Spotlight
Ozone Applications
and Measurements
By Marianne Metzger
O Bottled water use
zone is a triatomic molecule consisting of three oxygen
atoms. Ozone is a powerful oxidizer that it is used as a
disinfectant in many applications, including municipal
water supplies, bottled water and wastewater. It is also used in
many other industrial applications, including the following:
• To disinfectant laundry in hospitals and other health care
facilities
• Deodorizes air and objects after fires
• Used extensively in fabric restoration
• Kills any bacteria on food or other surfaces in which food
may be in contact
• Sanitization of pools and spas
• Beginning to replace chemical fumigant to kill insects in
grains in storage facilities
• Used to kill yeast and mold spores in food processing
facilities
• Used in washing of fruit and vegetables
• Used in water treatment to aid in the removal of
contaminants, which cause taste, odor and color (such as
iron, manganese and hydrogen sulfide)
• Used to control algae in aqua features and/or fountains
• Used as a sanitizer in pharmaceutical applications
Ozone is a gas that cannot be transported because of its short
half-life, so it must be generated onsite. Ozone has a half-life of
about 30 minutes in water, which means every half hour the initial
ozone concentration will be reduced by one half. There are many
other considerations, such as pH, temperature, the presence of
organics or the presence of inorganics (such as iron) that can
further shorten the half-life, so the concentration of ozone can
diminish quickly.
Ozone can be generated using either corona discharge or
UV lamp generators. It is gaining in popularity due to its benefits
over other traditional chemicals used for disinfection, such as
chlorine.
As a disinfectant in potable water, it doesn’t produce as many
disinfection byproducts (DBPs) as chlorine and still provides some
residual protection regardless of the brief half-life. It can produce
DBPs if there are naturally occurring precursors in the water.
Specifically, if there is bromide present in raw water, using
ozone can produce a byproduct called bromate, which is regulated
by the US EPA as a known carcinogen. The US EPA has established
a maximum contaminant level (MCL) for bromate at 0.01 mg/L
and the FDA has also adopted this standard for bottled water.
Water Conditioning & Purification
The Food and Drug Administration (FDA), an agency within
the US Department of Health and Human Services, is responsible
for ensuring public health by overseeing the safety, efficacy and
security of pharmaceutical drugs, biological products, medical
devices, food supply (including bottled water), cosmetics and
products that emit radiation. In 1982, the FDA classified ozone
as generally recognized as safe (GRAS) for use as a disinfectant
in bottled water with a residual concentration of up to 0.4 mg/L
of dissolved ozone.
Ozone is used almost exclusively in the bottled water industry
as a primary disinfectant due to the FDA approval as GRAS.
The FDA has further recognized ozone treatment to be good
manufacturing practice (GMP) for the bottled water industry.
The FDA recommends using a minimum treatment of 0.1
mg/L of ozone in water in a closed system with a contact time of
at least five minutes. Additionally, in June 2001, the FDA issued
a final rule regarding the use of ozone as an antimicrobial agent
for food, including meat and poultry, so it is becoming a more
common disinfectant in the entire food industry.
Safe usage
While ozone provides excellent disinfection and oxidizing
properties to many industries, at high concentrations it is harmful
to human health when inhaled. When people are exposed
to high levels of ozone they can experience certain health
symptoms, which include dryness of the mouth and throat,
coughing, headaches and chest pains. The Occupational Safety
and Health Agency (OSHA) has proposed maximum acceptable
concentrations (MAC) for ozone in air.
The MAC value is the concentration which a human is
allowed to be exposed to over a certain period of time. For ozone,
the MAC value established is 0.06 parts per million for eight
hours a day, five days per week, with a maximum of 15 minutes
of exposure to levels of 0.3 parts per million of ozone.
Monitoring for ozone is important in many applications.
First, when using ozone that is being released into the air, it is
important not to exceed levels that may present a danger to people
working in that area.
Secondly, ozone that is used as a disinfectant in drinking
water can produce the formation of bromate, which is a known
carcinogen. The level at which ozone is applied becomes very
important in controlling bromate formation.
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Ozone measurement
There are many ways in which to measure residual ozone
concentration depending upon application, accuracy needed,
budget and available resources. This article will focus on
commonly used methods that are designed to measure ozone
levels in water. Some methods are better than others, depending
on the application in which you need to measure.
One way to measure ozone concentrations is to utilize a
probe or electrode that measures oxidation-reduction potential,
commonly referred to as ORP or Redox. ORP is not a measure-
ment specifically for ozone but rather all oxidizing agents,
including other disinfectants such as chlorine, chlorine dioxide
and peroxide. It is commonly used to measure the disinfection
of pools and spas.
The disadvantage of this method is the interference of high
turbidity in water. This can cause ORP readings to be below what
is expected (potentially, even a reducing or negative value). Using
ORP to measure ozone can only be done accurately if measuring
clean water systems that have low turbidity levels.
Another way ozone is measured is the DPD (N,N-diethyl-
p-phenylenediamine) method, which is more commonly used to
measure chlorine. It is a US EPA-approved method for measuring
chlorine in municipal water supplies.
As with ORP, the DPD method also measures other disinfec-
tants that may be present, including chlorine, bromine and iodine.
This can cause higher readings if these substances are present in
the water being tested.
A colorimetric test is used in which DPD reacts with oxidizers
in water (mostly used for measuring chlorine) causing a red color
change that is proportional to the amount of oxidizer present.
This is an inexpensive way to measure ozone, but is only useful
if it is known that no other disinfectants are present. There are
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other more reliable methods if more accurate results are desired
or if other oxidizers are known to be present.
Additional processes
Another ozone test is based upon the DPD method and is
referred to as the DDPD Method (a proprietary method developed
by CHEmetric, Inc.). This method can also be used to measure
chlorine and other disinfectants; if other disinfectants are known
to be present, this may not be the best for determining ozone
levels.
In applications where ozone is the only disinfectants being
used, the DDPD Method can be an accurate and cost-effective
option for monitoring. The sample is initially exposed to an excess
of potassium iodide, with which ozone will react.
Ozone oxidizes iodide into iodine. Iodine in turn oxidizes
DDPD (a methyl-substituted form of DPD) that forms a
purple colored species, which is in direct proportion to ozone
concentration. The colored sample can then be compared to color
comparator ampoules or analyzed in a colorimeter.
The DDPD reagent was developed because it is less
susceptible to low-level chromate interferences that can affect
the DPD Method. This was especially important in treatment of
cooling tower water, where chromate has been used to control
corrosion. Since it was found that chromate presents other health
problems, it has been banned from use in comfort cooling towers
in the 1990s.
A widely accepted method for testing ozone concentration
is the indigo blue method, which is based upon Standard Methods
4500-O3 B (APHA, AWWA, WEF, 1995). This method uses an indigo
trisulfonate reagent that reacts with the ozone present. Ozone
actually bleaches the blue color in direct proportion to the amount
of ozone. The color change is then measured using a colorimeter.
Water Conditioning & Purification
 There is some interference with this Ozone is being used
method; for instance, if hydrogen peroxide in more applications
(H2O2) is present, it will slowly bleach the
indigo blue. This interference can be alleviated
every day, so effective
if samples are analyzed less than six hours after monitoring is important. Ozone being used as a disinfectant requires
reagents are added.
Chlorine can interfere, but can also be corrected for by using other common disinfectants, including chlorine, chloramine and
malonic acid. The presence of bromine in samples can cause
interferences that cannot be fully corrected by the use of malonic
acid, so an accurate measure of ozone with this method cannot
be made if bromine is known to be present.
In-line monitoring
Ozone can also be monitored inline by use of an electrochemical will help meet task requirements and stay within the operating
cell. This method works by passing ozone through a membrane
that converts it into oxygen. This level of oxygen is then measured
by an oxygen-sensitive cell.
This a common method for monitoring ozone levels within
a process, so it can provide constant measurements of the ozone
level. The drawback to this method is that it is fairly costly to
maintain, as the probes need to be cleaned and recalibrated on
a frequent basis.
Ultraviolet absorption can also be used to measure ozone
levels (primarily in air) but can be used to measure directly in
water if a high level of ozone is used in clean-water applications,
where there is low turbidity and dissolved-solid content.
Otherwise, ozone can be stripped from the water and analyzed
using UV absorption.
This is a highly accurate method for detecting ozone and it
is capable of measuring varying concentrations. The equipment,
however, may be somewhat costly for small systems or applica-
tions.
Water Conditioning & Purification
Application selection
Ozone is being used in more applications
every day, so effective monitoring is important.
monitoring to ensure a residual is present, just like
chlorine dioxide. Precise measurement of ozone in water can be
problematic because of potential interferences, unpredictable half-
life in different waters and time of sample collection in relation
to time of analysis.
It is important, therefore, to choose a sampling and monitor-
ing method that will give you the accuracy levels needed. This
budget.
References
1. APHA, AWWA & WEF, “Standard methods for the examination of water
and wastewater,” 19th edition, Method 45000-O3 B (1998).
2. Bader, H. and Hoigne, J. “Determination of Ozone in Water by the
Indigo Method,” Water Research Vol. 15, 449-456. 1981.
3. Delimpasis, Konstantinos J., Ozone and Color Removal, http://ozoneso-
lutions.com/Ozone_Color_Removal.html.
4. International Bottled Water Association, Plant Technical Manual, Jan 2005,
Revision 6.0.
5. Kilham, Lawrence, “Measuring Dissolved Ozone”, Water Quality
Products, October 2003.
6. Steeves, Susan, January 20, 2003, Purdue News, “Ozone may provide
environmentally safe protection for grains.”
7. Technical Data Sheet, Ozone DDPD Method, CHEMtric, Version 5,
December 2008.
8. US Department of Health and Human Services, Food and Drug
Administration Center for Food Safety and Applied Nutrition.
Bottled Water: Residual Disinfection and
Disinfection Byproducts Small Entity
Compliance Guide, www.cfdsan.fda.gov.guidance.
html, May 2009.
9. US EPA, Office of Water April 1999, Alternative
Disinfectants and Oxidants Guidance Manual.
10. What is ORP? , Ozone Solutions, Inc. http://
www.ozoneapplications.com/info/orp.htm.
11. WQA Ozone Task Force, “Ozone Treatment,”
Water Conditioning & Purification, September
2008.
About the author
 Marianne R. Metzger is National Testing
Laboratories, Ltd.’s GPG Business Manager.
She handles various market
segments including water
treatment, well drilling,
public water supplies and
homeowners. Metzger has
a degree in environmental
geology and political science
from Case Western Reserve
University of Cleveland and
spent a couple of years with
Accent Control Systems as a Sales Engineer,
working with water treatment equipment on
commercial and industrial applications. She
previously spent over 10 years with NTL in a
variety of positions including customer service,
technical support and business Group Manager.
Metzger can be reached by phone at 1 (800)
458-3330 EXT 223 or via email at mmetzger@
ntllabs.com
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