Ozone Hazards incurred in γ-Plant Operation

Introduction

THE IRRADIATION of air produces some toxic gases such as ozone, nitric oxide, nitrogen
dioxide, nitrogen trioxide, nitrogen tetraoxide, nitric anhydride and nitrous oxide. Of these gases,
ozone is the most important because of its toxicity and may be produced in such quantities as to
constitute a health hazard within the irradiation room (IAEA79) (with the possible exception of
nitrogen from relatively harmless nitric acid). Safety requirements in the operation of the γ-irradiation
plant at the Centro Nuclear de México may be conservatively centered around ozone production. In
addition to personnel safety, the effect of enhanced concentration of ozone on irradiated materials
must be considered. This is especially true for food preservation by radiation since ozone in low
concentration is strongly germicidal and may also cause injury to the tissues of the irradiated
materials.

Toxicity and explosive characteristic of ozone

Ozone in any appreciable concentration is very toxic. the LD 50 of ozone for a 3-hr exposure is
1.26 X 10-5 by volume for mice and 1.31 X 10-5 for rats(Mi56). Man, in some cases, is believed to be
even more ozone sensitive than the usual laboratory animals. Concentrations as low as 2 X 10 -6 may
cause severe irritation in less than 1hr for man. Therefore, in 1971, The American Conference of
Governmental Industrial Hygienists (ACGIH) adopted a maximum allowable concentration by volume
as 0.1 ppm (1 X 10-7) for personnel exposure based on an 8-hr work day, 40-hr work week.

The explosive hazard of ozone in concentrated form is well recognized, even in cases where
experiments were conducted at liquid nitrogen temperature.

Quantitative aspects of ozone production

The production rate, p, of a chemical species is related to the integral dose to the air volume
irradiated via the radiolytic yield, G, the number of molecules formed per each 100 eV of energy
deposited. Recent studies have reported the radiolytic yield of O3 in pure oxygen to be around G=13
molecules per 100eV. In air, an efficient charge-transfer mechanism (positive charge transfer from
N2+ ions to O2) enhances the O3 yield, and G-values are believed to be in the range from 7.4 to 10.3
molecules per 100eV, depending on the instantaneous dose rate, even though air is only one-fifth
oxygen. Such values imply that more than one ozone molecule is formed for every ion formed (34 eV
per ion pair). This yield represents an efficient conversion mechanism for O 3. The yields for the other
toxic gases are smaller; NO is consumed by the more copious O 3 to produce NO2 and, therefore, NO2
is the predominant oxide of nitrogen.

Ozone decomposes spontaneously, reacts chemically with air impurities and other materials,
and is decomposed by the radiation itself. The effective decomposition time will therefore depend on
room size, wall material, temperature, and impurities in the air and ozone concentration. The
decomposition time in a typical research installation has been found to be about to be about 50 min.

Concentration build-up

The first step in estimating the concentration of ozone is the determination of its production
rate, p, for each situation in question. In this note, we express, p, in units of liters per minute, which is
convenient when the room volume is also expressed in liters. Using G=11, which is the G-value from
air reported by Shah and Maxie and density of the air equal to 0.001293 g/cm 3, and assuming a
spherical room of radius R, cm, the production rate, p, of ozone in liters per hour is 1.3838 X 10-
10 3
R D, where R is the radius of the spherical room in cm and D is the dose rate in gray per hour.
 The average dose rate, D, in the air considering a point source of 60Co situated in the center
of a spherical room of radius R cm, is 3.84 X 102 S/R2 gray per hour, where S is the strength of the
source in curies. It is difficult to calculate the dose rate for a room other than spherical, but in all
instances the average dose rate received from a given source is smaller than the average dose rate
in a sphere of equal volume. Hence, if calculations are made for a normal room, the results for a
sphere of equal volume will provide a safety margin.

If we assume an average dose rate of 3.8 X 10 2 S/R2 gray per hour, the volume of ozone at
standard temperatures and pressures produced per hour in the room will be equal to 5.314 X 10 -8SR
liters per hour.

Ventilation requirements

It is now possible to estimate the amount of ventilation required to eliminate the danger to
health. Methods other than ventilation could be considered (Ki60), but as ventilation, which is
required for the present purpose, is not in excess of normal practice, ventilation would seem to be the
method of choice.

Table 1. Toxic gases produced by radiation at γ-plants

GAS TLVa(ppm) G (air )b (molecules Decomposition time

per 100 eV) assumedc (min.)

Ozone O3 0.1 11 50
Nitric oxide NO 25
Nitrogen dioxide NO2
Nitrogen trioxide NO3
(0.15)
Nitrogen tetraoxide N2O4 5
Nitric anhydride N2O5
Nitrous oxide N2O
a
Threshold limit value. Maximum concentration averaged over any 8-hour work shift assuming
40-hour work week. From the American Conference of Governmental Industrial Hygienists
(ACGIH).
b
Values from Shah and Maxie and Willis et al., theoretical values are in parentheses.
c
Decomposition time for ozone may depend on size of room and nature of material present.
This value from George et al. was found in a typical research installation.

The concentration build-up of ozone, C(t), is described by the formula:

C(t) = pT (1 – e-tb/T) e-t/T

V
Where C(t) is the concentration (dimensionless), p is the production rate of ozone in liters per
minute, T is the effective removal time in in minutes, V is the room volume in liters, t b is the build-up
time or “on time” in minutes and t is the decay time after turnoff in minutes. T is determined by the
removal process as follow:
T = T (vent) . T (decomp)
T (vent) + T (decomp)

Where T (vent) is the room volume divided by the air volume exhausted per unit time in minutes and
T(decomp) is the decomposition time of the gas in question. For ozone, we take the decomposition
time to be 50min.
If the ozone concentration in the air is to be kept at a concentration, c, in ppm, then, assuming
complete mixing, 5.314 X 102 SR/c liters of air per hour must be removed from the room. For a room
volume having 4/3 π R3cm3 and assuming c equal to 0.1 ppm this entails 126.8 S/R2 air changes per
hour.
Ventilation at the calculated rate would permit uninterrupted working while breathing the air
removed form the source room, or would permit uninterrupted working in the source room, if prior to
entry the ventilation were switched off at the same time as removal of the source.
In the same cases the ventilation requirements to maintain the ozone concentration below the
maximum permissible level might be excessive. In such instances it would be preferable to maintain a
reasonable ventilation rate and, after switching off the gamma plant, wait for a lapse before entry into
the irradiation room. The Gamma Plant installed at the Nuclear Center of Mexico is an irradiator
designed for the sterilization of disposable products with 60Co. The system is comprised of a flat
vertical plaque carrying the 60Co source pencils, a source raising and lowering device and a water
storage pool to shield the source when not in use. 60Co is doubly encapsulated in AECL type C-188
stainless steel pencils. Each pencil contains 112g of 60Co and, at 30 Ci per gram, will have a total
activity of 3360 Ci. The total activity of the irradiator is 0.96 MCi. The volume of the irradiation room is
107m3, then assuming a spherical volume of 4/3 π R3 cm3, the radius is equal to 294 cm. The
production rate of ozone in liters per hour, p, is (5.314 X10-8)(9.6 X 105) (294) = 15 liters per hour.
The ozone concentration just after the source shut-down, assuming 20 changes of air per
hour, will be 13 ppm.
The steady-state concentration of ozone can be calculated for various ventilation rates,
assuming complete mixing. The time in hours, t, after the irradiation stops and before the
concentration is reduced to c ppm, can be calculated from the following formula:
t = 1 ln C
γ c
where γ is the number of air changes per hour and C is the ozone concentration in ppm when the
irradiation stops.

Table 2. Number of air changes per hour and time after irradiation stops for the ozone level to reach
0.1ppm into the irradiation room of the γ-plant
Number of air changes per hour (h-1) Waiting time for the ozone level to reach 0.1ppm
(min.)
20 12
30 7.3
40 5
50 3.8
60 3
70 2.4
80 2.0
90 1.7
100 1.5

Table 2 shows the number of air changes per hour and the time (in minutes) after irradiation stops for
the ozone level to reach 0.1ppm into the irradiation room of the gamma plant installed at the Nuclear
Center of Mexico.
Sense of smell provides an additional aid to safety. The smell of ozone can be detected at a
level of about 0.1ppm; hence if one requires that the ozone concentration be reduced to below the
level where it can be detected by smell, there will be no danger to health, provided 0.1ppm is
accepted as the maximum permissible level for safe working conditions.

Acknowledgements – the authors are grateful to Dr. and for their helpful suggestions and comments
during the preparation of this manuscript.