Ozone and UV –

a tool for “multi-barrier concepts” in water treatment

Authors: Dr. A. Ried, Dr. J. Mielcke
Xylem Water Solutions Herford GmbH • Boschstr. 4 - 14 • 32051 Herford • Germany
phone: +49 5221 930-144 • fax: +49 5221 930-783 • e-mail: [email protected]

Abstract

The use of ozone and/or UV for water treatment processes is often a combination of an ozone and/or
UV-step with additional treatment steps, e.g. biological treatment, flocculation, filtration and activated
carbon. Therefore it is necessary to develop an optimized combination of these different steps.
This article will demonstrate the advantages presenting two examples for drinking water treatment and
two examples for municipal waste water treatment.

Key words

Disinfection, persistent substances, ozone, UV, multi-barrier system, drinking water, municipal waste
water, advanced oxidation

Introduction

The supply of the world population with safe and sufficient drinking water is one of the most important
tasks of mankind in the future. For that purpose it is crucial to protect the natural drinking water
reservoirs and to develop strategies for a reduction of the consumption. One way is to intensity the
reuse of process- or waste water.
In many national water strategies waste water re-use is already integrated as rational resource
management and alternative option for agriculture. However, the micro-biological and chemical
composition of waste water limits the re-use. Therefore, modern and economic water treatment
techniques are required, which enable the re-use of sewage water.

The combination between biological steps and ozone dosage is well established to remove chemical
contaminants like non-biodegradable COD, adsorbable halogenated organic compounds (AOX),
halogenated hydrocarbons (HCX) or polyaromatic hydrocarbons (PAH).
The purposeful use of ozone and UV for conventional water treatment plants (as well drinking water as
waste water) presents a successful additional treatment technique.

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 Principle aspects of ozone and UV barriers in drinking water treatment

In drinking water treatment it is common practice to have different treatment steps depending on the
raw water source and the treatment goals. Beside the treatment efforts in the water works the drinking
water distribution and the network is another important issue. Tab. 1 will give some basic information
on the principle treatment scheme and effects.

Pre-treatment Main oxidation Filter/BAC Final

disinfection
Pre ozone Sand filter Membrane
Technique
Chlorination
Flocculation Activated carbon Chlorination
Ozonation
Filtration Biological UV
activated carbon
Effects COD removal COD removal
Ozone Colour removal Removal of specific
Odour removal persistent compounds
Disinfection Disinfection effect
Improvement for
flocculation e.g. on sand filter
Further colour and (reduction of
Fe, Mn, As removal odour removal threadworms)
Partial disinfection Increasing of AOC

Improvement for Improvement for

UV T(%) UV T(%)

Effects Disinfection

UV (Photolysis,
Photooxidation)

Tab.1: treatment steps for drinking water and principle effects

The following two practical examples will give more detailed information using UV and ozone in
drinking water treatment.

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 Mülheim-Styrum / Germany

The city of Mülheim is situated in Western Germany, not far from the mining and heavy industry centre
of the Ruhr, the so called “Ruhrgebiet”. The Styrum-Ost waterworks was constructed in 1912, when
the Rheinisch-Westfälische Wasserwerksgesellschaft (RWW) was established by merging the
Thyssen and Oberhausen waterworks. Just one year later the RWW supplied more than 30 million
cubic metres of fresh drinking water to the population of the surrounding area [1].

Groundwater is in short supply in the Ruhr valley. Even in its early days the Styrum-Ost waterworks,
like many waterworks in the Ruhr valley even today, artificially recharged the groundwater by taking
surface water directly from the river Ruhr and infiltrating it through slow sand filtration beds into the
sand and gravel substrate. After several days’ passage through soil, the enriched groundwater, partly
mixed with bank-filtered water from the Ruhr and natural groundwater, was extracted, disinfected with
chlorine and pumped into the water supply network.

Growing demand for water in the 1960s and 70s, together with periods of extreme drought and ever
increasing periodic contamination of the Ruhr, resulted in considerable problems with regard to the
quantity and quality of drinking water. These problems could no longer be solved by the traditional
method of artificial groundwater recharge by means of slow filtration through sand.

In 1982, therefore, the RWW introduced additional treatment stages in its Mülheim-Styrum-Ost
waterworks, making use of the Mülheim Method. This method was developed by the RWW in the mid
1970s, in cooperation with the Engler-Bunte Institute of the Technical University of Karlsruhe and was
first used in its Ruhr waterworks in Mülheim-Dohne in 1977. Today it is an internationally recognised
method for the advanced treatment of river water. As a multi-barrier system with several treatment
stages, including the use of ozone as an oxidising agent and disinfectant, together with adsorptive and
bioactive active carbon filtration and subsequent disinfection, which is now carried out with UV light.
It yields drinking water of constantly high quality, even when the raw water conditions are at their most
unfavourable.

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 Fig. 1: The Mülheim Method in the Mülheim Styrum-Ost waterworks

Ozone is produced in the Styrum-Ost waterworks from atmospheric oxygen by three ozone generators
(capacity per generator 6 kg = 18 kg O3/h in total) from WEDECO-Trailigaz. The system includes air
purification equipment with blower, refrigerator and air drier, and can handle a maximum water
throughput of 6,000 m³/h. The ozone input is 1-3 g O3/m³ water. Any excess ozone is eliminated with
the help of catalysts. The treated water is pumped from the clarified water tanks to the filtration plant.

The ozone oxidises any dissolved iron or manganese in the water, forming filterable suspended solids.
Poorly biodegradable organic substances are oxidised, so that they can be biodegraded or adsorbed
in the downstream active-carbon-containing filtration stages. Ozone also has a disinfectant action, so
that microorganisms in the water from the Ruhr can be inactivated before the filtration stage. This is an
important microbiological prerequisite for the following filtration stages.

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 Filtration (3rd stage)

Filtration takes place in a pressure filter system with 12 double-chamber filters, designed to cope with
a maximum water throughput of 6,000 m³/h.

Filter properties:
Diameter 6.3 m
Height 13.5 m
Throughput 500 m³/h
Speed max. 16.5 m/h

Filter material, top chamber:

VA coke (particle size 0.5 – 1.6 mm) 1.2 m
Filter sand (particle size 0.4 – 0.8 mm) 0.8 m
Gravel support layer (particle size 1.2 – 6 mm) 0.45 m

Filter material, bottom chamber:

Active carbon (particle size 0.5 – 2.5 mm) 4m

The filter system holds back the iron and manganese oxides, while dissolved organic substances are
biodegraded and adsorbed.

After filtration, i.e. before the water passes into the municipal supply network, the water is again
disinfected. This safety disinfection was previously carried out with chlorine gas (Cl2) or chlorine
dioxide (ClO2). Due to the ever-present health risks associated with the use of chlorine-containing
disinfectants, and the impairment of the smell and taste of the water, the Styrum-Ost waterworks
switched to non-chemical disinfection methods such as UV technology.

Finally the corrosivity of the water is reduced by adjusting the pH with sodium hydroxide (NaOH).

After this treatment the water is stored temporarily in two round tanks. Each of them has a capacity of
3,500 m³. A total of 14 single-stage centrifugal pumps then transport the drinking water through three
pressure zones into the RWW supply network.

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 UV disinfection

The new UV disinfection system came into operation in 2003, replacing the previously used chlorine-
based safety disinfection system. The system was installed while the waterworks was in operation. A
total of 4 UV reactors based on low pressure technology were installed in the pipe gallery. The system
is designed for a maximum water throughput of 8,000 m³/h.

Fig. 2: WEDECO K3000 UV reactor for disinfection of drinking water

The technical data of the four UV reactors are as follows:

Water throughput per reactor max. 2,000 m³/h
Designed for spectral adsorption coefficient of 1.6/m
Power input per reactor 6-17 kW
Length of the reactor with inflow and outflow sections 3,800 mm

Each reactor contains eight rows of nine Spektrotherm low pressure gas-discharge lamps, which can
be switched and dimmed in groups. This ensures that the performance of the system can be
automatically adjusted to the disinfection requirements when the flow rate is low. The system can thus
be operated very economically.

The radiation of at least 400 Joule/m² generated in the UV reactors at a wavelength of 254 nm
ensures more than 4-log inactivation of the microorganisms. At this level of irradiation, photo-
reactivation (the ability of certain microorganisms to repair the damage to their DNA enzymatically) is
also reliably suppressed.

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The whole UV system is controlled by a programmable logic controller with highly complex programs.
The fully automatic filter plant is also integrated into the control system, with flow control for each
reactor. The UV system is DGVW-certified with regard to four operating points.

The introduction of UV disinfection in the Styrum-Ost waterworks replaced the use of health-
endangering chlorine in the final disinfection. The final safety disinfection of the drinking water is an
essential part of the treatment of surface water. UV technology avoids the impairment of the smell and
taste of the water that can be caused by chlorine and its reaction with other substances in the water.
This applies especially to the odour-intensive chloramine, which can be formed when chlorine reacts
with the small quantities of ammonium that are present in the water from the Ruhr. This can be a
recurrent problem during cold winters in particular, when there is limited nitrification. In addition the
formation of other by-products of chlorination, such as haloforms and other chlorinated organic
compounds, is avoided. These substances are suspected or being a health risk.

Another advantage of UV disinfection is that it eliminates the risk of microbic recontamination of the
drinking water in the supply network, which is present when chlorination is used. The formation of
microbiologically useful substances as by-products of chlorination is thus avoided.

“Good water from a healthy environment” - this claim is simultaneously an inspiration and a blueprint
for the RWW Rheinisch-Westfälische Wasserwerksgesellschaft mbH, so that it can achieve its
objective of providing more than 1 million customers with good quality drinking water every day. The
largely biologically based Mülheim Method was developed by the RWW and first used on the Ruhr. It
has set new standards throughout the world for obtaining drinking water from rivers.

Klungset Water Work, Fauske / Norway

In Norway are many smaller municipalities who are responsible to deliver safety and healthy drinking
water. The Fauske municipality decided in 2003 to install the compact water treatment system “Aqua
Zone”. Beside disinfection the main treatment goals are colour and humus removal. Therefore the
treatment system consists different barriers including ozone, filtration and UV. The system overview is
described in Fig. 3.

Klungset is the first water work in Norway with the process combination ozone, carbon/bio filter and
UV. This process will replace chlorine in the future. The capacity of the plant is 144 m³/h. The quality
of the raw water from a lake is as follows:
Colour: 20 - 30 mg Pt/L
Organic compounds: 3 – 4 mg/L
Bromides: 0 – 11.8 µg/L

The installed ozone capacity is 1.2 kg ozone/h. The UV system is biodosimetricly tested and certified
following a DVGW Standard for a dose of 40 mJ/cm².

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 AIR OUT
OZONE
DESTRUCTOR

BARRIER 1
RAW WATER INLET

PRE FILTRATION
(OPTION)

BIO FILTER
CONTACT TANK
TANK

EJECTOR

OZONE BARRIER 2
PRODUCTION UV SYSTEM

OXYGEN
PRODUCTION
PRODUCTION
CLEANED WATER

Fig. 3 : Process description Fauske

Principle aspects of ozone and UV barriers in municipal waste water treatment

Municipal waste water is often a complex mixture of waste from house holds and different kind of
industries. Traditional treatment techniques include coagulation/flocculation/sedimentation processes,
biological steps and filtration steps. With the improvement of waste water treatment techniques and
the extension of regulations given by the authorities, nowadays further treatment steps are under
discussion, e.g. membrane filtration, UV-disinfection, ozone oxidation, adsorption.

A well-known example of such regulation is the EU bathing waters directive. For effluents from waste
water treatment plants to be discharged into bathing water, standards applicable to germ reduction
must be met in the treated water. Also for the re-use of municipal waster water, e.g. for agriculture,
strict limits have to be met.

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Another topic that throws light on a debate of the need of further treatment techniques is connected
with substances that are not or hardly biodegradable. They are referred to as persistent substances.
These may be of various anthropogenic origins. The main compounds/areas of origin discussed in this
connection include industrial chemicals (e.g. nonylphenols, organotin compounds, PCB, phthalates),
pesticides (e.g. DDT, Gammexane), medicines and cosmetics.
Furthermore public debate is currently focusing on what are called endocrine disrupters. The term
“endocrine” denotes substances that affect the hormone system [2]. Negative effects on the hormone
system of fish in surface water have been reported [3]. Effects such as reduced fertility of fish are to
be observed in particular in the area of influence of sewage plant outlets. Possible effects on humans
are still the subject of controversy. Aspects under discussion include general reduction of fertility,
impaired development of sexual organs in young males and greater incidence of tumours.

In principle recycling of polluted water is mostly limited or even excluded by contamination of

persistent substances, germs, odours and/or colour. This limitation is evident as long as no additional
treatment is available.

In Tab. 2 some principle treatment steps and the main effects of ozone and UV are described.

Primary Biological Clarifier Additional

treatment treatment Filter treatment

Technique Membrane
Flocculation Activated sludge Sedimentation
Chlorination
Coagulation Fixed-bed Sand filter
Ozone
Sedimentation Different kind of Different
UV
Filtration reactors membrane filters
Adsorption (AC)
Effects COD removal
Ozone Removal of specific
persistent compounds
Disinfection
Further colour and odour
removal
Improvement for UV T(%)
Effects Disinfection
UV
(Photolysis, Photo-
oxidation)

Tab.2: Treatment steps for municipal waste water and principle effects

The following two practical examples will give a more detailed picture of advantages using ozone in
the municipal waste water treatment.

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 Tubli plant / Bahrain

The Ministry of Works and Agriculture of the State Bahrain decided to use an ozone treatment step for
the municipal waste water treatment plant Tubli. The total treated water flow is 200.000 m³/d
(300.000 m³/d future extension). The traditional primary and secondary treatment steps cannot reach
the limits given by the World Health Organisation Guidelines in association with California standards
and United States Environmental Protection Agency Guidelines for the unrestricted agricultural
irrigation.

Beside certain types of bacteria the main focus, in this case, is the removal of the helminth
“Strongyloides stercoralis”. The established treatment techniques are not able to remove it to
acceptable limits (< 1 helmith/L).

Pilot tests conducted by Associated Consulting Engineers (ACE) showed that in comparison with
chlorine ozone is the more powerful agent for helminth removal [4].

The experimental results illustrate strongyloides stercoralis removal rates of more than 95% with an
ozone dosage of 10 mg/l and 25-30 min reaction time. For the same removal rate a chlorine dosage of
30 mg/l and a reaction time of 120 min were determined.

For that reason an ozone plant with an overall capacity of 144 kg ozone/h (3 times 48 kg/h) was
installed. The designed ozone dosage is 12 mg ozone per litre secondary effluent. For gas
introduction a diffuser system is used. The overall ozone dosage of 12 mg/L is split into two dosage
points – into a pre-ozonation and a post-ozonation step (see Fig. 4). Each ozonation step comprises a
3-chambered contact basin. In each case the retention time is around 25 minutes.

Air Dryers &

Air Filters Ozone
compressors generators

ROD ROD

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Biology Sedimentation Pre-ozonation Sandfilter Post-ozonation

Fig. 4: Flow chart ozone plant Bahrain

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Fig. 5: Ozone plant Bahrain (WEDECO Effizon HP generators)

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 Kalundborg / Denmark

The water treatment plant Kalundborg purifies and clarifies mixed sewage consisting of 20% municipal
and 80% industrial waste water. The industrial fraction largely derives from a sizable international
pharmaceutical company, which operates one of the largest insulin production plants worldwide at this
site.

Although the character of Kalundborg is that of a smallish town, the treatment plant is designed to
purify and clarify the waste water of nearly 350.000 residents resulting from the adjacent
pharmaceutical company. The waste water contains difficult-to-degrade organic impurities monitored
as COD value. Due to the extension of production scheduled by the pharmaceutical company, the
authorities of Kalundborg had decided to redevelop the treatment plant completely.
As last treatment stage an ozone treatment was projected within the recirculation system, for
degrading a volume of up to 1,250 kg COD per day. Therefore the ozone system was designed for
180 kg ozone/h (2 times 90 kg/h).

After passing through treatment stages typical for water treatment plants, the biologically pre-clarified
waste water is treated by ozone within the recirculation system. This ozonation takes place in six
reaction vessels with a total volume of 300 m³. Within a period of only 15 minutes of total contact, a
drastic reduction of the stubborn organic impurities occurs. The COD level before the oxidation step is
between 100-150 mg/l. The treatment goal is to achieve a COD < 70 mg/l.

Such types of waste water not only contain organic impurities as mentioned above, but can also
contain drugs and hormonally active residues, so called “endocrine disruptors”. By conventional
purification and clarification processes these impurities are not degraded sufficiently and endanger the
environment. Research results prove that ozone is an appropriate means to degrade these harmful
substances in municipal waste water. Thus the oxidative treatment of waste water by ozone plays a
decisive role in multi-barrier concepts [5, 6].

technical data:

Waste water flow rate: 1200 m3/h

Ozone generator: WEDECO Type PDO 6500
Ozone capacity: 2 x 90 kg/h O3 at 10 wt% by oxygen
Gas transfer system: 4 booster pumps + 4 injectors
Reaction volume: 300 m³ (6 times 50 m³ vessels)
Reaction time: 15 minutes
Feed gas: VPSA oxygen (1216 Nm³/h)

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 offgas
1100 Nm³/h
Ozone
generator 50 m³ 50 m³ 50 m³
90 kg/h
OUTLET
O2

VPSA-unit INLET
O2/ O3
1216 Nm³/h
O2

Ozone
generator 50 m³ 50 m³ 50 m³
90 kg/h 150 m³/h -
1200 m³/h

O2/ O3

Fig. 7: Flow chart Kalundborg

Conclusion

The described examples highlight many advantages for the use of ozone and UV in drinking and
waste water treatment. Of course these advantages are not really new, but still today these
advantages are not always present in discussions about the right treatment strategy.
In drinking water treatment we are on the way to use more and more UV-disinfection and ozone
oxidation instead of chlorination. And the experience from existing plants can help to find the right
decision designing a new plant.
As advanced treatment of municipal waste waters the use of ozone and UV enables to meet future
water clarification and recycling standards in an economic feasible way. Especially the existing
regulations for disinfection and the possible future regulations for different kind of persistent
substances, e.g. industrial chemicals, hormones and pharmaceuticals can be achieved by ozone and
UV treatment.
Beside the principle, well-proofed treatment effects, cost calculations and operation experience have
to demonstrate the overall advantages of ozone and UV treatment.

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 References
[1] V. Niechiol, M. Schöpel, D. Wittich, R. König, The Mülheim Method – an environmentally friendly
method of obtaining potable water from rivers, using UV light and ozone;
Worldwater and Environmental Engineering, September/October issue 2003, p 32.

[2] M. Schlumpf and W. Lichtensteiner, Hormonaktive Xenobiotika – Störungen von Fortpflanzungs- und
Entwicklungsprozessen (Endocrine xenobiotics – impairment of propagation and development
processes); UWSF-Z. Umweltchem. Ökotox. 8 (1996) pp. 321-333.

[3] H. Seibert, Störungen der Entwicklung and Funktion des männlichen Reproduktionssystems (Impaired
development and function of the male reproductive system), UWSF-Z. Umweltchem. Ökotox. 8 (1996)
pp. 275-284.
[4] R. J. Abumaizar et al., Disinfection of treated Waste Water for Reuse in Irrigation,
International Conference for water technology, Bahrain 2003, conference papers pp. 353-363.

[5] A. Ried, T. Ternes et. al, Ozone and UV - Processes for additional Wastewater Treatment to
meet existing and future Limits regarding Disinfection, Pharmaceuticals and Endocrine Disrupters
th
IOA-16 world congress, Las Vegas, 2003, - Wastewater Applications, p. 61.

[6] A. Ried, T.Ternes et. al, Ozonation: A tool for removal of pharmaceuticals, contrast media and musk
fragrances from wastewater?, Water Research Vol. 37/8, April 2003, pp. 1976-1982.

Acknowledgement

The authors are grateful to the Styrum-Ost water works/Mülheim, Sterner Aqua Tech/Norway,
Associated Consulting Engineers/Bahrain and the municipality of Kalundborg/Denmark for their
contribution, for providing data and for good co-operation.

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