Jacek MAJEWSKI

Lublin University of Technology, Faculty of Electrical Engineering and Informatics

Methods for measuring ozone concentration in ozone-treated

water
Abstract. The ozone measurements are gaining in importance as the area of environmental ozone applications to liquids and especially to water
grows. Some a few methods can be enumerated, and each of them has only limited area of applications. The comparison of the methods shows that
there still is a need for rugged, reliable, ozone-specific, direct measurement methods and sensors for measuring ozone concentration in ozonated
water.

Streszczenie. Przyrządy i metody do pomiaru stężenia ozonu w cieczach, a zwłaszcza w wodzie, nabierają coraz większego znaczenia w miarę
rozszerzania się obszarów zastosowań ozonu ze względu na ochronę środowiska. Porównano kilka współcześnie stosowanych metod i wykazano,
że każda z nich posiada tylko ograniczony obszar przydatności. (Metody pomiaru stężeń ozonu w wodzie ozonowanej)

Keywords: water ozonation, dissolved ozone concentration measurement, water disinfection systems.
Słowa kluczowe: ozonowanie wody, pomiary stężeń rozpuszczonego ozonu, układy do dezynfekcji wody.

Introduction ozone solubility, but increase in reaction rates. Since the

The global increase in pollution of surface fresh water as bubbles contain a few percents of ozone, and the solubility
well as seawater is mainly caused by human industrial is low, the mass transfer and, in consequence, the reaction
activity. This problem is even more urgent in highly rates are moderate, even for such powerful oxidant as
populated areas of developed countries, since the ozone (only fluoride exhibits higher oxidation potential) [10].
environment becomes ecologically damaged – and this When the ozone is dissolved in water, there is a need of
degradation is a factor enhancing e.g. the risk of water- measuring the ozone concentration at the inlet. The
spread epidemies [1]. On the other hand, consumers concentration level of the applied ozone depends on the
require from the manufacturers better quality of water and kind of microorganisms or inorganic pollutants to be
food for realizing healthy lifestyle. For these reasons, an destroyed, and on the required reduction ratio (expressed in
intensive search for fast and efficient methods of water logarithmic scale). This level also depends on the designed
purification without residual taste, odour or toxic by- treatment time; the disinfection standards take into account
products is continued. The method of water ozonation both factors (e.g. exposure to 4 ppmw ozone concentration
seems to satisfy these requirements to highly promising for 4 minutes is required) [5]. In practice, the applied ozone
degree [2]. exhibits concentrations from 0.2 ppmw to 10 ppmw; only
Although ozone was discovered in 1839 (by C. F. some processes in wafer technology require ultra-pure
Schonbein) and used for tap water treatment in the water treated with 30 ppmw ozone.
Netherlands (1880’s), Nice (1907) and St. Petersburg A long-term exposure of the personnel to 0.2 ppmw is
(1910) [3], the water ozonation process is still widely harmful for lungs and respiratory tract. A person who
investigated [4, 5]. This research was intensified after 1982, doesn’t work around ozone, may smell in air the
when the US Food and Drug Administration (FDA) concentration 40 μgO3/1 m3air (i.e. 18.7 ppmvO3, or 0.03
recognized safe status for ozone usage in bottled water, ppmwO3= 30 ppbwO3) – “sniff test”. Ca. 0.1 ppmv ozone is
and later for liquid food and beverages processing (in present in the ambient air; so for workspace the US
1997). The designing of optimal water ozonation system is Occupational Safety and Health Administration limits the
a complex task because of unique features of gaseous allowable ozone concentration to 0.1 ppmv. For these
ozone technology as chemical agent. Firstly, the ozone reasons, the residual dissolved ozone in the exit water
generators can operate on either air (the output is 1-3% should be checked and maintained at 5-50 ppbw; if
ozone) or pure oxygen (the output is ca. 6 % ozone) – if the necessary, it should be decomposed using UV radiation of
corona-discharge or other high voltage-based generator is ca. 250 nm wavelengths [6, 11].
used The UV or VUV generator outputs are insufficient
(0.5% ozone or less). So, the gaseous concentrations are Methods for measuring dissolved ozone in water
small. The methods for measuring ozone in water can be
Secondly, ozone is a highly unstable gas which cannot categorized as specific or not specific to ozone. The
be stored [6]. The half-life time of ozone in distilled water is dissolved ozone-specific methods are: the UV absorption
ca. 20 minutes [7] (in raw potable water ca. 10 min.), It method, the indigo method, the amperometric-membrane
facilitates the problem of excess ozone utilization, but method, and the stripping and gas phase detection method.
enforces the installation of the ozone generator as integral The dissolved-ozone not specific methods are: the
part of the ozonation plant [8, 9]. potassium iodide method and the amperometric-bare
Thirdly, the solubility of ozone in water is rather low – method. The absolute method for measuring ozone
approximately 10 times lower than solubility of chlorine [10] concentration is based on the change in volume which
(for this reason, chlorine is still used; although the ozone accompanies the ozone decomposition:
killing power of microorganisms is 400 times stronger than
chlorine). Therefore, a special chamber (bubble column, or (1) 2O3 → 3O2;
contact tank, or contactor) is necessary to allow diffusing
the ozone gas into water [11]. The ozone (mixed with the air the alternative manometric method is based on change in
or oxygen from the generator) is injected into the water in pressure at fixed volume. Unfortunately, these methods are
fine gas bubbles, and the turbulent mass transfer (by time-consuming, and inaccurate because of minute
diffusion) occurs. Higher temperatures mean decrease in changes at low concentrations.

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 The UV absorption method was developed mainly for The diffusion rate is linearly proportional to the ozone
measuring the ozone concentration in air, but it is also concentration in the water (Fig.2).
applicable to dissolved ozone in water – because the UV
radiation at 254 nm wavelength is absorbed only by ozone;
air, water or oxygen are “transparent” to this radiation of
low-pressure mercury lamp. The main equation [12] is as
follows:

1 2
0
6 3

0
O  ppmw  
T I
3

7
(2) log ,
Pkl It

where: T – the absolute temperature; P – the total pressure;

k – the extinction coefficient of ozone; I0 – the intensity for
the ozoneless medium; It – the intensity with ozone present;
l – the pathlength (in cm).

Fig.2. Schematic of a membrane-type amperometric ozone

sensor

The membrane-type ozone sensors are either

amperometric or polarographic electrochemical cells which
transform the measurement in water into measurement in
air. The headspace of the sensors should be periodically
filled with air and the ozone-containing air after the
measurement should be removed.
Fig.1. Schematic of the single beam arrangement of UV method
The stripping and gas phase method is similar to the
membrane-type sensors, but the process of stripping the
The arrangement for measuring ozone in water is shown
ozone from the water can be realized either by bubbling an
in Fig.1; other setups (dual beam or splitted beam) are
inert gas like nitrogen (or air) through the sampled water or
possible. The corrections for temperature and pressure
by intensive shaking a vessel containing the sample – in
inside the sample chamber are necessary for measurement
order to derive the dissolved gas by turbulent flow of water.
in air; for water these corrections can be neglected. The UV
Thin film semiconductor heated metal oxide sensors
absorption method is sensitive to bubbles in water or other
(HMOS) use the change in resistivity on the grain
impurities; the sample should be filtered and protected from
boundaries evolved by the ozone adsorbed on the surface
degassing.
of the semiconductor for sensing the ozone concentration.
In 1953, the first colorimetric oxidant recorder was
The theoretical support of the stripping process is
elaborated. Only in 1978 in Switzerland, the indigo method
Henry’s law which states that the concentration of a gas
was invented. The indigo “blue jeans” dye was chosen
dissolved in the water is linearly proportional to the partial
because the selective rapid reaction of ozone with the
pressure of that gas in the air over the surface of the water
double bond of indigo is useful for its simplicity and lack of
is Higher pressures increase the solubility; according to the
interferences. The decolourization of indigo trisulfonate
so called unitless Henry’s law:
(ITS) under ozone influence causes linear drop in
absorbance with increasing ozone concentration. The (4) p=Hu·c,
indigo method is recommended when the UV absorption
method cannot be performed or the concentration is lower where: p and c are in the same concentration units (e.g
than 100 ppbw. The main drawback of indigo method is its mg/L) for air (p) and water (c), and Hu is the unitless Henry’s
off-line performing. The equation applied to calculate the constant - for ozone Hu =3.71 (gas/aq) at 20ºC. The law is
ozone concentration is expressed as [13]: observed for equilibrium (or steady) state; in practice, that
condition is not met, and the stripping process does not
1
0
0

strictly agree with Henry’s law what in turn influences the

 A
O  ppmw  
3

(3) , accuracy of that method.

fbV
Comparison of different dissolved ozone measurement
where: ΔA – the difference in absorbance between sample methods
and blank solution; b – the pathlength of the cuvette in cm; The electrochemical or HMOS sensors can be
V – the volume of sample added into the ampoule, normally calibrated using both the indigo and the UV methods – but
90 mL); f – the experimentally obtained factor (0.42). the whole range is covered only by the UV method. The
The amperometric bare-electrode sensors use the ozonated sensors can be calibrated against spectrophotometers or
water as the electrolyte. The oxidants present in the water UV absorption analyzers – but these instruments
are reduced at the cathode, and the generated current is themselves must be calibrated against reference solutions
linearly dependent on the concentration of all oxidants or chemical methods like gas-phase titration or iodometry,
present in the water. These sensors require removing of all which are cumbersome and require very skillful staff. For
oxidants but ozone first or correcting for oxidants other than testing if an ozone sensor is still responsive to ozone
ozone. (“bump test”) portable ozonators are used.
These drawbacks can be got around by using an ozone- For reporting low concentrations of ozone dissolved in
specific membrane which is wetted with the flow of water the ppmw (part per million weight by weight) or the
ozonated water; the ozone diffuses through the membrane. ppbw (part per billion weight by weight) units are used. On
the other hand, low concentrations of ozone in air are given

PRZEGLĄD ELEKTROTECHNICZNY (Electrical Review), ISSN 0033-2097, R. 88 NR 9b/2012 254

in ppmv (part per million volume by volume) or ppbv units. Conclusions
In many cases the abbreviation ppm (or ppb) is used which The general trend toward low allowable levels of ozone
can cause confusions. Especially when the membrane-type in air or its residuals in water claims for designing new
or gas stripping sensors are used, the concentration unit meters or sensors for the range of a few tens of ppbw.
must be carefully explained. As the concentration in air is For better control of ozonation plants, there is a need
temperature- and pressure-dependent, one should check if for sensors of short response time, allowing fast reaction to
the results displayed are recalculated by the instrument to unexpected events within the installation.
standard conditions. For better metrological characteristics of ozone
sensors, active sampling should be introduced to improve
the contact of the sensing device with the sample.
The great problem is the calibration of the instruments
for measuring dissolved ozone concentration. The UV
method is most reliable as the reference method, but the
trouble is to compose accurate reference solutions to check
the UV analyzers. The same concerns the indigo method.
Unfortunately, there are not reference standards for
calibrating instruments for measuring dissolved ozone.
Some attempts to calibrate the membrane-type
amperometric ozone sensors against reference gas
mixtures containing oxygen are made. Oxygen is not
unstable like ozone, and its concentration in air is well
Fig.3. The dissolved ozone measurement range of different known all over the world. However, the measurements of
methods (in ppmw) – average accuracies are shown over the bars the gaseous ozone from a sample are not as reliable as of
the dissolved ozone, obtained directly in water.
In recent years, a tendency for expanding the There still is a need for rugged, reliable, ozone-specific,
measurement range toward lower limits of measurable direct measurement methods and sensors for measuring
ozone concentrations can be observed. This is caused by ozone concentration in ozonated water.
reducing the allowable concentrations in workplaces as well
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Author: dr inż. Jacek Majewski, Lublin University of Technology,

Faculty of Electrical Engineering and Informatics, Nadbystrzycka
Street 38, 20-860 Lublin. E-mail: [email protected]

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