced diffusion rate compared to waste water
can be treated well by oxidizers due to the reaction kinetics.

A variety of oxidizers is available for this purpose. An indication about the suitability is given in
guideline VDI 3679 B4:2014-10, but the focus is on chemical scrubbers and not on water treatment.
The suitability of several oxidizing agents is described regarding different targeted contaminants,
and most reagents work for H2S. However the efficiency is not stated in detail.

A rough price comparison is given in Table 1, based on the prices indicate by Alibaba.com
(09.05.2017). The list indicates that there are significant differences in the price per weight of active
ingredient. As a consequence, product efficiency is key to identify a most suitable product, and a
realistic comparison is not possible just evaluating a volume specific dosage.

Table 1: Prices of different oxidizers based on www.alibaba.com (05/2017)

Substance State of Approx. Lower Approx. Upper Average, 50% solution
aggregate Price [USD/t] Price [USD/t] equivalent [USD/t]
Hydrogen Peroxide (H2O2) Liquid 50% 200 900 550

Sodium Permanganate (NaMnO4) Liquid 40% 500 1500 1250

Sodium Hypochlorite (NaClO) Liquid 12% 200 500 1460

Sodium Chlorite (NaClO2) Solid 80% 580 1600 680

The use of hydrogen peroxide (H2O2) as an oxidizer is perhaps most common within sewage
systems. H2O2 is available in a large quantity, and it is easy to apply. Downside of H2O2 are shelf
life and price of the chemical. In addition, H2O2 is not reacting selectively with certain substances
like sulphide but interacts with any kind of organic matter, too; therefore the efficiency is limited.

7th IWA Odour 2017, Warsaw, Poland 3

The use of permanganate solutions is also possible, but the handling requires an intense safety
awareness, and the application costs are high.

Another common oxidizer is sodium hypo-chlorite (NaClO). NaClO is widely used for cleaning and
commonly also known as “bleach”. Negative aspects of NaClO are a lower chemical stability and
its aggressiveness towards organic matter – which indicates that the efficiency in a sludge matrix is
low. Largest disadvantage of NaClO is the release of chlorine when reacting with inorganic and
organic compounds. NaClO is commonly used in a 12 M% solution. Per 1 L of the product 65 g of
Chlorine are released, as the active matter consists of 47 M% chlorine. Thus chlorine emissions can
be significant.

Sodium chlorite (NaClO2) is not yet commercially established as a common oxidizer. The chemical
seems to be related to NaClO, but this chemical is comparatively easy to handle and significantly
less reactive in lower concentration. A simple experiment with different oxidizers (25 M%
solutions) was conducted by the authors, with the target to remove a contamination of 1.5 mg/L
sulphide from an aqueous solution. The results presented in figure 1 indicate that NaClO is more
efficient than H2O2 concerning sulphide removal. The apparent selectiveness for sulphide of
NaClO2 is the most obvious advantage against H2O2. Thus NaClO2 oxidizes sulphide, but leaves
carbon compounds untouched. In case of NaClO2 application there is no formation of chlorinated
organic compounds as reaction by-products, and the overall chlorine emission is strongly reduced
compared to NaClO. The cost overview indicates that NaClO2 is per weight comparable to H2O2
and significantly cheaper than both NaClO and NaMnO4. Therefore NaClO2 appears to be
competitive from performance, health and safety aspects as well as from economic point of view.

Stochiometric addition of oxidizer

100
90
% sulphide reduction

80
70
60 H2O2
50
40 NaClO
30 NaClO2
20
NaMnO4
10
0
0 2 4 6 8
ml oxidizer added

Figure 1: Comparison of several oxidizers regarding sulphide removal

The main target of oxidizer application is waste water sludge treatment. Waste water sludge is a
typical product of either an anaerobic fermentation and/or a separation process. In most cases the
material is kept under anaerobic conditions for a certain time, thus fostering sulphide formation.
The emission of the sulphide as H2S is often linked to turbulences during transport and discharge of
waste water or sludge, but can also originate by diffusion. As a consequence oxidizer application is
required just before the movement of the sludge.

Photo-ionization combined with activated carbon filters for vapour phase treatment

7th IWA Odour 2017, Warsaw, Poland 4

Vapour phase treatment is a curative method to treat evaporated contaminants inside of air streams.
Those might originate from sources which cannot be treated with chemicals, like in industry,
processing (also sludge and waste) and storage, or generally diffuse sources. They might also
originate from the waste water to the atmosphere. Those emissions typically occur at waste water
streams without (sufficient) chemical treatment.

Prior to the installation of a vapour phase treatment the identification of the exact location is
essential, where contaminants are emitted. In certain cases of a clearly identified location of
emissions a vapour phase treatment might be more efficient than a chemical dosage.

There are various vapour phase treatment methods available, to be distinguished e.g. in physical,
chemical and bio-chemical processes. Such a summary is given by FRANKE (2011). Chemical
processes, like chemical scrubbers, are usually targeting one certain type of contaminant, for
instance using a caustic scrubber against H2S. In contrast, bio-chemical systems like bio-filters, are
more useful to treat a wide range of low concentrated contaminants. Physical processes, like
activated carbon filters, are selective, similar to the chemical methods, but can be modified to target
a wider range, for instance by combination with activated carbon filters. Combinations of different
vapour phase systems might be useful in order to combine their benefits in a synergetic way, while
weaknesses of the individual processes are eliminated. A common combination would be the
sequential treatment in a chemical scrubber and a bio-filter. Technical designs of various processes
are described in the guidelines of the VDI 3679 series.

An example of this kind of combined vapour phase system is the photo-ionization followed by an
activated carbon filtration. The Ultra violet (UV) light cracks some contaminants and forms ozone,
which acts as a strong oxidizer and decomposes additional molecules. The remaining contaminants
are adsorbed by the activated carbon filter. Moreover, the ozone acts as an in-situ regeneration agent
for the activated carbon filter. This hybrid process combines the benefits of photo-ionization
including ozone formation and activated carbon filtration. Based on this combination a wide range
of contaminants can be destroyed/adsorbed, and the weaknesses of the single methods will be
compensated by each other.

Photo-ionization is a well-established vapour phase treatment technology – copied from nature: UV

light is able to ionize oxygen if the radiation has a wave length of 185 nm. UV light of 254 nm
wave length is ionizing certain contaminants, but does not affect oxygen. Already CHAPMAN
(1930) explained the natural ionization impact on air, and the formation of ozone and in particular
hydroxyl ions has been described by ENGELMANN (1965). The impact of this oxidizer on
contaminants was investigated for instance by CHAMEIDES und WALTER (1973) or by LEVY
(1974). A first patent to implement UV radiation to treat air was published in 1976 (United States
Patent 3977952).

Activated carbon filters have been used for many decades for different cleaning purposes, and there
are various grades available. Contaminants are getting adsorbed to the surface of the carbon, which
is different to a chemical bond. Some activated carbon products have pores on their surface to
increase the total surface area in order to enhance their adsorptive capacity. Activated carbon can be
regenerated by exposing to high temperature (e.g. by steam) or to an oxidizer.

A UV treatment combined with activated carbon system can be designed to treat H2S concentrations
over a wide range, as an activated carbon filter can handle high concentrations of several hundred
ppm H2S. There is only one limitation by the oxidation process: The oxidation of H2S results in
sulphur oxide (SOx), and there are potentially limits for SOx emissions. Another point to be

7th IWA Odour 2017, Warsaw, Poland 5

considered is heat formation by the ozone production part of the system due to the UV lamps. A
treatment of highly contaminated gas streams might require special measures to cool the UV lamp
units, because a larger part of the consumed energy would be converted to heat instead of UV light.
Typically a UV treatment system combined with activated carbon will treat at least 15 ppm H2S in
average.

CASE STUDIES
Nitrate dosage is an established method to prevent odour formation.

Case study 1: Dosage systems with a demand calculation are sufficient for ordinary sewage systems
without industrial discharge. Such a system is typically able to prevent the H2S emission to the
desired level. In figure 2 the development of H2S concentration within a manhole is presented. In
the untreated situation the H2S concentration reaches health risk relevant levels. After adding the
calcium nitrate the H2S concentration remain on a healthy level of in average < 1 ppm H2S.

100
90 Municipal wastewater
80
70
H2S without dosage H2S with dosage
60
H2S [ppm]

50
40
30
20
10
0
1 2 3 4 5 6 7 8

time [days]
Figure 2: H2S concentration at a manhole at a real case prior to and during preventive chemical
H2S treatment by a calcium nitrate solution.
Case study 2: The use of a control loop (“feedback dosage”) is state of the art on the top of nitrate
dosage technology. This strategy is based on a H2S concentration signal downstream that is used to
adjust the nitrate solution dosage upstream. For this purpose the H2S concentration data are
uploaded from an online measuring device to a server that forwards the signal to the dosage-
controller. The controller adjusts the required dosage automatically within a given time frame. The
dosage-control itself is based on several input signals at the dosing site. The control loop is used to
adjust the dosage in addition, but not to control it completely. In case the H2S signal is disturbed the
system still doses according to the programmed dosing algorithm.

In the presented case a concentration of 2 ppm H2S had to be maintained, and STEL or TWA limits
had to be respected. The measurement results are illustrated in figure 3 for a period without and
with activated control loop. The conditions at the site changed with the season, as illustrated in
figure 4: The site was exposed to a lower discharge and higher temperatures during the period of
active control loop (FB dose) compared to the period with standard dosage (Std dose). Both aspects
indicate increased demand of the nitrate dosage during the period with active control loop. In
contrast to this expectation the statistical analysis illustrates that the controlled loop system
achieved results that were closer to the target values than the results of the standard dosage (figure
5). Additionally, the applied dosing amounts during both periods were comparable (4,3 L/h in
average and 12 L/h as maximum; data not shown in detail), whereas the desired average of 2 ppm

7th IWA Odour 2017, Warsaw, Poland 6

H2S and the compliance with TWA and STEL limits were still achieved. As a result the combined
controlled dosing strategy enables a more demand oriented product application.

Figure 3: Measurement data from the dosing site of a nitrate solution (raw data)

Figure 4: Statistical analysis of the flow and temperature data of standard (Std) and combined
control loop (FB) dosing strategies

Figure 5: Statistical analysis of the H2S concentration measurement; active control loop (FB dose)
and standard dose without active loop (Std dose)

Oxidizer for for rapid sulphide neutralization

In the presented case the curative H2S treatment of waste water sludge with oxidizer was evaluated.

7th IWA Odour 2017, Warsaw, Poland 7

The sludge was typically stored for 2 weeks during winter time and for 1 week during summer time.
The storage building was encapsulated and emissions did not appear unless the sludge was
transported: The sludge was transported onto a truck using a conveyor belt. Emitted H2S
concentrations are illustrated in figure 6. During application of NaClO2 solution the H2S emissions
were significantly reduced. The first peak is representative for untreated conditions (approx. 17
ppm), the second peak (approx. 11 ppm) represents a medium dosage and the third one (approx. 7
ppm) the result of high dosage level.

Figure 6: H2S concentration at the conveyor belt while sludge was discharged to truck

The direct evaluation of the sludge treatment by FeCl3 and compared to NaClO2 revealed that the
NaClO2 application was more cost efficient and more effective (data not presented).

Vapour phase treatment with photo-ionization and activated carbon

Air from a waste treatment facility was treated with a combined system of photo-ionization and
activated carbon filter in the following case in 10 treatment lines: 4 lines were equipped with an
additional photo-ionization unit. The measurement results are given in Table 1 (olfactometry
performed according to SS EN 13725). The photo-ionization itself had a treatment efficiency
(minus 41%). The overall treatment efficiency of the activated carbon filter without any additional
system compared to the combination of both, photo-ionization plus activated carbon filter was
basically the same (minus 93% versus minus 94%). In this case about 7% of the odorous
contaminants were not adsorbeable in the activated carbon filter, no matter if pre-treated with UV
light. However, this measurement campaign does not reflect the long term effect: As the ozone
regenerates the carbon filter, there are longer time intervals for the activated carbon replacement
compared to a system without ozone formation. In addition the reduction of the contaminants by the
UV light suggests that the filter is also less loaded, what might allow a reduction of filter size
compared to single activated carbon filter units.

7th IWA Odour 2017, Warsaw, Poland 8

Table 1: Results of odour measurement at several treatment lines
Odour concentration cod [ouE/m3] Elimination efficiency ηod
Sample raw gas after UV after UV+AF after AF after UV after UV+AF after AF

1 5 312 3 158 197 -41 % -96 %

2 5 312 3 158 256 -41 % -95 %
3 11 585 1 625 -86 %
Air treatment line

4 6 502 456 -93 %

5 4 598 215 -95 %
6 4 598 279 -94 %
7 6 317 431 -93 %
8 6 317 395 -94 %
9 9 742 645 -93 %
10 6 502 362 -94 %

DISCUSSION AND CONCLUSIONS

The presented methods of preventive and curative odour emission control are well established
technologies. The case studies illustrate that there are particular situations where each of the
methods is favourable.

The controlled nitrate dosage is a common approach, and the observed results based on an
additional controlled loop “feedback” dosage indicate an option that might improve the existing
technology in certain cases.

The oxidizer treatment indicates a new option for waste water sludge treatment. To verify the
efficiency of the treatment each case has to be evaluated according to the specific differences of
every sludge and also of the sludge transport and storage systems.

The vapour phase treatment consisting of photo-ionization and activated carbon filtration leads to
high removal efficiency rates. The effect of the photo-ionization is has a long-term effect, as the
regeneration of the activated carbon by the UV produce ozone is improving the cost efficiency.

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