2.

RADIOACTIVE TRACERS

2.1.TYPES OF TRACERS

A tracer is any substance whose atomic or nuclear, physical, chemical, or biological properties
provide for the identification, observation and following of the behavior of various physical, chemical or
biological processes (dispersion, mixing, kinetics and dynamics), which occur either instantaneously or in
a given lapse of time (Fig. 10). There are many kinds of tracers. The radioactive tracers are mostly used
for online diagnosis of industrial reactors.

FIG.10. Tracer principle

For conducting a radiotracer investigation, various requirements need to be met before starting the
actual test. The most important of all the requirements is the “Radiotracer” itself. It is of fundamental
importance that the radiotracer compound should behave in the same way as the material to be traced.
Therefore, the selection of an appropriate tracer is crucial to success of a tracer study. For reliable and
meaningful results, an industrial radiotracer must meet the basic requirements such as suitable half-life
and energy of radiation, physical and chemical stability, easy and unambiguous detection. It is often
difficult to meet all the requirements of an ideal tracer and certain compromises have to be made. Even if
a radiotracer meets the required criteria, it may not be available to tracer groups in developing countries.

The behavior of tracer under conditions of the system (physical & chemical conditions) is very
important. One must know, before injecting a tracer, how it will behave in the system. In certain
circumstances, the tracer injected into a system may undergo decomposition, phase change, undesirable
absorption and adsorption, chemical interaction with system constituents leading to incorrect results. For
example, para-dibromobenzene when used at high temperature is adsorbed on the surfaces or packing
inside the reactor vessel and does not follow, faithfully, the organic liquid phase.

While tracing fluid movement in oilfield (inter-well tracing), the reservoir physical and
geochemical conditions pose constraints and an undesirable tracer-loss or delay occurs. Sometimes,
tracers found to behave properly in one reservoir, may not behave satisfactorily in another reservoir.
While tracing aqueous phase (in a liquid/solid phase system like, waste water treatment plant, oil
reservoirs, etc), cationic tracers, with certain exceptions, may lead to problem of sorption and ion
exchange with host material.
2.1.1. Intrinsic and extrinsic tracers

Intrinsic (or chemical) tracers are molecules containing an isotope (radioactive or stable) of one of
the molecule‟s natural elements, which makes the labelled molecule particularly detectable by nuclear or
conventional methods in systems where the dynamic characteristics of the non-labelled molecules have to
be followed. For example, in the case of water, Tritium (1H 3H16O) measured by nuclear techniques (in
practice liquid scintillation counting) is an intrinsic tracer. In this case, the water molecule is traced from
the inside, in the intimacy of it nucleus, consequently the water tracer will (in practice) follow all
movements and reactions of water itself.

Extrinsic (or physical) tracers are made up of atoms or molecules supposed to share the same
dynamic characteristics and, in general, the same mass flow behavior as the investigated medium.
Belonging to this category are all the substances that allow tracing outside the molecular or ionic
structure. For example, in case of water, Na131I and 51Cr-EDTA are examples of extrinsic tracers for
water.

2.2. ADVANTAGES OF RADIOTRACERS

 Most of the radiotracer applications in industrial reactors make use of artificially produced
radionuclides. They have high detection sensitivity for extremely small concentrations, for instance,
some radionuclides may be detected in quantities as small as 10-17 grams.
 The amount of radiotracer used is virtually insignificant. For example, 1 Ci of 131I- weighs 8 μg, while
1 Ci of 82Br- weighs only 0.9 μg. That‟s why, when injected, they do not disturb the dynamics of the
system under investigation.
 They offer possibility of “in-situ” measurements, providing information in the shortest possible time.
 A gamma emitting radiotracer can be measured through radiation transmission, from the outside of a
pipe or vessel. This is of special importance for many industrial plant studies.
 Disappearance of the radiotracer from the medium under investigation through radioactive decay
provides for a repetition of experiments on the same location with the same tracer, all while pollution
declines to a minimum.
 Radioactive tracer can be selective. Several tracers may be employed simultaneously and owing to
their characteristic radiation emissions, they can be measured accurately with the help of
spectrometry.

One of advantages of radiotracer is based on simple fact that it is easier to detect radioactive than
non-radioactive isotopes of the same elements. Vigorous development of analytical technology making
possible the attainment of lower and lower detection limits has challenged radioisotope techniques in their
most conspicuous stronghold: the limits of detectability.

Advances in the performance of modern instrumental analysis in such branches as gas and liquid
chromatography, fluorimetry, atomic emission, and mass spectrometry are reaching ppb levels. In some
applications radiotracers may rank lower (on a comparative basis) than chemical, fluorescent, or stable
isotopes regarding some practical aspects. If a non-radioactive tracer can perform the task, it should be
preferred. Let‟s see some examples.

Example 1: Comparing radiotracer 24Na versus stable isotope 23Na

Chemical behavior of radiotracer 24Na is the same of stable 23Na. Detection limits of conventional
analytical techniques for sodium are typically of the order of nanograms, that is (10 -9/23) x 6.02 x1023 =
2.6 x1013 atoms. In routine work radiotracer will allow to detect quantities 105 times smaller than
conventional techniques.

Example 2: Comparison of tritium measurement techniques

Isotope ratio mass spectrometry (IR-MS) detects tritium at the level of 5 TU = 0.59 Bq/L. Low
background liquid scintillation counter (LSC) detects tritium in routine at the level of 1 TU (1 TU equals
1 tritium atom in 1018 hydrogen atoms), so it is clear that LSC is an exceedingly sensitive method.

Example 3: Radiotracer versus rhodamine in water field measurements

Let‟s compare radiotracer NH482Br commonly used in wastewater hydrodynamic investigations,
with fluorescent dye Rhodamine-WT, which also is used frequently as water tracer. Rhodamine-WT can
be measured down to ppb range in portable fluorometers. Activity concentration of 80 mCi (~3GBq) per
g of NH482Br is obtained at a low flux reactor at 6.6x1011 n/cm2s. Assuming that 10 g of this irradiated salt
suffers a quite high dilution in about 106 m3 of water, resulting mean activity concentration is about 3x104
Bq/m3 = 30 Bq/L, which can be measured very easy. Rhodamine-WT is sold as a 20% solution. Thus,
after it suffered same dilution concentration would be 2 ppb. This is only slightly above detection limit of
fluorometers, but many times higher than the concentration required for radiotracer. It is thus evident that
radiation detection is a much more sensitive method. However, if one looks at mass of dye, it would
correspond to 2 mg/m3 x 106 m3 = 2000000 mg = 2 Kg, that means 10 L, which still is a handy volume to
manipulate elsewhere in fieldwork. This explains why rhodamine is becoming competitive as water
tracers, especially in rivers and other water basins.

2.3. SELECTION OF A RADIOTRACER

Factors that are important in selection of a radiotracer are given as follows:

 Physical/chemical compatibility with the material to be traced

 Half-life
 Specific activity
 Type and energy of radiation emitted
 Availability and cost
 Method of measurement (sampling or in-situ measurement)
 Handling of radioactive materials, radiological protection/regulations.

Under certain circumstances, tracer has to be chemically identical with the traced substance and
then one has to use an intrinsic tracer (also called „chemical radiotracer‟). This is the case when studying
chemical reaction kinetics, solubility, vapour pressures, processes dominated by atomic and molecular
diffusion, etc. Radioactive isotopes of the traced elements and labelled molecules are used as intrinsic
tracers, for example, 1H3HO for water, 24NaOH for NaOH or 14CO2 for CO2, etc..

Whenever the chemical identity of the tracer with the material it follows is not required, the tracer
has merely to fulfill a limited number of not very stringent physical and physiochemical conditions. This
type of tracer is commonly referred to as an extrinsic (or physical) radiotracer. The majority of tracer
techniques applied in industry make use of these extrinsic radiotracers. When tracing elements or
compounds in systems where no chemical changes occur, the radiotracer does not have to be chemically
representative of the element or compound. For example, when water in a plant process is being traced,
the only requirement of the tracer is that it behaves as the water behaves under the conditions of the plant
process.
 Some of the many radiotracers that have been successfully used in this case are 198Au as gold
chloride (effective tracer 198AuCl4-), 24Na as sodium nitrate (effective tracer 24Na+), 131I as sodium iodide
(effective tracer 131I-).

Table I lists some of the commonly used radiotracers in industry.

TABLE I. COMMONLY USED RADIOTRACER IN INDUSTRY

Isotope Half-life Radiation and Energy Chemical Form Tracing of phase

(MeV)
Tritium (3H) 12.6 y Beta, 0.018(100%) Tritiated water Aqueous
Sodium-24 15 h Gamma: Sodium carbonate Aqueous
1.37(100%)
2.75(100%)
Bromine-82 36 h Gamma: Ammonium bromide, Aqueous
0.55 (70%) p-dibrom-benzene, Organic
1.32 (27%) Dibrobiphenyl Organic
CH3 Br, C2H5Br Gases
Lanthanum-140 40 h Gamma: Lanthanum chloride, Aqueous/Solids
1.16 (95%) Lanthanum oxide Solids
0.92 (10%)
0.82(27%)
2.54 (4%)
Gold-198 2.7 d Gamma: 0.41 (99%) Chloroauric acid Aqueous/Solids
Mercury-197 2.7 d Gamma: 0.077(19%) Mercury metal Mercury
Iodine-131 8.04 d Gamma: Potassium or Sodium Aqueous
0.36 (80%) iodide,
0.64 (9%) Iodobenzene Organic
Chromium-51 28 d Gamma: 0.320 (9.8%) Cr-EDTA, CrCl3 Aqueous
Technetium-99m 6h Gamma: 0.14 (90%) Sodium pertechnetate Aqueous
(TcO4-)
Scandium-46 84 d Gamma: Scandium oxide Solids
0.89(100%) Scandium chloride Aqueous/Solids
1.84(100%) ScCl3 (Sc3+)
Xenon-133 5.27 d Gamma: 0.08 (100%) Xenon Gases
Krypton-85 10.6 y Gamma: 0.51(0.7% ) Krypton Gases
Krypton-79 35 h Gamma: 0.51 (15%) Krypton Gases
Argon-41 110 min Gamma: 1.29(99% ) Argon Gases

2.4. METHODS AND TECHNIQUES FOR LABELLING

2.4.1. Solid materials

A. Internal (mass) labelling

A common method for labelling of a solid material is direct activation i.e., to irradiate a portion of
the traced material in a neutron flux and induce the necessary activities. Table II gives examples of widely
used tracers labelled by direct activation of solids. Specially produced glasses containing a chemical
element that can be activated by (n, γ) reactions, are available to any given size distribution and are used
very extensively as sand tracers. 198Au, 51Cr, 192Ir and 46Sc are the radioactive nuclides often induced.

TABLE II. SOME RADIOACTIVE TRACERS INDUCED BY DIRECT ACTIVATION OF SOLIDS

Irradiated material Induced radionuclides

46
Coal Sc, 59Fe
24
Clinker, cement Na, 140La
140
Cracking catalyst La
198
Gold ore Au, 59Fe, 42K, 140La, 56Mn, 24Na, 46Sc,51Cr
64
Copper ore Cu, 42K, 140La, 24Na, 59Fe

Activity calculation of irradiated target in the nuclear reactor

Two major producers of artificial radioisotopes are nuclear reactors and accelerators. Radioisotopes
produced in nuclear reactors represent a large percentage of the total use of radiotracers due to a number
of factors. The nuclear reactor offers relatively large volume for irradiation, simultaneous irradiation of
several targets, economy of production and possibility to produce a wide variety of radioisotopes. There
are more than 50 reactor-produced radioisotopes, many of them suitable for using as radiotracers. The
accelerator-produced isotopes relatively constitute a smaller percentage of total use, mostly in nuclear
medicine, in particular for PET (positron emission tomography) diagnosis. The accelerators are generally
used to produce those isotopes which can not be produced by nuclear reactors or which have unique
properties, such as F-18 and radioisotope generator 88Ge/88Ga.

Radioisotopes are produced by exposing suitable target materials to the neutron flux in a nuclear
reactor for an appropriate time. The nuclear reactors mostly used for radioisotope production are with the
power of around 1 MW. The 250 kW Triga Mark II reactor, which is in operation in some developing
countries, still offers the possibility to activate various substances. Despite the degrees of freedom
provided by many reactors it is not always applicable as the reactor time is restricted and neutron flux is
too low for some applications.

When a target is under irradiation in a nuclear reactor, the activation per second can be represented
by:
dN*/dt = Φ σ NT
where:
 Φ is the neutron flux (n/cm2 s)
 σ is the activation section (neutron capture cross-section, 1024 barn)
 N* is the number of activated atoms (atoms/g)
 NT is the total number of atoms present in the target (atoms/g)

Since the product radioisotope starts decaying with its own half-life, once production starts, the net
growth rate of active atoms can be written as:

dN*/dt = Φ σ NT - λ N*

where: λ = ln2/T1/2 = 0.693/ T1/2 is the decay constant of the being created radioisotope, and T1/2 is
its half-life.
 The above equation can be solved to determine the value of radioactive atoms at the end of
irradiation time ti, as follows:
N* = σ Φ NT [1- exp(-λ ti)]

If a delay time (cooling time) td applies after end of irradiation before the radiotracer can be used,
the activity A of the irradiated sample at the end of the delay time is:

A = σ Φ NT [1 - exp(-λ ti)] [exp(-λ td )]

Example of sample irradiation and activity calculation

Routinely irradiated samples are e.g. KBr-powder to produce 82Br, NaCO3-powder to produce 24Na,
argon filled in a 30 ml quartz capsule at a pressure of 10 bars to provide 41Ar, and many others.

Let us assume an experiment using 82Br as a radiotracer in the aqueous phase has to be performed.
Normally the target material for production of 82Br is potassium bromide (KBr). What is the needed
irradiation time to achieve an amount of activity given a reasonable amount of target material, a relatively
standard flux in a nuclear reactor and a desired cooling time for decay of undesired radioisotopes before
application?

The production activity is calculated according to the above mentioned formula:

A = σ Φ NT [1- exp(-λ ti)] [exp(–λ td )]

where:
 = the thermal neutron reaction cross section in barn (1 barn=10-24 cm2)
 = the neutron flux (in neutrons/cm2s)
NT = the number of target atoms in the target used
ti = irradiation time in the nuclear reactor (normally from few minutes to several days)
td = cooling time after reactor irradiation (manipulation in the hot cells for preparing the appropriate
radiotracer compound, transport to the experimental site) till injection in the radiotracer test (normally
from several hours to few days).

Here, NT may be expressed in terms of the weight of the target compound:

wc  N A  N E  I N
NT 
M c  100

where
 wc = weight of target compound used in g
 NA = Avogadro‟s number (= 6.023 x 1023 atoms)
 NE = number of equivalents of the target element in the target compound
 IN = natural abundance of the target nuclide in the target element (in %)
 Mc = molecular weight of the target compound

Combining both above described equations, it gives:

wc  N A  N E  I N
A     (1  e  ti )  e  td
M c 100
 This formula gives an estimate of the activity of the radiotracer provided that all the other relevant
parameters are known.

If the irradiation time in the nuclear reactor is limited then the amount of target material (wc ) has to
be calculated (as the unknown parameter) to obtain the optimal activity (A) required for an experiment.
The expression for wc becomes:

A  M c 100  e td
wc 
    N A  N E  I N  (1  e  ti )

If irradiation time ti is freely selected, the equation may be solved with respect to ti to give:

1 A  e td  M c 100
ti    ln(1  )
     wc  N A  N E  I N

Example:
Let the target material be KBr and the product radionuclide 82Br. The normal activation reaction is
81
Br(n, γ) 82Br. Then, Mc = MKBr = 119, NE = NBr = 1, IN = 49.3%, = 2.64 barn and T½ = 36 h. Let further
wc = wKBr = 10 g,  = 1012 n/cm2s and td = 24 h. The activity required for the radiotracer test to be
executed one day (24 h) after the irradiation in the reactor is estimated: A = 1 GBq (27 mCi).

Then, the irradiation time ti in order to obtain the activity A = 1 GBq is:

ln 2
24
36 10  e 9
 119.100
36
ti    ln(1   24
)
ln 2 2.64.10  10  10  6.023  10 23  1  49.3
12

ti = 1 h

Normally, the irradiation times for commonly radioisotopes used as radiotracer range in several
minutes to few hours in medium neutron flux reactors. There are some radioisotopes that need irradiation
times from several hours till few days.

B. Surface labelling

The adsorption of a radiotracer (or radionuclide) on the surface of a solid has been used as a
labelling method for sand particles and many powdered materials. The solid particles are first soaked in
stannous chloride (SnCl2) and then placed in an aqueous solution of gold chloride containing radioactive
198
Au. The gold exchanges with tin, through a reduction-oxidation process, to produce labelled particles.
The labelled sand can be used in aqueous systems with no appreciable loss of tracer. Some materials like
cement, carbon black, aluminum powder, etc. can also be labelled with 198Au.

Surface labelled sand and silt with 198Au, 51Cr, or 46Sc have been widely used in sediment transport
studies. Another method for surface labelling is to absorb, soak or sprinkle the material with radioactive
solution. This method has been used for labelling coal and refractory materials.

With surface labelling methods, unlike direct activation, the activity becomes proportional to the
surface area of the material rather than its mass, and it thus depends on the grain size distribution.
2.4.2. Aqueous systems

Tritiated water (HTO) is the only intrinsic radiotracer for water. Other tracers most commonly used
in aqueous solutions are 51Cr-EDTA complex, 113mIn-EDTA complex, Na131I, K131I, 24Na2 CO3,
24
NaHCO3, NH4 82Br, H198AuCl4 and pertechnetate, 99mTcO4-.
2.4.3. Organic materials

The only intrinsic radiotracers for organic materials are 3H, 14C, 32P and 35S labelled compounds.
Being beta-emitters, these are measured through sampling followed by liquid scintillation counting.
Therefore these are rarely used for plant investigations. However they are extensively used in laboratory
investigations and in oilfield tracer tests (inter-well tracing).

Extrinsic tracers are more widely used for tracing organic fluids including dibromobiphenyl and
para-dibromobenzene (C6H482Br2), 131I-kerosene and iodobenzene (C6H5131I), 113mIn in oleate or stearate
form. Validation of these tracers in harsh reactor conditions (high temperature and pressure) has to be
investigated.

For example, Br-82 as dibromobiphenyl was tested in a trickle bed reactor operating at high
temperature and pressure. The boiling temperature of dibromobiphenyl at atmospheric pressure is 370OC.
Since the pressure in the reactor was about 170 kg/cm2, the tracer will not vaporize and will remain in
liquid phase at 400 OC. The results of the tracer tests carried out at temperature of 250 0C show that the
tracer did not appear at the outlet of the reactor indicating the adsorption of the tracer on the catalyst
particles. Another test carried out at lower temperature (~150 0C), showed the tracer did appear at the
outlet but the intensity was much less than in the inlet. This indicates partial adsorption of the tracer on
catalyst particles. In tracer test carried out at temperature about 100 OC the area under concentration
curves recorded were almost equal and the tracer balance was achieved. The results of the tests indicated
that at temperature more than 100 0C, the tracer (Br-82 as dibromobiphenyl) gets adsorbed on catalyst
particles.

2.4.4. Gaseous materials

Some gas radiotracers can be produced by direct neutron activation in nuclear reactors such as 41Ar
and Kr. Methyl bromide (CH382Br) is produced through synthesis of radioactive K82Br. Other commonly
79

used gas radioactive tracer, despite its low energy is 133Xe.

2.5. RADIONUCLIDE GENERATORS FOR INDUSTRIAL APPLICATIONS

2.5.1. Major radionuclide generator-based radiotracers for industrial applications

A radionuclide generator is a chemical/-physical/mechanical devise that is based on mother-

daughter nuclear genetic relationship and allows for the separation and extraction (elution) of the short-
lived daughter from the longer-lived stationary mother (Fig.11).
 FIG.11. Principle of radioisotope generator

Several forms of radionuclide generators exist. For the simplest and most common, the parent
radionuclide produced in a nuclear reactor or a cyclotron is adsorbed in a support material such as an ion
exchange resin, which is packed in a small column. The short-lived daughter is eluted from the system by
using suitable solvents (elutant). After each elution, system is ready for the next elution after about three
to four half-lives of the daughter product, during which the daughter product build up will reach near
saturation level.

The daughter radionuclide extracted from the generator can sometimes be in a chemical form
directly suitable as a radiotracer for defined systems. One example is the elution of 99mTc in the form of
pertechnetate, 99mTcO4-, which is a suitable tracer for water flow under certain defined conditions. Most
often, the radionuclide extracted needs to be subjected to a labelling procedure to produce the suitable
radiotracer. An example of the latter may be the extraction of 113mIn3+ from an 113Sn/113mIn-generator,
which needs some form of complexing before use as a water tracer. However, when complexes with
ethylenediamine tetra-acetic acid, EDTA, it becomes a suitable water tracer for certain defined conditions.

For a radionuclide generator to be suitable for industrial use, several criteria need to be satisfied.

 Availability: Ideally, the parent radionuclide should be commercially available, at moderate cost.
 Half-life of the parent radionuclide: For use at remote locations it is important to select a generator
with an appropriately long half-life.
 Half-life of the daughter radionuclide: The daughter radionuclide, used as a radioactive tracer or tag
on the radioactive tracer should have a half-life that is as short as possible, consistent with achieving
the objectives of the test. Half-lives varying from several minutes to several hours have been found to
be particularly useful. It should also be noted that the shorter the half-life of the daughter, the more
rapidly the "cow" regenerates itself after elution of the daughter.
 Type and energy of radiation from the daughter radionuclide: Gamma-ray emitting radionuclides are
preferred for most industrial applications because of the ability of gamma radiation to penetrate the
often-substantial thicknesses of material from which process plant is constructed. Gamma rays of
energy 140 keV and upwards have been found to be useful.
 Physico-chemical properties of the eluted daughter: Ideally, the material eluted from the generator
should be in a form that is physically and chemically compatible with the material to be traced so that
it can be injected into the process stream of interest without delay and without complicated chemical
treatment.

In line with the above criteria, four generators have been found to be particularly suitable for
industrial use. They are briefly described below.
 99
Mo/99mTc Generator

This generator is used extensively in nuclear medicine and is widely available worldwide. For this
reason the somewhat short half-life of the 99Mo is not too severe a disadvantage. The half-life of the
daughter 99mTc, i.e. 6 hours, is appropriate for a wide range of studies in industry and environment.

The gamma-ray (140 keV) has a half-thickness of 5 mm of steel. Thus, the 99mTc is suitable as a
tracer for vessels of wall thickness up to about 20 mm. It is not appropriate for use on high-pressure
plants. The low gamma-ray energy of 99mTc is sometimes an advantage. The radiotracer, which is usually
eluted as sodium pertechnetate solution, has been used to study the detailed fluid dynamics of large-scale
water like systems such as wastewater and sewage treatment installations. Detectors submerged in the
pond sense only tracer in the immediate vicinity so that localized flow patterns can be observed.

The main advantage of this generator is its availability worldwide from a number of suppliers,
usually at a few days notice and at a cost that is not prohibitive. A 37 GBq generator costs approximately
US$2000, which is small in industrial terms. Additionally, from a public relations point of view,
prospective clients often perceive a tracer that is used for medical applications as more user-friendly. For
all of these reasons, the 99Mo/99mTc generator can be a powerful weapon in the armoury of industrial
radiotracer groups and it should not be neglected.
137
Cs/137mBa Generator
137
Cs/137mBa generators are available commercially, but with very low activity (typically 370 kBq),
suitable only for use in educational establishments for demonstration purposes. 137Cs/137mBa generator for
industrial applications is not commercially available. However, the parent radioisotope, 137Cs, may be
purchased from a number of suppliers (137CsCl3) at a reasonable cost, which has led to a number of
radiotracer applications groups constructing generators to meet their own particular needs. To provide a
generator system it is necessary:

 To attach the cesium chemically onto appropriate support medium.

 To provide a suitable system for eluting the 137mBa daughter.

The main drawback to this type of generator is the short half-life (2.55 minutes). Even so, the
generator is suitable for many industrial applications. The typical application of this generator is the flow
rate measurement for calibration.

The half-life of the parent isotope at 30 years facilitates long-term storage and the gamma ray
energy of the daughter at 660 keV is high enough for most industrial applications. The potential
usefulness of this generator together with a relatively small price tag, warrants its promotion.
113
Sn / 113mIn Generator

This generator is commercially available, packaged in a lead container that can be eluted readily
using HCl solution injected from a hypodermic syringe. The gamma-ray energy of 390 keV together with
the useful half-lives of the 113Sn parent (115 d) and 113mIn daughter (100 min) makes this generator
suitable for many industrial applications.
68
Ge/68Ga Generator
 68
Ge/68Ga generator has much to recommend as a source of industrial radiotracer. This is in many
respects similar to the 113Sn/113mIn generator. The parent has a reasonably long half-life (271 days) and the
radiations from the daughter (1.08 MeV gamma ray, plus 511 keV annihilation radiation) are sufficiently
high to allow its use as a radiotracer on most types of industrial applications, in particular for
investigation of processes inside the thick-walled pipes and vessels. The half-life of the 68Ga, at 68
minutes, is relatively short, but sufficiently long for many industrial applications. Commercially available
68
Ge/68Ga are currently expensive (approximately US$17000 for 1.85 GBq) and this has acted as a barrier
to their acceptance by radioisotope applications groups. The identification of a production route that
allows this generator to be offered at a significantly reduced price would be a worthwhile objective for the
near future.

2.5.2. Application of radionuclide generator-based radiotracers

Some typical applications of radionuclide generator-based radiotracers can be summarized as

follows:
99m
Tc in sodium pertechnetate form

 Water tracing in wastewater treatment plants for RTD measurement, injected activity  4 to18 GBq,
 Water tracing in surface bodies (rivers, sea) for dispersion of effluent studies (outfalls) and dispersion
coefficient measurements, injected activity  37 GBq,
 Water tracing for water infiltration coefficient measurement in soil (K < 10 -9 m/s), injected activity 
5 MBq,
 Determination of water channelling in petrol borehole (2000 m depth), injected activity  6 MBq,
 water flow rate measurement in a petrol production borehole (2800 m depth), injected activity  4
MBq,
 SPECT tomography in an auxiliary circuit of a nuclear power plant to determine mixture efficiency of
cold water in hot water, injected activity 300 GBq, 12 injections.
99m
Tc in reduced SnCl2 medium

 Sludge labelling-tracing in wastewater treatment plants for RTD measurements, injected activity  4
to 18 GBq,
 Mud labelling-tracing in surface bodies (rivers, sea) for particle dispersion of effluent studies
(outfalls) and dispersion coefficient measurements, injected activity  37 GBq,
 Mud labelling-tracing in sea for dredging products dumping studies (dumping efficiency, advection,
dilution, dispersion coefficients, etc…), injected activity  150 GBq.
99m
Tc for organic phase tracing (solvent extraction from sodium pertechnetate elutant)

 Lubrification studies on a jet engine prototype, injected activity  890 MBq, 15 injections,
 Leakage detection in a high voltage cable (oil insulation), injected activity  5 MBq
113m
In in chloride solution

 Sludge labelling-tracing in wastewater treatment plants for RTD measurements, injected activity 
3.7 GBq,
 Mud labelling-tracing for laboratory channel mud dumping studies for CFD model validation,
injected activity  3.7 GBq, 45 injections,
 Catalyst labelling-tracing for RTD and SPECT measurements in a slurry reactor at a pilot plant scale,
injected activity  925 MBq.
113m
In in EDTA complex

 Water tracing in various hydraulic pilot plants and laboratory facilities, injected activity  0.37 to 3.7
GBq,
 Organic phase tracing for RTD and SPECT measurements in a slurry reactor at a pilot plant scale for
IFP, injected activity  925 MBq.

The table III below summarizes some application cases and conditions.
Some applications of radionuclide generator-based radiotracers
Generator Cs-Ba Mo-Tc Sn-In
Surface water X X X + EDTA
Groundwater X X + EDTA
Water WWTP X X X + EDTA
Sludge WWTP X + SnCl2 X
Mud in surface water X + SnCl2 X
Organic phase X + TBP X + EDTA
tested < 120 °C
Catalyst in organic phase X
tested < 120 °C
Water high temperature X X
under high pressure
tested < 350°C, 40 bars

2.6. MIXING LENGTH ESTIMATION

2.6.1. Definition of mixing length

Mixing length (or good mixing length) is defined as the distance beyond which the variation in the
duct cross-section of tracer concentration C is smaller than some previously chosen value. The mixing
length depends among others from the position of injection inside the pipe.

Injection at the centre of the pipe

The following equations can be used to estimate mixing length, in terms of length to diameter L/D
ratio (or equivalently in number of pipe diameters), as a function of the admissible variation of the tracer
concentration in the cross-section of the pipe, flow Reynolds number Re and wall friction.

L 8 ln x  
 1.18  2.94   (1)
D  2.3 

L  ln x   8
  2.95   (2)
D  2.4  
 1
1   2
L
 20.5  2.85ln x Re 10  smooth  (3)
D   
 pipe 
where

x is the maximum percentage of variation of tracer concentration over the cross-section of the pipe,
λ is the pipe friction coefficient ( smooth : value for a smooth pipe),
 pipe is the value for the real pipe.

Reynolds number in pipe flow is defined as:

Re = U.D/ν
where:
 U is the fluid velocity (m/s),
 Ν is the fluid kinematic viscosity (in m2/s),
 D is the pipe diameter (m).

Eq. 1 is derived on the assumption of constant radial diffusion coefficient and flat velocity profile;
Eq. 2 on the assumption of parabolic radial diffusion coefficient profile and flat velocity profile; Eq. 3
assumes a parabolic radial diffusion coefficient profile and a logarithmic velocity profile. These equations
are plotted in Fig. 12. They show that for Reynolds numbers equal to 105 and a smooth pipe, the “mixing
length” (predictably) decreases when x increases.

FIG. 1. Mixing length (L/D) versus maximum variation of tracer concentration.

2.6.2. Examples of injection techniques for reducing mixing length

Experience has shown that good cross-sectional mixing may require as many as 100 pipe diameters
to be achieved. It is often not possible to inject the tracer at such a distance upstream of the measurement
section. Therefore, it is required to reduce that length by using appropriate tracer injection techniques and
devices.

Multiple-orifice injectors
Substantial reduction in mixing length can be obtained by injecting the tracer through multiple
orifices uniformly distributed on the pipe wall or (if possible) inside the pipe.

High velocity jets

Injecting the tracer counter-currently at a velocity much larger than bulk flow velocity induces high
mixing at the end of the jet. The reduction in good mixing length depends on the number and momentum
of the jets and on their angle with respect to the main flow direction. A simple jet arrangement can bring
about 30% reduction in mixing length as compared to the single central injection point.

Vortex generators
Incorporating obstacles within the pipe, just after tracer injection point, produces turbulence that
enhances mixing and reduces mixing length. As an example, injecting the tracer through three triangular
plates, at an angle of 40o to the main flow direction, reduces mixing length by one third with respect to a
central single injection point.

Pumps and turbines

If tracer is injected upstream of a pump or a turbine, mixing length is considerably reduced.
Centrifugal pumps reduce mixing length by about 50 pipe diameters.

Bends, valves and other obstacles

Every singularity in the pipe promotes turbulence that tends to decrease good mixing length.
However, it is advisable to use straight lengths of pipe without obstacles whenever transit times are to be
measured.

Fig.13 shows variation in mixing length for four different types of injection.

FIG.13. Mixing length L/D vs. maximum variation of tracer injection with four types of injection.
 Examples of injectors
Injection systems are generally home made, built and adapted for specific applications. They vary
considerably in design from the simplest (a syringe or a reservoir with a peristaltic pump) to the most
complex (devices for remote injection into pressure vessels). Simple devices for gas and liquid pulse
injections are presented in figures 14&15:

FIG.14. Gas tracer injector.

FIG.15. Liquid tracer injector