Advanced Oxidation a Powerful Tool for Pool Water Treatment

T. Glauner1, F.H. Frimmel1

Introduction
Swimming has become a year round activity, widely enjoyed for leisure as well as for exercise.
In Germany about 250 million people visit public pools each year. Therefore pool water is
regarded as a health priority which should be free of infectious feces-associated microbes such
as viruses, bacteria and protozoa. Pool water disinfection with chlorine is therefore widely
accepted. Further key elements of pool water treatment are flocculation and sand filtration
which were derived from a single-pass drinking water treatment. In contrast to the drinking
water treatment pool water is continuously recirculated to reduce heat energy and fresh water
use. The continuous introduction of chlorine and organic compounds by bathers which are not
necessarily similar to natural organic matter are further features of pool water chemistry. As a
result disinfection by-products (DBPs) are formed at relatively high concentrations which are
known to be responsible for eye and skin irritations or may cause allergic asthma [1-3]. Beside
the chloramines the major DBPs in pool water are the trihalomethanes (THMs) with
concentrations up to several hundreds of microgram per litre [4-6]. As potential carcinogens
maximum permissible concentrations of THMs are regulated for pool water in several European
countries [7]. Recent work showed that pool water may also contain genotoxic and low
molecular weight compounds which are not eliminated by filtration techniques not even with
nanofiltration [8].
An efficient elimination of pool water DBPs therefore requires advanced treatment technologies
which comprise an additional oxidation. Ozone was first used for pool water treatment in 1964
and is an integral part of several treatment combinations for public pools in Germany today. The
main objective of the ozonation has been the oxidation of organic water contaminants to
minimize the formation of halogenated DBPs in the subsequent chlorine disinfection. In addition
ozone has the ability to inactivate even chlorine resistant pathogenic microorganisms like
Cryptosporidium parvum oocysts or Giardia lamblia [9]. According to the German standard DIN
19643 ozonation of pool water is performed with an ozone concentration of 0.8 to 1.5 mg/L and
with a contact time of 3 to 10 minutes [10]. In contrast to a single-pass drinking water treatment
which mostly uses ozone for preoxidation the ozonation of recirculated pool water has to cope
with previously formed halogenated DBPs. Because of the low electron density at the carbon
centers oxidation of chlorinated DBPs by ozone is slow and therefore not very efficient [11].
Investigations of Eichelsdrfer et al. [12] showed that a prolonged contact time of 20 minutes
and more was advantageous in respect to the elimination of DBPs. In terms of the required
reactor sizes such long contact times are not realizable for the usually in pool water treatment
applied flow rates. Compared to ozone the reactions of OH-radicals with pool water
contaminants are less selective but much faster. For the reaction of chloramine with ozone
which was studied in detail by Haag and Hoign [13] the rate constant is 2.6101 L/(mol s) and
2.8109 L/(mol s) for the reaction with OH-radicals [14]. As a further example the rate constant
for the reaction of chloroform with ozone is less than 1.010-1 L/(mol s) [13] and 5.0107 L/(mol s)
for the reaction with OH-radicals [15]. Therefore even if the concentration of OH-radicals is
much lower compared to ozone advanced oxidation processes (AOPs) might be advantageous
for pool water treatment. The application of AOPs may result in shorter residential times in the
treatment process and in smaller oxidation reactors. However, previous investigations showed
for a single-pass drinking water treatment an increased AOX and THM formation potential
compared to ozonation due to the formation of carbonyl compounds and activated aromatic

compounds [16]. The formation of DBP precursors could be also a drawback for the application
of AOPs in pool water treatment which might undo the benefit of a possible DBP elimination.
In this study we show model experiments for the application of ozone based AOPs to the
treatment of pool water samples. The elimination of pool water DBPs and their precursors by
AOPs was compared to ozone and UV irradiation. Furthermore the DBP formation in a
subsequent chlorination was compared for the different oxidation technologies to simulate the
continuous chlorination in the pool water circulation. In conclusion we propose a treatment
combination for swimming pool water treatment with a superior elimination efficiency and
reasonable operation costs.
Material and Methods
Sample collection and analytical procedure
Pool water samples were collected directly from an indoor (IP) and an outdoor pool (OP) in 25 L
glass bottles. Both pools were operated with filling water from the same drinking water supply
system and were treated by flocculation sand filtration chlorination. At the pool site electrical
conductivities and pH values were measured and given at a reference temperature of 25C. The
concentration of free and total chlorine were estimated photometrically with a commercially
available chlorine cell test (Merck, Darmstadt, Germany) after reaction with N,N-dipropyl-pphenylenediamine. Additional samples were taken for the measurement of trihalogenmethane
(THM) concentrations. In this samples residual chlorine was quenched by addition of sodium
thiosulphate. Characterization of oxidation experiments was performed by measurement of the
AOX (on activated carbon adsorbable organically bound halogens) concentration (Euroglas
ECS 1200, Thermo Electron GmbH, Dreieich, Germany) and the dissolved organic carbon
(DOC) concentration (Sievers 820 PMT, Ionics instruments, Boulder, Colorado, USA). In
addition the DOC was characterized in detail by size exclusion chromatography (TSK-HW40S;
Merck, Darmstadt) with continuous UV254nm and DOC detection. THMs were measured with a
temperature-programmed gas chromatograph (Chrompack CP 9000, Varian Inc., Palo Alto,
USA) with electron capture detection after dynamic headspace extraction. Brominated THMs
were normalized to chloroform and given as total THMs (TTHM).
Model experiments
All oxidation experiments were performed in a laboratory loop-type reactor with a total volume of
2 litres. Ozone entered the reactor through a glass frit counter current to the sample flow of 1.6
L/min which was generated by a stirrer. Ozone was created with an ozone generator (Ozomat
COM, Anseros, Germany) from dried air or oxygen with an flow rate of 20 L/h. The ozone
concentrations in the reactor inflow and in the reactor exhaust were measured with ozone
detectors (Ozomat GM, Anseros, Germany). The ozone dose in solution was adjusted to 3 and
10 mg/L respectively based on an ozone balance in the reactor inflow and exhaust gas. On
average an ozone dose of 3 mg/L was reached after 5 minutes, and an ozone dose of 10 mg/L
was reached after 20 minutes of ozone application. Hydroxyl radical generation was accelerated
by hydrogen peroxide dosing in the stoichiometric ratio of 0.5 moles H2O2 per mole ozone
immediately before ozone introduction or by UV irradiation with a pre-equilibrated mercury
medium pressure lamp (Heraeus TQ 150). After the ozone dose was reached the ozone
injection was stopped and the sample was left in the reactor for another 10 minutes to ensure
sufficient reaction time. Due to the storage the free active chlorine (FAC) concentration in IP
water at the beginning of the oxidation experiments was always below the detection limit of 0.1
mg/L. For several experiments water of the outdoor pool was spiked with human urine and
sodium hypochlorite solution to reach a DOC level of 2.7 mg/L and a FAC level of 2.5 mg/L. For
TOC and AOX measurements the residual oxidant was quenched by adding an excess amount
of sodium sulfite. Details to the used reactor assembly and further experimental conditions were
described elsewhere [17].
Furthermore the raw waters and the oxidized water samples were chlorinated in a subsequent
model experiment to estimate the predictable DBP formation in pool water treatment. Therefore
the samples were buffered with phosphate buffer to neutral pH and hypochlorite solution (12%
FAC, Roth, Karlsruhe, Germany) was added to the sample to reach an initial FAC concentration
of 10 mg/L. The samples were filled gas free in 500 mL glass bottles which were tightly sealed

and protected from light. After a reaction time of 48 hours residual chlorine was quenched by
adding an excess amount of sodium thiosulphate and TOC, AOX, and TTHM concentrations
were measured.
Results and Discussion
For the IP sample the pH was 7.3 and for the sample OP-spike the pH was 7.5. Table 1 shows
the FAC concentration and the load with organic compounds and DBPs for the two pool waters
and the OP-spike.
Table 1:

Characterization of the pool water samples and the pool water spiked with urine and
hypochlorite.

Sample
IP
OP
OP-Spike

FAC
in mg/L
0.7
0.5
2.5

DOC
in mg/L
1.3
0.7
2.7

AOX
in g/L
220
130
147

TTHM
in g/L
44
n.a.*
26
* n.a. = not analyzed

The IP sample showed a much higher contamination compared to OP since IP was taken
shortly after swimming lessons of a primary school whereas OP was taken at a rainy day with
only few pool visitors. Therefore it was decided to spike OP with human urine prior to oxidation.
For IP a chlorination with an elevated chlorine concentration of 10 mg/L resulted in an additional
AOX formation of 12 g/L whereas the OP-spike showed a much higher AOX formation of 122
g/L. That can be explained by the introduction of fresh contaminants with the urine which can
readily react with chlorine to form DBPs. In contrast the additional IP chlorination led to a further
THM formation of 48 g/L whereas the chlorination of the OP-spike just resulted in further 25
g/L THM. A possible explanation for this observation might be the additional chlorine
consumption in OP-spike because of the higher concentration of urea and ammonia. The
suppression of THM formation in natural waters with high ammonia levels or after urine addition
was observed by Duong et al. and Kim et al., respectively [18, 19].
Ozonation, peroxone- and ozone-UV-treatment were compared on the basis of their DOC and
AOX elimination for IP at two different ozone doses. For ozonation and AOPs no DOC
elimination was observed for the lower ozone dose of 3 mg/L. In contrast the higher ozone dose
of 10 mg/L resulted in a DOC elimination of 15 % for ozonation and peroxone treatment and of
even 32% for ozone-UV treatment. The oxidation led also to an alteration of the DOC
characteristics which was studied by the coupling of size exclusion chromatography and on-line
DOC detection (SEC-OCD). Figure 1 shows a SEC-OCD chromatogram of the original sample
of IP and after ozonation, peroxone treatment, and ozone-UV treatment. It is obvious that
ozonation led to the decrease of the high molecular weight fraction F1 whereas the fractions F2
and F3 which represent polar compounds like carboxylic acids of lower molecular mass
increased. For both AOPs the fraction F1 was eliminated almost completely and for ozone-UV
treatment fraction F3 was decreased to a certain extent. Fraction F5 corresponds mainly to urea
which was hardly eliminated by ozonation and AOPs. The predominant elimination of high
molecular weight compounds by oxidation was proved in a previous study by the oxidation of a
pool water sample after membrane fractionation [8]. Whereas in this study the DOC of the
original pool water was eliminated to 21% the low molecular weight fraction was eliminated to
13% only although a higher ozone/DOC-ratio was applied.

KD
0

2,0

IP
IP after ozonation
IP after peroxone treatment
IP after ozone-UV treatment

F3

Abundance

1,5

F1

F5

F2
F4

1,0

0,5

0,0
20

30

40

50

60

70

80

90

retention volume in mL

Figure 1:

SEC-OCD chromatograms of pool water IP and after ozonation and AOP treatment.

In figure 2 the elimination of DBPs (measured as AOX) with the different oxidation reactions is
shown. One can see that ozonation and AOPs led to a significant reduction of AOX compounds
even with the lower ozone dose. Ozonation reduced the AOX concentration to 37% and 59% for
the lower and higher ozone dose, respectively. The AOPs offered even higher eliminations of up
to 52% for the lower and even 72% for the higher ozone dose with slight advantages for the
peroxone treatment.

3 mg/L O3
10 mg/L O3

AOX elimination in %

60

40

20

0
ozone

Figure 2:

peroxone

ozone-UV

AOX elimination in the model experiments for the pool water IP for ozonation and the
two AOPs (relative to the original sample).

Compared to a previous study [17] which showed a 10 to 20 fold higher DOC and AOX
elimination of the AOPs compared to ozone for a reaction time of 3 minutes, in this study the
observed DOC elimination for ozonation and ozone-UV treatment in pool water was significantly
higher. This can be explained by the elevated ozone doses and reaction times in this study
which favor especially the ozone-UV treatment due to the additional introduction of radiation
energy. This was proved by a solely UV irradiation in the reactor assembly for a comparable
time interval necessary to reach an ozone dose of 10 mg/L which resulted in a DOC elimination
of 12% and an AOX elimination of 51%.

For OP-spike which was treated by ozonation and AOPs only at the higher ozone dose the
DOC and AOX elimination was significantly lower. For ozonation a decrease of 10% was
observed for the DOC and of 31% for the AOX concentration. The AOPs led to a DOC
elimination of about 25% and an AOX elimination of 28% for peroxone and 31% for ozone-UV
treatment. The reason for the lower elimination rates might be the reaction of ozone or hydroxyl
radicals with hypochlorite ions which results in a rapid ozone consumption [13].

120

THM formation IP
THM formation OP spike
AOX formation IP
AOX formation OP spike

DBP formation in %

100

80

60

40

20

0
ozone

Figure 3:

peroxone

ozone-UV

DBP formation in the model experiments for the pool water IP and for the OP spike
which contained an elevated residual chlorine level for ozone, UV irradiation and the
two AOPs (relative to the original sample).

For a pool water which is recirculated and continuously chlorinated the DBP formation in a
subsequent chlorination has to be considered. Therefore IP and OP-spike were treated with
chlorine at a concentration of 10 mg/L after ozonation or advanced oxidation. Figure 3 shows
the AOX and THM formation for the two water samples at the higher ozone dose of 10 mg/L. It
was observed that the AOX formation for IP was lowered by 17% for ozonation and by about
45% for the AOPs. The THM formation was decreased by 30% for ozonation, 54% for peroxone
treatment, and 39% for ozone-UV oxidation. In contrast Kleiser and Frimmel [16] showed for a
single-pass drinking water treatment that ozonation was in respect of DBP formation superior to
AOPs. A possible explanation for our observations might be that for the pool water the improved
DBP elimination by AOPs results in a net decrease of DBPs although the unspecific oxidation
produces additional precursors. For OP-spike which contained residual chlorine the THM
formation was not reduced by the oxidations. The AOX formation was lowered by 20% for
ozonation and by 15% for the peroxone treatment. The ozone-UV treatment led to an increased
AOX formation of about 12% which was also observed for a solely UV irradiation. A reason for
the lower efficiency of the oxidations might be the previously considered ozone consumption by
hypochlorite ions. One possible reason for the increased AOX formation at the UV treatment
might be the photolytic cleavage of hypochlorous acid which results in chlorine radicals and
hydroxyl radicals which both can readily react with organic pool water contaminants [20].
Conclusion
In this study ozonation and ozone based AOPs were applied successfully for the treatment of
swimming pool water in a lab scale oxidation reactor. The results of this study led to the
following conclusions:

Both applied AOPs were superior to ozonation considering the elimination of DOC and
DBPs. Due to the application of higher ozone doses and longer reaction times compared
to a previous study the elimination rates were even higher.
The oxidations led to a DOC elimination which was highest for the high molecular weight
fraction. It has to be proved whether high molecular weight compounds were directly

mineralised or form low molecular weight intermediates which were mineralised in a

subsequent reaction which is more likely.
The efficient elimination of AOX compounds after AOPs led to a net decrease of DBP
formation in a subsequent chlorination. Nevertheless THM precursor formation due to
the AOPs has to be considered since for lower ozone doses and reaction times in a
previous study THM formation after AOPs was slightly increased.
For a real world application one would choose a maximum ozone dose of 3 mg/L or less
because for pool water treatment with a cycle time of about 5 hours an elimination of 30
to 50% for one individual cycle leads to an outstandingly good water quality.
Because of economic reasons and because of the increased THM formation after
ozone-UV treatment the peroxone treatment is most promising. Compared to ozonation
an additional hydrogen peroxide dosing would raise the operational costs by about 0.03
/m3 treated water [21]. Since the elimination rates are much higher for the AOPs
compared to ozonation smaller reactors and an overall reduction of the amount of
treated water is conceivable.

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