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SECTION IV
EXPERIMENTAL DETAILS
Radiation Sources
Several irradiation facilities were employed in performing the test
work and some work was done to develop additional equipment to enlarge
the potential for performing dynamic flow tests.
1. Cesium-137 Source
A 12,000 curie cesium-137 source is available at Georgia Tech
for static irradiation tests. This source is housed in a 20 ft deep, sub-
surface well and is arranged to provide uniform irradiation in an annular,
coaxial configuration to as many as 12 vial specimens at a time. The dose
rate in aqueous samples in the standard geometry is fixed at 1.0 Mrad per
hour and total doses are varied by varying the exposure time. Sample in-
sertion takes less than one second from a negligible field region.
2. Cobalt-60 Sources
To provide greater variability in total dose and dose rate and
to obtain flow test capability, use was made of a number of high intensity
cobalt-60 sources, ranging in activity from 5000 to 75,000 curies. These
sources were available, through the courtesy of Gamma Industries, Inc.,
while they were stored in the storage pool at the Frank H. Neely Nuclear
Research Center, at Georgia Tech, prior to secondary encapsulation. They
were suspended in baskets about 15 ft below the pool surface and samples
were irradiated in an aluminum pipe positioned an appropriate distance
from the source. A dose calibration curve was obtained in this arrange-
ment by means of thermoluminescent dosimeters.
3. Reactor Activation Source
Before the cobalt-60 sources became available for this work, con-
sideration was given to the utilization of the Georgia Tech Research Re-
actor as a source of intense gamma radiation in a shielded facility outside
the reactor itself. This activity would be produced by circulating a so-
lution of a high-capture-cross section material, such as manganese or
aluminum through a loop system inserted in one of the reactor beam holes.
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The solution would be activated in passing through the flux region in the
reactor; it would then flow through an external loop system where the dye
samples could be irradiated statically or dynamically. By choosing a
fairly short-lived target material, the activity would decay away rapidly
whenever the reactor is shut down or the circulation loop is turned off,
making access for tests or modifications simple and safe. A design study
of such a system was performed as well as some computations on radiation
fields and equilibrium activation levels. Some of these details will be
found in Appendix B.
Procedure
In the initial phase of this work, aqueous solutions of commercial
dyes were used. These were prepared at a concentration of 0.25 g/A which
was considered to be the maximum dye content of any normal textile waste
effluent. This concentration proved to be very convenient as solutions
were seldom completely decolorized, and it was therefore possible to
determine relative resistance to treatment of the colored solutions.
It is to be noted that, in actual textile finishing practice, a waste
14
containing a dye concentration this high would seldom be encountered.
The transfer of dye to fiber is usually efficient enough to leave a lower
dye concentration in the dye bath itself. When diluted with other efflu-
ents, the actual dye concentration is therefore lower. In very concen-
trated test solutions, particularly those with dark color, treatment may
actually destroy much of the color, but the change in transmittance is
not easily observable because of the large concentration of dye molecules.
If treated and untreated solutions are diluted and then compared, the
difference in transmittance is readily apparent. The effects of treatment
were more readily observed with lighter colored or less concentrated so-
lutions without further dilution.
The actual dyes were chosen on the basis of their chemical composi-
tion, their manner of use, and the quantity being used. Selections were
made after discussions with a large textile finisher and a major dye manu-
facturer .
Table 1 lists the various dyes used in the study. In addition to
trade name, the Coloui
information is available.
the trade name, the Colour Index name and number are given where this
8
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Table 1. Dyes Investigated
Trade Name
Colour Index Name and Number
Artisil Blue Green 100%
Artisil Violet RL
Aso Silk Red 3B 100%
Benzyl Cyanine 6B
Benzyl Fast Yellow GNC
Benzyl Fast Yellow 2CG
Brilliant Alizarine Milling Violet FBL
Calcocid Fast Yellow 36 Ex.
Calcofast Neutral Red 3 GL
Calcofast Neutral Yellow R
Calcosperse Blue CG
Calcosperse Yellow 4RL
Denivat Blue 57
Kiton Fast Blue 4GL
Lanasyn Black M
Lanasyn Orange RL
Lanasyn Yellow LNW
Latyl Cerise N
Latyl Cerise Y
Lumicrease Yellow EFUL
Merpacyl Red G
Neolan Blue 2G
Nylosan Blue E-2GL
Pyrazol Fast Turquoise GLL
Sandothrene Blue NCR
Sodyesul Brown GNCF
Acid Red 18
Disperse Violet 4
Mordant Blue 1
Disperse Blue 7 62500
Disperse Violet 18
Acid Red 151 26900
Acid Blue 83 42660
Acid Yellow 76 18850
Acid Yellow 40 18950
Acid Violet 48
Acid Yellow 34 18890
Acid Yellow 152
Disperse Blue 73
Disperse Yellow 23 26070
Acid Blue 23 61125
Acid Black 107
Acid Orange 86
Acid Yellow 151
Direct Yellow .106
Acid Red 337
Acid Blue 158 14880
Acid Blue 40 62125
Direct Blue 86 74180
Vat Blue 6 69825
Sulfur Brown 14 53246
Acid Red 18 16255
Disperse Violet 4 61105
Mordant Blue 1
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A number of actual dye wastes have also been studied. These solu-
tions were obtained from textile finishing plants at Dalton and Columbus,
Georgia and Lanett, Alabama. Most of the samples were taken directly
from operating dye becks and consequently contain a higher concentration
of dye than would have been present in the waste at the conclusion of the
dyeing operation. The composition of these dye baths is a trade secret,
but all of them are mixtures of different dyes, blended to produce a de-
sired color. A typical dye bath may contain as few as two dyes or as
many as seven or more, but the average seems to be about 3 or 4. Chemical
additives such as wetting agents, dispersing agents, and dye assists, are
also typically present.
The wavelength of minimum transmittance of each solution was deter-
mined by examination of the visible spectrum obtained with a recording
spectrophotometer. Subsequent readings of transmittance of that solution
were all made at the same wavelength. Experiments involving the effects
of an oxidant without radiation were performed by adding the oxidant to
the test solution, mixing, then transferring a sample to a spectrophotom-
eter cuvette. The non-recording spectrophotometer was adjusted to the
appropriate wavelength, and readings of transmittance were made at inter-
vals as desired.
In experiments involving both radiation and an oxidant, the oxidant
was added to 15 ml of the test solution which was in a 20-ml screw-cap
culture tube. The tube was quickly capped, and the solution mixed by
inverting the tube several times. The tube was then lowered into the
opening of the radiation source, and timing was started as the tube
entered the radiation field. After the desired period of irradiation,
the culture tube was withdrawn from the radiation field, and a sample of
the solution placed immediately in the spectrophotometer. The transfer
of material from the radiation field to the spectrophotometer required
only a few seconds, so readings could be easily taken as early as one
minute after the end of the irradiation period.
Transmittance readings were usually continued at intervals as long
as significant changes were being observed. In some cases this required
an hour or longer, but more frequently the major changes had occurred in
less than 10 minutes. Some experiments were performed in which the oxidant
10
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was added while the test solution was in the radiation field. This was
accomplished by placing the oxidant in a pipette to which a rubber tube
and bulb were attached. The long narrow tip of the pipette was positioned
near the bottom of the test solution so that pressure on the bulb caused
the oxidant to be expelled into the test solution. The air expelled with
the oxidant provided a thorough mixing of the oxidant with the test solu-
tion.
The initial experiments were all performed using the 12,000 curie
cesium-137 source which provides a uniform radiation field of constant
intensity. Later experiments utilized the cobalt-60 source with which
control of the radiation intensity was possible.
Determination of biochemical oxygen demand and chemical oxygen demand
was carried out according to the customary procedures which are described
in Standard Methods. Measurements of total organic carbon were made
with a Beckman Total Organic Carbon Analyzer, Model 915, utilizing a
Hamilton automatic syringe.
Solutions of dyes of a number of different chemical types have been
subjected to treatment with radiation alone, a chemical oxidant alone,
and with both radiation and an oxidant. Experiments with sodium hypochlo-
rite, hydrogen peroxide, chlorine dioxide, and ozone revealed that the
hypochlorite is the most effective, although estimation of ozone concen-
tration was not very accurate. Sodium hypochlorite was used in most of
the experimental work, although gaseous chlorine would probably be used in
large-scale operations. The effect is the same, according to the follow-
ing equations. Chlorine in dilute solution gives:
C12 + H20 - 2H+ + Cl" + OCl"
Sodium hypochlorite in dilute solution is essentially ionized:
NaOCl -* Na+ + OC1~
Sodium hypochlorite concentrations are hereafter expressed in terms of
their chlorine content.
The various dyes studied will be discussed individually, although
attention will be drawn to similarities and differences in behavior between
different dyes. It is to be noted throughout this report that the
11
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initial transmittance reading for a given dye is not always the same.
These differences, usually no more than two or three percent, are caused
by instability of the spectrophotometer and slight variations in the
weighing and mixing of the solution. Ageing of solutions may also be ac-
companied by change in transmittance; fresh solutions were frequently
prepared. Precise details of the radiation chemistry are difficult to
establish owing to the proprietary nature of most of the dye formulations.
In general terms, the dye degradation is probably determined by the rate
of free ion generation in the water produced by irradiation and by the
competing tendency for recombination of the individual dye molecules.
The irradiation effects in ionizing and dissociating the dye molecules
and the water molecules in most cases promote oxidation both by the
chlorine present and by the oxygen ions in the radiolyzed water. An
upper limit to this effect is set by backward reactions in the water and
the finite mobility of the dye molecules and chlorine ions.
12
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SECTION V
TEST RESULTS
Comparison of Oxidants
Acid Yellow 40, a monoazo type dye, and Disperse Violet 18, an an-
thraquinone, were used to compare the relative effects of sodium hypochlo-
rite, chlorine dioxide, and hydrogen peroxide. The results are summarized
in Fig. 1 and Fig. 2, where the time scale begins at the moment the re-
agent was added to the dye solution. It may be seen that hydrogen per-
oxide, either with or without radiation, is the least effective of the
chemical reagents. Sodium hypochlorite with radiation is the most effec-
tive treatment for Acid Yellow 40, but chlorine dioxide plus radiation is
the most effective by a slight margin for Disperse Violet 18. The slight
advantage of chlorine dioxide is offset by its considerably higher cost,
and subsequent work was confined to the use of sodium hypochlorite.
Treatment of Dye Solutions
To understand the results for the various dye solutions tested, it
is important to point out certain common features that appear in the ma-
jority of the figures that follow. In comparing irradiated samples with
those treated with chlorine only, optical transmittance is plotted against
a common time scale. In general, decolorization occurs with chlorine
treatment alone at a slow rate indicated by a nearly straight line in most
cases. When a sample is irradiated, the first point shown is measured
immediately after removal from the gamma source. Different exposures
account for the different starting time for irradiated samples. From the
time of removal, transmittance in general is seen to increase further,
usually at a rate parallel to the "chlorine only" or "no gamma" line. The
increase in transmittance due to the combined effect of radiation and
chlorine is the effect desired in these tests. By extrapolating back the
final slope of the transmittance curves one can obtain a measure of the
beneficial effect of the combined treatment. In the cesium source with
its fixed dose rate, the minimum gamma doses required for a given effect
are not directly obtainable. This aspect will be discussed in a later
section.
13
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Anthraquinone Dyes
Acid Blue 23 (Kiton Fast Blue 4 GL) -- This dye responds readily
to the combination radiation-oxidant treatment. Sodium hypochlorite at
80 ppm chlorine produces higher transmittance values than 40 ppm chlorine
at each radiation dose, but 160 ppm produces effects almost identical to
80 ppm. The optimum treatment would seemingly consist of 80 ppm chlorine
plus 35-50 krads. Graphs showing the results of different hypochlorite
levels for different radiation doses in neutral solutions are shown in
Figs. 3, 4, and 5.
Acid Blue 40 (Nylosan Blue) -- Decolorization of this dye is pro-
portional to both the hypochlorite dose and the radiation dose. The best
results were obtained from 160 ppm chlorine and 170 krads (94% transmit-
tance) , but the same chlorine dose with half as much radiation does nearly
as well (88% transmittance). These results are graphically presented in
Figs. 6 and 7.
Acid Violet 48 (Brilliant Alzarine Milling Violet FBL) -- Sodium
hypochlorite alone is rather effective in the decolorization of this dye,
but the effect is enhanced by radiation. At the 80 or 160 ppm chlorine
concentration, high transmittances result upon standing. Irradiation en-
hances the effect by producing higher transmittances more rapidly. These
findings are detailed in Figs. 8 and 9.
Disperse Blue 7 (Artisil Blue Green 100%) -- Treatment with 17
krads of gamma radiation with 160 ppm chlorine shows little improvement
over the chlorine alone. A marked improvement results when the radiation
dose is increased to 85 krads. See Fig. 10.
0:1 sperse Violet^^ -- This dye is sparingly soluble in water, al-
though it is well dispersed by chemical agents present in the commercial
material. In order to achieve a true solution, the water dispersion was
mixed with an equal volume of methanol or ethanol. Disperse Violet 4 is
very soluble in these alcohols, and a true solution was obtained with
either of them.
The methanol-water solution was treated as shown in Fig. 11, where it
appears that sodium hypochlorite is more effective alone than in combina-
tion with radiation. The same behavior occurs in ethanol-water, with
either 80 or 160 ppm chlorine, as illustrated in Figs. 12 and 13. These
results are interpreted as indicating that, in the absence of radiation,
14
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the hypochlorite reacts with both dye and alcohol. Reaction with the
methanol is favored because more methanol is present; this leaves more
unreacted dye.
Vat Blue 6 (Sandothrene Blue NCR) -- Comparisons were made of
the behavior of this dye in water, water-methanol, and water-ethanol. In
water, 80 ppm chlorine had no effect in the absence of radiation. Radia-
tion doses of a few kilorads were ineffective, but a one megarad dose
produced a distinct decrease in transmittance. When the dye was dissolved
in ffater-methanol, 80 ppm chlorine was not very effective with or without
radiation. Transmittances were somewhat improved by 80 ppm chlorine plus
large doses of radiation. Details are set forth in Fig. 14.
Disperse Blue 73 (Calcosperse Blue CG) -- The behavior of this
dye is typical of many of the dyes involved in this study. Figs. 15, 16,
and 17 show the results of adding 40, 80, and 160 ppm chlorine, respec-
tively. Fig. 15 shows that a minimum amount of chlorine is required for
radiation to have a significant effect. Figs. 16 and 17 show that de-
colorization increases with increased radiation dose with an apparent
leveling off at the higher doses. This is confirmed in Fig. 18 where the
effect of radiation is shown on solutions containing different amounts of
hypochlorite. It may be seen that the first 34 krad dose produces pro-
portionally more effect than greater doses in the presence of 160 ppm
chlorine. At 80 ppm chlorine, the radiation dose effect is linear up to
51 krads.
Latyl Cerise Y -- This material showed only low sensitivity to
the radiation effect. At 40 ppm chlorine, added radiation increased the
transmittance by a significant amount. At a hypochlorite content of 80
ppm chlorine, radiation effects were insignificant at a total lapsed time
of 10 minutes. The transmittance continued to change rapidly after the
end of the irradiation period; it appears that the continuing change is
merely a manifestation of prolonged reaction with the hypochlorite. Figs.
19, 20, and 21 illustrate these results.
Azo Dyes
Acid Yellow 34 (Calcocid Fast Yellow 3G EX) — In this dye, and
the following, it was observed that chlorine alone led to rapid decolori-
zation. Further or concomitant radiation exposure had little if any effect
15
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as is seen in Fig. 22, bearing in mind that the initial slope in the
longer irradiation is of no significance as such. The decrease in trans-
mittance observed at 17 krad occurs in occasional samples; it may repre-
sent the formation of a light-absorbing species. However, since it is
not evident in higher dose samples, it may be merely a transient condition.
Acid Yellow 40 (Benzyl Fast Yellow 2 CG) -- This dye is decolor-
ized less readily than most of the compounds studied. One series of tests
was made (see Fig. 23) and it was noted that at radiation doses less than
85 krads there was a slight recovery of color at 10 minutes after the '
start of the various radiation exposures. At a dose of 85 krads, no
further change in transmittance was observed.
Acid Red 151 (Azo Silk Red) — Two azo groups are present in the
molecules of this dye, which is rather resistant to the various experi-
mental conditions investigated. Sodium hypochlorite at the 80 ppm chlo-
rine level has very little effect, about the same as 160 ppm chlorine.
In both cases, the transmittance increase is proportional to the radia-
tion dose, as shown in Figs. 24 and 25.
Acid Red 337 (Merpacyl Red G) — This material decolorizes in an
unusual nonlinear fashion in the presence of chlorine alone, as shown in
Figs. 26 and 27. Adding irradiation to the process speeds up decoloriza-
tion markedly and comparable decolorization is obtained in only a fraction
of the time at 182 krad, compared with one hour in the presence of chlo-
rine alone. Going to a megarad irradiation leads to the same ultimate
decolorization as the one hour chlorination treatment, but it is evident
that a saturation effect has occurred at much lower dosages.
Acid Blue 158 (Neolan Blue 2G) — When treated with sodium hypo-
chlorite at 40 ppm chlorine, this dye showed little response. When radia-
tion was added, the response was greatly increased, as shown in Fig. 28.
Higher transmittance values can be reached more rapidly with chlorine
levels of 80 or 160 ppm, as illustrated in Figs. 29 and 30, respectively,
for the usual dose values. It is interesting to note that the higher
chlorine level leads to a significant reduction in the gamma-ray dose
needed for comparable decolorization.
Disperse Yellow 23 (Calcosperse Yellow 4 RL) -- This water-
insoluble disazo dye was dissolved in 50% methanol and was found to behave
similarly to Disperse Violet 4 (Fig. 11). With no radiation applied, the
16
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hypochlorite alone increases transmittance from 15.5 to 30% whereas 85
krad with no chemical oxidant produced almost no change. This is depicted
in Fig. 31.
Metallized Azo Dyes
Acid Yellow 151 (Lanasyn Yellow LNW) -- Of intermediate resistance
to decolorization, this dye responded to sodium hypochlorite at the 80 ppm
chlorine concentration, but to a slightly greater extent and more rapidly
when radiation treatment followed addition of the hypochlorite. See Fig.
32.
Acid Yellow 152 (Calcofast Neutral Yellow R) -- Sodium hypochlo-
rite alone was quite effective in decolorizing this light-colored dye.
Radiation at the 17 krad level did not increase the effect of the hypochlo-
rite, although a dose of 170 krads caused a significant increase in trans-
mittance. See Fig. 33.
Acid Orange 86 (Lanasyn Orange RL) -- Without radiation, sodium
hypochlorite had little effect on this dye, as shown in Fig. 34. By
treating also with 51-85 krads, very good decolorization was achieved.
Acid Black 107 (Lanasyn Black M) -- This product is the most re-
sistant of the several metallized azo materials investigated. Sodium
hypochlorite at 80 ppm chlorine produced a transmittance increase of about
6%, and even with the addition of 204 krads of radiation, the increase was
only about 15% as shown in Fig. 35. The situation is improved, however,
when the oxidant content is increased to 160 ppm chlorine and the radia-
tion level is in the 85-170 krad dose range. Fig. 36 shows the results
of this experiment.
Calcofast Neutral Red 3 GL -- Irradiation was necessary to pro-
duce any appreciable change in the color of this dye solution. As Fig.
37 reveals, the effect of hypochlorite alone is negligible, but 85 krads
raised the transmittance from 7.5 to 31.5%, and 170 krads raised it to 82%.
Sulfur Dyes
Sulfur Brown 14 (Sodyesul Brown GNCF) --It was found that de-
colorization of this dye could best be achieved with a sodium hypochlorite
concentration of 160 ppm chlorine. The transmittance of the solution in-
creased as the radiation dose was raised. This is similar to the results
obtained with the other sulfur dye studied, Denivat Blue 57. The manner
17
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in which these dyes are applied makes it unlikely that an effluent would
ever contain a dye concentration as high as that of the test solutions.
The experiments with Sulfur Brown 14 are summarized in Fig. 38 and a com-
parison of the relation between radiation dose and transmittance for both
Sulfur Brown 14 and Denivat Blue 57 is shown in Fig. 39, compared 10
minutes from the start of the test in all cases. It is evident that
Denivat Blue 57 is much more radiation-sensitive.
Denivat Blue 57 — At 0.25 g/J& this sulfur dye of indeterminate
structure shows little response to treatment with radiation and a sodium
hypochlorite concentration of 40 ppm chlorine (Fig. 40). The 17 krad dose
actually appears somewhat more effective than higher radiation doses, but
the differences are small and none are very effective. Considerable im-
;
provement can be seen in Fig. 41 which illustrates the effectiveness of
doubling the chlorine concentration to 80 ppm. The increase in transmit-
tance with even the minimum radiation dose is significant. The best re-
sults were obtained when the chlorine content was 160 ppm (Fig. 42).
..After a 66 krad dose, the solution approaches 90% transmittance and ap-
pears almost clear upon visual inspection; it should be acceptable for
any industrial effluent. The maximum applied dose of 83 krads raised the
transmittance above 95%, and the solution appeared colorless to the eye.
When either 80 or 160 ppm chlorine are present, the transmittance
increases proportionally with the radiation dose. This is shown in Fig.
43, where transmittance at six minutes after the beginning of the irradia-
tion period is plotted against radiation dose, and in Fig. 39, for a dif-
ferent chlorine content.
Triphenylmethane Dyes
Acid Blue 83 (Benzyl Cyanine 6B) -- This material is one of the
two triphenylmethane compounds studied. In aqueous solution it is de-
colorized appreciably by sodium hypochlorite alone at 40, 80, and 160
chlorine, but when radiation is applied, decolorization is more rapid and
more complete. These results are shown in Figs. 44, 45, and 46. However,
increasing either chlorine content or radiation dose leads to only mar-
ginal increases in final transmittance.
Mordant Blue 1 — When sodium hypochlorite was added to a solution
of this dye, almost no change in transmittance occurred. Transmittance is
18
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greatly increased when radiation treatment follows addition of hypochlo-
rite at a concentration of 80-160 ppm chlorine. The higher chlorine con-
tent gives a higher transmittance at 85 krads, but 80 ppm is equally as
effective as 160 ppm when the radiation dose is 170 krads. These conclu-
sions are drawn from Figs. 47 and 48.
Dyes of Other Chemical Types
Direct Yellow 106 (Lumicrease Yellow EFUL) -- The exact chemical
formula of this dye is not published in the Colour Index, but it is listed
as a stilbene type. It is the only dye of this type that was included in
the study. By reference to Figs. 49 and 50, it is seen that the effect of
sodium hypochlorite alone is negligible. Seventeen krads plus 80 ppm
chlorine increases transmittance to 47% from an original of 12%, and if
the radiation dose is held at 17 krads, 160 ppm chlorine raises the trans-
mittance to 52%. Greater radiation doses are proportionally less effec-
tive. Optimum conditions for decolorization of this dye therefore appear
to consist of approximately 17 krads of gamma radiation and chlorine in
the range of 80 to 160 ppm. With this dye, no change in transmittance
occurred following the irradiation period; all changes occurred during
irradiation, since the chlorine effect alone was insignificant.
Direct Blue 86 (Pyrazol Fast Turquoise GLL) -- This is the only
phthalocyanine type dye investigated during this study, and it is decolor-
ized quite readily by a combined radiation plus hypochlorite treatment.
The optimum combination appears to be in the range of 160 ppm chlorine and
68 krads of gamma radiation. Figs. 51 and 52 summarize the experimental
work on this material. With this dye, there appeared to be slow-acting
chlorine effects after irradiation that were different from those for
chlorine acting alone.
Commercial Dye Wastes
To evaluate the usefulness of the combined oxidation-radiation
treatment on actual dye wastes, samples were obtained from several tex-
tile mills. Solutions were collected directly from dye baths that were
being used to dye fabric or yarn. None of the baths was exhausted, and
the dye content was higher than it would have been at the completion of
the dyeing process. Also, the usual dilution with other plant effluent
had not occurred, so these solutions were several times more concentrated
19
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than the flow normally released by the plant."
As the composition of these solutions is unknown, they were numbered
for identification purposes. The liquid labeled Dalton No. 1 was reddish-
brown in color, and responded to treatment with sodium hypochlorite at 80
ppm chlorine. When treated additionally with 51 krads of radiation, the
solution exhibited a transmittance increase from 10 to more than 55%.
This information is detailed in Fig. 53.
Dalton solution No. 2 was a very pale straw color, and would have
presented no objectionable color had it been discharged directly to a
stream. At the wavelength of maximum absorbance, it transmitted 81%, and
this value was increased by 6% when 40 ppm chlorine was added. When sub-
jected to irradiation, transmittance values remained constant or declined
slightly as revealed in Fig. 54. The behavior and appearance of this solu-
tion make it seem doubtful that the color is due solely to an organic
dye; other processing chemicals may be the source of color.
Dalton solution No. 3 was a deep yellowish-brown; it was diluted
with an equal volume of water before treatment. It did not respond very
well until the sodium hypochlorite level was raised to 160 ppm chlorine.
At this chlorine concentration, decolorization was proportional to the
radiation dose, as shown by Fig. 55.
Dalton solution No. 4 was a very opaque dark green that had been in
use for only a few minutes, so its concentration was near the maximum.
It was necessary to dilute it with 3 volumes of water in order to obtain
a transmittance of as much as 5%. Sodium hypochlorite alone at 160 ppm
chlorine produced little effect, but when radiation was included, trans-
mittance values around 70% were obtained as illustrated in Fig. 56.
Effect of pH on Decolorization of Dye Solutions
A series of experiments was performed in which phosphate buffers
were used to obtain pH values in the ranges of 4.0, 6.5, and 8.7 in the
dye solutions. No broad generalizations are possible with the small num-
ber of dyes investigated, as no distinct relationship was found between
ease of decolorization and pH. In some instances the lowest pH produced
the greatest effect, and in other instances the least effect. The effects
on some dyes were the same at all three pH values.
20
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Acid Yellow 76 (Benzyl Fast Yellow GNC) — This dye was tested
at three pH values in the presence of sodium hypochlorite at the 40 ppm
chlorine level. Radiation was supplied by cobalt-60 at 8000 rads/minute.
A dose of 40 krads raised the transmittance from its initial 17.5% to the
55-60% range at all pH values; transmittance then declined to 407o at pH
4.0 and 6.5, while the decline was only to about 48% at pH 8.5. With 8 or
24 krad doses the first post-irradiation readings were all in the 65-75%
range, but subsequent readings all declined with the single exception of
the sample which received 8 krads at pH 4.0. Figs. 57, 58, and 59 illus-
trate these findings. No pH readings were obtained during the tests and
the pH may well be changed by the irradiation.
This effect will require further investigation, especially under
flow conditions.
Acid Orange 86 (Lanasyn Orange RL) — This dye exhibited no color
recovery under any conditions utilized. When a solution of this dye was
subjected to radiation from cobalt-60 at 6000 rads/minute, the transmit-
tance was increased most at pH 4.0 for any radiation dose. A somewhat
lesser effect was noted at pH 6.7 and the minimum effect at pH 8.7. These
findings are set forth in Figs. 60, 61, and 62. Further experiments were
performed with this dye in the presence of high hypochlorite concentra-
tions. The general pattern of the curves at pH 8.7 (Fig. 63) is similar
to those at pH 6.7 (Fig. 64), but differs markedly from the pattern at pH
4.0 (Fig. 65). The increased speed of decolorization at pH 4.0 is well
illustrated by comparison of the readings at 20 minutes of the solutions
receiving 6 krads. At pH 8.7 the transmittance is 21%; at 6.7, 24%; but
at 4.0 it is 62%. All these effects are dominated by the extremely slow
action of the chlorine on this dye. Note the longer time scale in these
figures which are numbered 66 and 67. The effects of pH on the decolori-
zation of several dye solutions by sodium hypochlorite plus radiation are
discussed in detail in the Interim Report of August 31, 1971. Informa-
tion is given there on Acid Yellow 40, Acid Blue 23, Acid Red 18, and
Acid Blue 158.
Biochemical Oxygen Demand of Dye Solutions
Determination of the biochemical oxygen demand (BOD) of dye solutions
is difficult because of the low biodegradability of the dyes. BOD values
21
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obtained using activated sludge as the seed were not satisfactory, so
attempts at acclimatization were made. A portion of the activated sludge
was placed in some of the dye solution and allowed to stand. In some in-
stances the dye color faded, indicating that biological decomposition was
occurring. The faded supernatant was replaced at intervals with fresh dye
solution. After three or more days, some of the sludge was used to inocu-
late the dilution water used in the BOD test on the dye to which the
sludge had presumably become acclimated. This required the preparation of
a different seed for each different dye.
The results of .the tests were disappointing. The values obtained
were not very consistent and for the most part appeared independent of
the amount of dye used in the determination. It was concluded that the
dye itself was taking little, if any, part in the consumption of dis-
solved oxygen; the values obtained were due almost exclusively to nitri-
fication. Ammonium ion is a component of the buffer used in preparing
dilution water and is apparently utilized by the bacteria present. The
results obtained with dye solutions subjected to radiation were indis-
tinguishable from those obtained with untreated solutions.
Tests were made on Pyrazol Fast Turquoise GLL, Latyl Cerise Y,
Sodyesul Brown GNCF, Acid Red 18, Acid Blue 158, Acid Blue 23, and Acid
Yellow 40. It is concluded from these determinations that the BOD exerted
by these dyes is very small and perhaps zero, and a few kilorads of radi-
ation dose has little or no effect on the BOD.
Chemical Oxygen Demand of Dye Solutions
The chemical oxygen demand (COD) test indicates the quantity of
material present in water or a waste that is chemically oxidizable under
specified conditions. Although some inorganic interference is possible,
it is taken as a measure of organic matter present. There is a rough
correlation between COD, biochemical oxygen demand (BOD), and total or-
ganic carbon (TOC) in some instances, but large differences may exist.
COD determinations are very useful as they can be made in a few hours
while a standard BOD requires a five day incubation period. COD is also
used to determine organic loads when the presence of toxic substances
precludes measurement of BOD.
The results of a number of COD determinations are summarized in
Table 2.
22
-------
Table 2. Chemical Oxygen Demand of Solutions Containing 0.25 g/JL of Dye
N3
OJ
Trade Name
Acid Red 18
Artisil Blue Green 100%
Azo Rhodine 6B
Benzyl Fast Yellow 2CG
Brilliant Alizarine Milling
Violet FBL
Calcocid Fast Yellow 3G EX
Calcofas.t Neutral Blue 3GL
Calcofast Neutral Red 3GL
Calcofast Neutral Yellow R
Calcospere Blue CG
Calcospere Red FFB
Calcosyn Brilliant Scarlet BN
Calcosyn Sapphirine Blue 2GS
Calcosyn Yellow GCN
Cibalan Navy Blue RL
Kiton Fast Blue 4 GL
Lanasyn Black M
Lanasyn Yellow LNW
Latyl Cerise Y
Lumi crease Yellow EFUL
Mordant Blue 1
Neolan Blue 2G
Nylosan Blue E-2GL
Waste dye effluent
Colour Index Name
Acid Red 18
Disperse Blue 7
Acid Violet 7
Acid Yellow 76
Acid Violet 48
Acid Yellow 34
Acid Blue 171
____
Acid Yellow 152
Disperse Blue 73
Disperse Red 60
Disperse Red 1
Disperse Blue 3
Disperse Yellow 3
___-
Acid Blue 23
Acid Black 107
Acid Yellow 151
____
Direct Yellow 106
Mordant Blue 1
Acid Blue 158
Acid Blue 40
....
Untreated
Solution
245*
317
91
191
163
278
307
152
275
355
294
370
317
373
270
93
124
280
303
89
128
110
280
257
80 ppm
Chlorine
*
171
« _ —
_ mm Mi
134
• — —
193
234
M *m _
• •• ••
284
_ _ _
297
234
200
54
229
80
63
238
80 ppm Cl2
+ 85 krads
167*
132
193
230
280
234
282
232
303
192
57
217
80
63
vJ -J
229
>
All values are expressed in p.g/1.
-------
It is to be noted that there is wide variation in the COD of the untreated
solutions although they were all prepared at the same concentration, 0.25
g/A. These differences are due to some degree to differences in the chem-
ical structure of the dye molecules, but primarily to differences in the
organic content of the commercial dyestuff. The actual compound which
produces color may be blended with dispersants, wetting agents, or other
non-colorants; the commercial product may also contain an inert diluent
to provide the proper concentration for commercial application.
The general pattern observed was that the initial COD of the solution
was reduced more by combined oxidation-radiation treatment than by oxida-
tion alone, although the differences were small. The amount of change is
proportional to the susceptibility of the dye to oxidation by the sodium
hypochlorite with or without radiation. Radiation alone in small doses
has been shown to produce little change in color, and it is reasonable to
expect only limited accompanying changes in the COD value at the radiation
levels used in this work. To obtain significant changes in COD values in
dye solutions, doses in the megarad range would need to be employed, as
18
shown by Garrison et al.
Effect of Radiation Dose Rate
If it is assumed that the combined radiation-chlorine effect is due
to the competition between chlorine and radiolysis products in the solu-
tion bath for interaction with dye molecules on the one hand and backward
recombination reactions on the other, then the decolorization process
should depend primarily on the total dose received, since the chlorine-
induced oxidation process is relatively slow. Some dose-rate dependence
may be expected where total decolorization effects are large and rapid.
A few tests have been conducted in the cobalt facility to test for
optimum dose and dose-rate dependence. Since this information is crucial
for the optimization of the treatment facility design, further tests will
need to be conducted for several of the more important sample solutions.
Acid Blue 23 was irradiated for various lengths of time at dose rates
of 6000 rads per minute and 13,000 rads per minute, with a constant amount
of added sodium hypochlorite. At a pH of 8.7, there was no great differ-
ence between effects produced by different dose rates if the total dose
was similar and transmittance was measured at about 45 minutes or later.
24
-------
Higher transmittance values were generally associated with higher doses,
as shown in Figs. 66 and 67, although the 13 krad dose gave a transmit-
tance value lower than at 6 krads. Figs. 68 and 69 show that the situa-
tion is different at pH 6.4 where a 39 krad dose at 13 krad/minute gave
the same results as 60 krad at 6 krad/minute. Figs. 70 and 71 show a
less distinct pattern at pH 4.6. The highest dose, 65 krad, was least
effective, and 39 krad was found to be most effective. The recovery
shown on the 65 krad curve may be due to recombination, producing com-
pounds with lower transmittance values.
From consideration of these findings it is concluded tentatively
that radiation delivered at the rate of 13,000 rads per minute is more
efficient than radiation supplied at 6000 rads per minute. However,
this dose rate is not necessarily the optimum for this compound, let alone
for any combinations of dyes.
Preliminary Cost Evaluation
In order to make a rough estimate of the costs involved in applying
the oxidation-radiation treatment to wastes on a plant-size scale, it
was necessary to assume certain design factors. Two alternates are pos-
sible in positioning this process in the treatment sequence. It could be
used as the final step in a municipal or combined treatment plant before
releasing the effluent to the receiving stream. Many effluents are chlo-
rinated at least to some degree just prior to release, and at this stage
the cost of chlorine would be minimized. The obvious disadvantage of
this situation is the high volume of waste that would have to be treated.
The highly colored dye wastes usually constitute only a fraction of the
textile waste produced, and this would be diluted much more by. other non-
colored industrial or domestic sewage.
The alternative is to treat colored wastes at their point of maximum
concentration before they receive any dilution. This appears to be a more
likely arrangement, as the lower volume of liquid would allow smaller
physical facilities, and the effects of the oxidant and radiation would
be concentrated on the dye itself and not dissipated on other matter pres-
ent at later stages of treatment. The following design and cost consid-
erations are therefore based on having this process as the initial step
in the treatment scheme.
25
-------
Functionally, the facility would consist of chlorine injection, mix-
*g of chlorine with the waste flow, and retention of the mixture in a
radiation field for the time required to absorb the necessary radiation
dose. The addition of chlorine to a liquid flow is a very common pro-
cedure, and can be accomplished very readily with an injector inserted
into the pipe carrying the waste. Mixing can be accomplished by turbulence
in the pipes which can be easily created with vanes or baffles. The ir-
radiator itself is visualized as a pipe or channel, about 3 feet in diam-
eter. The cobalt-60 which provides gamma radiation would be contained in
tubes a few inches in cross section positioned inside the large pipe.
Optimization studies have not been made to determine the most efficient
configuration, but a symmetrical arrangement of four of the small tubes
is assumed for purposes of calculation. The large channel will be con-
sidered 100 ft in length for purposes of calculation, and the isotope-
containing tubes will total 400 ft. Encapsulation will be in one foot
lengths, so a total of 400 elements will be needed. The channel need not
be in a straight line and could consist of several folded segments.
The treatment characteristics chosen were 75 ppm chlorine and 60
krads of radiation. Actual operating conditions will be determined by the
chlorine feed rate and the flow rate of the waste through the irradiator.
As both of these factors can be easily controlled, a very flexible ar-
rangement will be provided.
The actual capacity of the facility depends on the flow rate chosen;
twice the amount of waste could be treated if the required radiation dose
were halved. Excess chlorine injection capacity would be provided by
selecting an injector larger than required for the design flow. Chlorine
addition would therefore not be the limiting factor.
A waste flow of 10,000 gallons per hour was assumed, and the design
radiation dose of 60 krads is to be delivered in ten minutes; this re-
quires an irradiation volume of 227 cubic feet.
The dose calculation is as follows:
A dose of 60 krads/10 min is desired, and
60 krads/10 min = 360 krad/hr
26
-------
(3.6 X 10s rads/hr)(l g/cm3)(2.83 x 104 cm3/ft3)(2.27 X 102 fts)
(3.6 X 103 sec/hr)(2.5 •—.
X 10"6 ergs/MeV)(l X 10
-2
rads >
ergs/gj
23.13
14.40 x 10'5
1.61 x 10 dis/sec
3.7 X 10
,16 d_is/sec
MCi
= 0.43 MCi
Therefore, 0.43 MCi is the amount of Co-60 needed to treat a volume
of 227 ft3 to a dose rate of 60 krads/10 min. This calculation assumes
100% source utilization and that all parts of the waste flow receive this
minimum dose rate while passing through the radiation zone.
pipe
line source
Figure 66 Cross Section of Irradiator
The irradiator contains within it four line sources each of which is
100 feet long. A cross section of the proposed configuration is shown in
the figure above.
In order to maintain a minimum cobalt-60 inventory of 0.43 MCi, it
is necessary to start with a larger amount. Since Co-60 decays about 12%
per year: 0.43 + .125 (0.43) = 0.484 MCI
initial cost = (4.84 X 10B Ci)($0.1/Ci) + $75/element (400 element)
= 4.84 x 104 + 3 x 10* = 7.84 X 104 $ for Co-60
27
-------
Irradiator and installation costs = 1 X 104 $
This cost will be amortized over a 20 year period, semi -annually, at
6% interest per year.
19
From an annuity rent table the cost is obtained:
0.08654 dollar/dollar/year
or
$7,649/yr including interest
The cost to replace 12.5% of the Co-60 each year is
($7.84 x 104)(0.125/yr) = $9,800/yr
The salvage value of Co-60 remaining at the end of 20 years is esti-
mated at half its initial cost, which gives a per year credit of
$43,000 = $
2 X 20 ?1'°75
The total cost per year with the semi-annual payment plan is:
Principle and interest 7,649
Annual isotope replacement 9,800
Salvage value 1,075
$16,374
At the design flow rate and a radiation dose of 60 krads, the cost of
radiation is
The cost of chlorine waa calculated as follows:
Amount required per thousand gallons at 75 ppm:
1000 gal. X 8.337 Ibs/gal. = 8337
8337 x .000075 = 0.625 Ib
Half the chlorine injected will form hypochlorite in the reaction with
water, so twice as much or 1.25 Ibs. At the current chlorine price of
$0.10/lb, the cost is
$0.10/lb x 1.25 lbs/1000 gal. = $0.125/1000 gal.
The total cost is therefore
$0.183 + $0.125 = $0.308 si $0.31/1000 gal.
28
-------
The amount of radiation and chlorine required will depend on the
concentration and composition of the waste being treated. Based on the
experiments performed, it appears that all normal effluents could be ade-
quately treated at the design levels of 60 krads and 75 ppm chlorine.
Where dye concentration in the waste is at a lower level or the color-
producing material is particularly sensitive to treatment, much higher
volumes of waste can be treated at proportionately lower unit costs.
29
-------
SECTION VI
ACKNOWLEDGMENTS
It is a pleasure to acknowledge the advice and assistance received
from many sources during the performance of this project. Mr. Charles
Ris, Office of Research and Monitoring, Environmental Protection Agency,
Washington was project manager and Mr. Edmond P. Lomasney of the South-
eastern Office of the EPA was project officer. Their assistance and
cooperation has been outstanding.
The project was carried out under the supervision of project director
Dr. T. F. Craft, Senior Research Chemist and grant director, Dr. G. G.
Eichholz, Professor of Nuclear Engineering. Others who were significantly
involved in the work were graduate research assistants Luis Y. Garcia,
R. D. Morris, Iqbal K. Mozawalla, Harry T. Taylor, and James T. West.
Mr. S. N. Millspaugh, research assistant, deserves particular mention
because of his careful preparation of the numerous graphs.
Thanks are due to those who furnished samples of dyes and dye solu-
tions. The A. French Textile School supplied several commercial products
and also some purified materials. We are particularly indebted to Mr.
Lewis M. Redd of the Atlanta Office of Sandoz, Inc. He not only sent
numerous dye samples, but was a continuing source of needed information.
Other manufacturers who cooperated were Southern Dyestuff Company and
American Cyanamid Company, both of Charlotte, N. C.
Mr. V. D. Parrott, Director of Utilities, City of Dalton, Georgia
was most helpful with information and discussions on the general and
specific aspects of textile waste disposal problems. He also introduced
Mr. W. K. Newman of West Point-Pepperell, Cabin Crafts Division, who
showed us the operation of a large dyeing operation and furnished numer-
ous samples of dye bath solutions.
We acknowledge and thank Gamma Industries, Inc. for allowing us to
use some of their cobalt-60 as a gamma source while it was being processed
at the Frank H. Neely Nuclear Research Center of the Engineering Experi-
ment Station.
31
-------
The keen interest of personnel of the Georgia State Water Quality
Control Board is appreciated. These include Mr. Warren 0. Griffin,
assistant to the executive secretary, Mr. Charles H. Starling, retired
director of industrial waste services, and his successor, Mr. William M.
Jernigan.
32
-------
SECTION VII
REFERENCES
1. Hyden, W. L., Becknell, D. F., and Elders, T. E., "Survey of the Nature
and Magnitude of the Water Research Needs of the Textile Industry of
Georgia," Water Resources Center, Georgia Institute of Technology, Re-
port WRC-0366 (1966)
2. Arnold, L. G., "Forecasting Quantity of Dyestuffs and Auxiliary Chemi-
cals Discharged into Georgia Streams by the Textile Industry," M.S.
Thesis, Georgia Institute of Technology, Atlanta, Georgia (1967)
3. Besselievre, E. B., "The Treatment of Industrial Wastes," McGraw-Hill
Book Company, New York (1969)
4. Flege, R. K. "Determination of Degraded Dyes and Auxiliary Chemicals in
Effluents from Textile Dyeing Processes," Environmental Resources
Center, Georgia Institute of Technology, Report ERC-0270 (1970)
5. Swallow, A. J., "Radiation Chemistry of Organic Compounds," Pergamon
Press, New York (1960)
6. Crapper, W. H., "The Radiation Chemistry of Organic Dyes," Sandia Cor-
poration, SCTM 139-59 (16), 1959
7. Hayon, E., Scholes, G., and Weiss, J., "Chemical Action of Ionizing
Radiations in Solution. XIX. Some Aspects of the Reduction of Methylene
Blue by X-rays in Aqueous Systems," J. Chem. Soc. 301-311 (1957)
8. Day, M. J., and Stein, G., "Chemical Effects of Ionizing Radiation in
Some Gels," Nature 166, 146-7 (1950)
9. Stein, G., "Some Aspects of the Radiation Chemistry of Organic Solutes,"
Disc. Faraday Soc. 12, 227-234 (1952)
10. Dale, W. M., "Protection Effect and Its Specificity in Irradiated Aqueous
Solutions," Disc. Faraday Soc. 1£, 293-99 (1952)
11. Minder, W., and Heydrich, H., "Radiation Chemistry of Organic Solutions,"
Disc. Faraday Soc. 12, 305-312 (1952)
12. Fair, G. M., and Geyer, J. C., "Water Supply and Waste Water Disposal,"
John Wiley, New York (1954)
13. Craft, T. F., and Eichholz, G. G., "Synergistic Treatment of Textile
Dye Wastes by Irradiation and Oxidation," Int. J. App. Rad. & Isotopes
22, 543-7 (1971)
33
-------
14. Trotman, E. R., "Dyeing and Chemical Technology of Textile Fibres,"
third edition, Griffin, London (1964)
15. "Colour Index," 2nd edition, The Society of Dyers and Colourists,
Yorkshire, England (1956)
16. "Standard Methods for the Examination of Water and Wastewater," Thir-
teenth edition, American Public Health Assn., New York (1971)
17. R. D. Morris, "Detection of Dye Degradation Products from Gamma Irradia-
tion Processes Coupled with Oxydizing Reactions," M.S. Thesis, Georgia
Institute of Technology, Atlanta, Georgia, August 1971
18. Garrison, A. W., Case, F. N., Smiley, D. E., and Kau, D. L., "The Ef-
fect of High Pressure Radiolysis on Textile Wastes, Including Dyes and
Dieldrin," 5th International Conference on Water Pollution Research,
San Francisco, July, 1970; Isotopes & Rad. Technol.. 9, 101-104 (1971)
19. Minrath, W. R., "Handbook of Business Mathematics," D. Van Nostrand,
Princeton, N. J. (1959), pg. 339
Additional references not directly quoted are the following.
Condren, A. J., "Radiation Induced Oxidation of Selected Organics in Waste
Water," Ph.D. Thesis, Purdue University (1969)
Friedlander, G., Kennedy, J. W., and Miller, J., "Nuclear and Radiochemistry,"
2nd edition, John Wiley, New York (1964)
Whittemore, W. L., et al., "Ionizing Radiation for the Treatment of Municipal
Waste Waters," Gulf General Atomic Final Report GA-9924, Contract AT-
(04-3)-167, A.E.C., Division of Technical Information (1970)
Lenz, B. L., et al., "The Effect of Gamma Irradiation on Kraft and Neutral
Sulphite Pulp and Paper Mill Aqueous Effluents," Pulp and Paper Magazine
of Canada 72, No. 2, T75-T80 (1971)
Ten papers on process radiation development appeared in Isotopes and Radia-
tion Technology 8_, No. 4, Summer, 1971. All of these are of interest
in the water or waste-water field, but particularly pertinent are these:
Ballantine, D. S., "Potential role of radiation in waste-water treat-
ment," page 415
Gerrard, Martha, "Sewage and waste-water processing with isotopic
radiation-survey of the literature," page 429
Mytelka, A. I., "Radiation treatment of industrial waste waters: an
economic analysis," page 444
Compton, D. M. J., "Destruction of organic substances in waste water by
ionizing radiation," page 453
34
-------
Ingols, R. S., "Factors Causing Pollution of Rivers by Wastes from the
Textile Industry," Am. Dyestuff Reporter . 358-359 (1962)
Prokert, K., and Stolz, W., "Dosimetry of Ionizing Radiations by Means of
Solid Dye Systems," Isotopenpraxis 6^ 325-330 (1970)
Michelsen, D. L., and Pansier, T. B., "The Treatment of Disperse Textile Dye
Wastes by Fram Fractionation," Bull. 34, Water Resources Research Center,
Va. Polytechnic Institute, Blacksburg, Va. (1970)
Publications
The portion of this work carried out by Mr. R. D. Morris was utilized
as the experimental phase of a thesis in partial fulfillment of the require-
ments for a Master of Science degree in the A. French Textile School, Georgia
Institute of Technology. This thesis was subsequently issued as an interim
project report.
Morris, R. D., "Detection of Dye Degradation Products from Gamma Irradiation
Processes Coupled with Oxidizing Reactions," M.S. Thesis, Georgia In-
stitute of Technology (1971)
Morris, R. D., "Detection of Dye Degradation Products from Gamma Irradiation
Processes Coupled with Oxidizing Reactions," Interim Report, FWQA Grant
No. 12090 FZB, Georgia Tech Project B-391. Engineering Experiment Sta-
tion, Georgia Institute of Technology (1971)
35
-------
SECTION VIII
APPENDIX
A. GRAPHICAL PRESENTATION OF DATA
37
-------
u
O
z
<
h
h
i
(A
Z
<
tt
h
100
90
80
70
60
50
40
30
20
10
10
ACID YELLOW40
(Benzyl Fast Yellow ZGC)
0.125 g/l
X •= 378 nm
17 kR/min.
CI2+85kR
H202+OkR
20
30
40
50
60
TIME (MINUTES)
Figure 1 Transmittance Curves for Acid Yellow 40 at 0.125 g/A
38
-------
100
90
80
70
DISPERSE VIOLET 18
(Artisil Violet RL)
0.125 g/l
X = 600 nm
17 kR/min.
ui
O
z
<
h
h
i
(I)
Z
<
K
h
60
50
40
30
CI2+85kR
20
10
160ppm
8
10
12
TIME (MINUTES)
Figure 2 Transmlttance Curves for Disperse Violet 18
39
-------
IU
U
z
£
cn
z
K
f-
*»P
100
90
80
70
60
50
40
30
20
10
8
ACID BLUE 23
(Kiton Blue)
0.25 g/l
40 ppm Chlorine
X= 600 nm
17 kR/min.
51 kR
85 kR
34 kR
17 kR
OkR
10
12
TIME (MINUTES)
Figure 3 Transmittance Curves for Acid Blue 23 with 40 ppm Chlorine
40
-------
u
U
z
<
h
h
i
(0
z
<
K
h
100
90 -
80 -
70 -
60 -
50 -
40 -
30 -
20 -
10
ACID BLUE 23
(Kiton Blue)
0.25 g/l
80 ppm Chlorine
A=600nm
17 kR/min.
12
TIME (MINUTES)
Figure 4 Transmittance Curves for Acid Blue 23 with 80 ppm Chlorine
41
-------
u
O
z
<
h
h
i
(A
100
90 -
80 -
70 -
60 -
50 -
40 -
30 -
20 -
10
85 kR
8
34 kR
17kR
OkR
ACID BLUE 23
(Kiton Blue)
0.25 g/l
160 ppm
X= 600 nm
17kR/min.
10
12
TIME (MINUTES)
Figure 5 Transmittance Curves for Acid Blue 23 with 160 ppm Chlorine
42
-------
Ill
u
z
<
h
h
£
h
100
90
80
70
60
50
40
30
20
10
NYLOSAN BLUE
0.25 g/l
80 ppm Chlorine
X= 600 nm
17 kR/min.
8
85 kR
34 kR
17 kR
OkR
10
TIME (MINUTES)
Figure 6 Transmittance Curves for Nylosan Blue with 80 ppm Chlorine
43
-------
Ill
o
z
V)
z
100
90
80
70
60
50
40
30
20 -
10 I
NYLOSAN BLUE
0.25 g/l
160 ppm Chlorine
A =600 run
17 kR/min.
170 kR
17 kR
OkR
8
10 12
TIME (MINUTES)
Figure 7 Transmittance Curves for Nylosan Blue with 160 ppm Chlorine
44
-------
IU
U
z
<
h
h
i
(0
z
<
K
h
100
90 -
80 -
70 r
60 -
50 -
40 -
30 -
20
10
ACID VIOLET 48
(Brilliant Alizarine Milling Violet FBI)
0.25 g/l
80 ppm Chlorine
X=550nm
17 kR/min.
8
10
12
TIME (MINUTES)
Figure 8 Transmittance Curves for Acid Violet 48 with 80 ppm Chlorine
45
-------
UJ
U
z
<
h
h
-
0)
100
90 -
80 -
70 -
60 -
50 -
40 -
30 •
20 -
10
OkR
ACID VIOLET 48
(Brilliant Alizarine Milling Violet FBI)
0.25 g/l
160 ppm Chlorine
X= 550 nm
17kR/min.
8
10
12
TIME (MINUTES)
Figure 9 Transmittance Curves for Acid Violet 48 with 160 ppm Chlorine
46
-------
100
90
80
70
DISPERSE BLUE 7
Artisil Blue Green
0.25 g/l
160 ppm Chlorine
X= 600 nm
17 kR/min.
U
Z
<
h
h
K
h
60
50
40
30
20
10
85 kR
17 kR
OkR
8
10
12
TIME (MINUTES)
Figure 10 Transmittance Curves for Disperse Blue 7
47
-------
IU
U
z
<
h
h
i
0)
z
<
K
h
100
90
80
70
60
50
40
DISPERSE VIOLET 4
0.25 g/l
Diluted 1:2 with Methanol
80 ppm Chlorine
X=600nm
17kR/min.
30
20
10
OkR
85 kR
O 34 kR
5 10 15
TIME (MINUTES)
Figure 11 Transmittance Curves for Disperse Violet 4
with 80 ppm Chlorine (Methanol)
48
-------
Ul
U
z
<
h
h
i
w
z
<
£
h
100
90
80
70
60
50
40
30
20
10
DISPERSE VIOLET4
0.25 g/l
Diluted 1:2 with Ethanol
80 ppm Chlorine
A = 600nm
17 kR/min.
OkR
85 kR
> 5 10 15
TIME (MINUTES)
Figure 12 Transmittance Curves for Disperse Violet 4
with 80 ppm Chlorine (Ethanol)
20
49
-------
UJ
O
z
100
90
80
70
60
50
40
30
20
10
DISPERSE VIOLET 4
0.25 g/l
Diluted 1:2 with Ethanol
160 ppm Chlorine
X=600nm
17 kR/min.
170 kR
0 5 10 15
TIME (MINUTES)
Figure 13 Transmittance Curves for Disperse Violet 4
with 160 ppm Chlorine (Ethanol)
20
50
-------
100
90 -
80 -
VAT BLUE 6
(Sandothrene Blue)
0.25 g/l
80 ppm Chlorine
X = 350 nm
17 kR/min.
70 -
u
u
z
<
H
h
i
W
Z
<
K
h
60
50
40
30
20
10
fc**
tfvoV
rt«**
Methanol - 85 kR
H20-1020kR,80ppmCI2
10
20
30
40
50
60
TIME (MINUTES)
Figure 14 Transmittance Curves for Vat Blue 6
51
-------
IU
0
z
<
h
h
100
90
80
70
60
50
40
30
20
10
DISPERSE BLUE 73
(Calcosperse Blue CG)
0.25 g/l
40 ppm Chlorine
X = 550 nm
17 kR/min.
34 kR
17 kR
51 kR
85 kR
UkH
6 8
TIME (MINUTES)
10
12
Figure 15 Transmittance Curves for Disperse Blue 73
with 40 ppm Chlorine
52
-------
100
o
z
h
h
i
in
z
90
80
70
60
50
40
30
20
DISPERSE BLUE 73
(Calcosperse Blue CG)
0.25 g/l
80 ppm
X=550nm
17 kR/min.
85 kR
51 kR
34 kR
17 kR
OkR
10
6 8
TIME (MINUTES)
10
12
Figure 16 Transmittance Curves for Disperse Blue 73
with 80 ppm Chlorine
53
-------
Ill
o
z
(0
Z
100
90 -
80 -
70 -
60 -
50 -
40 -
30 -
20 •
10
DISPERSE BLUE 73
(CalcosperseBlueCG)
0.25
160ppm
= 550 nm
17 kR/min.
6 8
TIME (MINUTES)
10
12
Figure 17 Transmittance Curves for Disperse Blue 73
with 160 ppm Chlorine
54
-------
100
iu
u
z
<
h
h
K
h
90
80
70
60
50
40
30
20
10
DISPERSE BLUE 73
(Calcosperse BlueCG)
0.25 g/l
40,80,160 ppm Chlorine
X = 550 nm
17
34
51
68
85
102
RADIATION DOSE (KRADS)
Figure 18 Transmittance Curves for Disperse Blue 73
with 40, 80, 160 ppm Chlorine
55
-------
100
LU
u
z
(A
Z
90
80 -
70 -
60
50
40
LATYL CERISE Y
0.125g/[
40 ppm Chlorine
X = 550 nm
17 kR/min.
30
34 kR
51 kR
17 kR
85 kR
OkR
20
10
8
TIME (MINUTES)
10
12
Figure 19 Transmittance Curves for Latyl Cerise Y
with 40 ppm Chlorine
56
-------
tu
u
z
<
h
h
i
(0
z
<
K
h
100
90
80
70
60
50
40
30
10
LATYL CERISE Y
0.125 g/t
80 ppm Chlorine
X =550 nm
17 kR/min.
51 kR
17 kR
34 kR 85 kR
OkR
8
10
12
TIME (MINUTES)
Figure 20 Transraittance Curves for Latyl Cerise Y
with 80 ppm Chlorine
57
-------
Ill
u
z
<
I-
h
100
90
80
70
60
50
40
30
20
10
LATYL CERISE Y
0.125 g/l
160 ppm Chlorine
X = 550 nm
17 kR/min.
17 kR
OkR
85 kR
34 kR
6 8
TIME (MINUTES)
10
12
Figure 21 Transmittance Curves for Latyl Cerise Y
with 160 ppm Chlorine
58
-------
Ill
u
z
<
h
h
i
(A
Z
100
90
80
70 -
60 -
50 -
40 -
30 -
20
10
ACID YELLOW 34
(Calcocid Fast Yellow 3G)
0.25 g/l
80 ppm Chlorine
X = 400 nm
17kR/min.
8
10
12
TIME (MINUTES)
Figure 22 Transmittance Curves for Acid Yellow 34
59
-------
100
90 •
80
70
ACID YELLOW40
(Benzyl Fast Yellow 2GC)
0.25 g/l
160 ppm Chlorine
X = 378nm
17 kR/min.
O
Z
<
h
H
i
(A
60
50
K
h
5?
40
30
20
10
A85KR
34 kR 51 kR
OkR
17 kR
6 8
TIME (MINUTES)
10
Figure 23 Transmittance Curves for Acid Yellow 40
with 160 ppm Chlorine
12
60
-------
100
90
80
ACID RED 151
(Azo Silk Red)
0.25 g/l
80 ppm Chlorine
X = 350 nm
17kRmin.
70
u
O
z
60
h
i
05
Z
<
K
h
50
40
30
20
10
85 kR
51 kR
34 kR
17 kR
OkR
6 8
TIME (MINUTES)
10
12
Figure 24 Transmittance Curves for Acid Red 151
with 80 ppm Chlorine
61
-------
100
90
80
ACID RED 151
(Azo Silk Red)
0.25 g/l
160 ppm Chlorine
X=350nm
17 kR min.
70
UJ
O
z
60
50
40
30
20
170 kR
10
6 8
TIME (MINUTES)
10
Figure 25 Transmittance Curves for Acid Red 151
with 160 ppm Chlorine
12
62
-------
UJ
O
z
<
h
h
i
CO
z
<
K
h
100
90
80
70
60
50
40
30
20
10 -
ACID RED 337
(Merpacyl Red G)
0.25 g/l
80 ppm Chlorine
X=500nm
17kR/min.
1020kR
10
20
30
40
50
60
TIME (MINUTES)
Figure 26 Transmittance Curves for Acid Red 337
with 80 ppm Chlorine
63
-------
Ul
O
z
100
90 -
80 -
70 -
60 -
OkR
50 -
40 -
30 -
20
10
ACID RED 337
(Merpacyl Red 6)
0.25 g/l
160 ppm Chlorine
X = 500 nm
17 kR/min.
10
15
20
25
30
TIME (MINUTES)
Figure 27 Transmittance Curves for Acid Red 337
with 160 ppm Chlorine
-------
IU
U
z
<
h
h
i
(A
Z
<
K
h
100
90 -
80
70 •
60
50
40
30
10
ACID BLUE 158
(Neolan Blue)
0.25 g/l
40 ppm Chlorine
X=600nm
17kR/mni.
85 kR
6 8
TIME (MINUTES)
10
12
Figure 28 Transmittance Curves for Acid Blue 158
with 40 ppm Chlorine
65
-------
IU
O
z
<
h
h
i
(A
Z
100
90
80
70
60
40
30
10
ACID BLUE 158
(Neolan Blue)
0.25 g/l
80 ppm Chlorine
X = 600 nm
17 kR/min.
85 kR
51 kR
34 kR
17 kR
OkR
6 8
TIME (MINUTES)
10
12
Figure 29 Transmittance Curves for Acid Blue 158
with 80 ppm Chlorine
66
-------
Ill
O
z
<
h
h
i
(A
Z
<
K
h
100
90 -
80 -
70 -
60 -
50 -
40 -
30 -
20 -
10
ACID BLUE 158
(IMeolan Blue)
0.25 g/l
160 ppm Chlorine
= 600nm
17 kR/min.
12
TIME (MINUTES)
Figure 30 Transmittance Curves for Acid Blue 158
with 160 ppm Chlorine
67
-------
UJ
O
z
<
H
100
90
80
70
60
50
40
30
20
10
DISPERSE YELLOW 23
(Calcosperse Yellow 4RL)
0.25 g/l
Diluted 1:2 with Methanol
80 ppm Chlorine
X=400nm
17kR/min.
OkR
85 kR
> 5 10 15 20 25 30
TIME (MINUTES)
Figure 31 Transmittance Curves for Disperse Yellow 23
68
-------
100
Ul
o
z
<
h
h
i
(A
Z
<
K
h
90
80
70
60
50
40
30
20
10 -
ACID YELLOW 151
(Lanasyn Yellow LNW)
0.25 g/l
80 ppm Chlorine
\ = 400 nm
17kR/min.
51 kR
Q 34 kR
17 kR
OkR
170 kR
8
10
12
TIME (MINUTES)
Figure 32 Transmittance Curves for Acid Yellow 151
69
-------
100
Ul
o
z
<
h
h
i
K
h
90
80
70
60
50
40
30
20
ACID YELLOW 152
(Calcofast Neutral Yellow R)
0.25 g/l
80 ppm Chlorine
X = 450 nm
17 kR/min.
170 kR
10
8
10
12
TIME (MINUTES)
Figure 33 Transmittance Curves for Acid Yellow 152
70
-------
100
UJ
o
z
<
h
h
i
W
Z
<
X
h
90
80
70
60
50
40
30
20
10
ACID ORANGE 86
(Lanasyn Orange RL)
0.25 g/l
80 ppm Chlorine
X = 450 nm
17kR/min.
170 kR
85 kR
51 kR
17 kR
O OkR
6 8
TIME (MINUTES)
10
Figure 34 Transmittance Curves for Acid Orange 86
with 80 ppm Chlorine
12
71
-------
ui
u
z
<
h
I-
i
(0
z
I-
5?
100
90
80
70
60
50
40 -
30 -
10 -
ACID BLACK 107
(Lanasyn Black M)
Q.25 g/l
80 ppm Chlorine
X=350nm
17 kR/min.
204 kR
85 kR
OkR
17 kR
6 8
TIME (MINUTES)
10
12
Figure 35 Transmittance Curves for Acid Black 107
with 80 ppm Chlorine
72
-------
100
90
80
ACID BLACK 107
(Lanasyn Black M)
0.25 g/l
160 ppm Chlorine
X = 350 nm
17kR/min.
70
iu
u
z
<
h
h
i
fl
z
60
50
170 kR
40
30
20
10
85 kR
OkR
6 8
TIME (MINUTES)
10
12
Figure 36 Transmittance Curves for Acid Black 107
with 160 ppm Chlorine
73
-------
100
ui
o
z
Z
<
K
I-
90
80
70
60
50
40
30
20
10
CALCOFAST NEUTRAL RED 3GL
0.25 g/l
80 ppm Chlorine
X = 450nm
17 kR/min.
170 kR
85 kR
17 kR
OkR
6 8
TIME (MINUTES)
10
12
Figure 37 Transmittance Curves for Calcofast Neutral
Red 3GL
74
-------
100
UJ
o
z
<
h
h
i
w
z
90
80
70
60
50
40
30
20
10
SULFUR BROWN 14
(Sodyesul Liquid Brown)
0.25 g/l
160 ppm Chloride
X = 350 nm
17kR/min.
170 kR
8
10
TIME (MINUTES)
Figure 38 Transmittance Curves for Sulfur Brown 14
75
-------
100
90 -
u
0
Z
h
H
i
W
z
£
I-
SULFUR BROWN 14
DENIVAT BLUE
X « 350 nm
17 kR/min.
160 ppm Chlorine
Values at lOmin.
0.25 g/l
o
D
2468 10
RADIATION TIME (MINUTES)
Figure 39 Transmittance Curves for Sulfur Brown 14
and Denivat Blue 57
12
76
-------
iu
U
Z
<
h
h
i
0)
Z
<
K
h
100
90
80
70
60
50
30
20
10
DENIVATBLUE
0.25 g/l
40 ppm Chlorine
X = 600 itm
17 kR/min.
17 kR
51 kR
34 kR
OkR
6 8
TIME (MINUTES)
10
12
Figure 40 Transmittance Curves for Denivat Blue 57
with 40 ppm Chlorine
77
-------
100
90
OENIVAT BLUE
0.25 g/l
80 ppm Chlorine
X = 600nm
17 kR/min.
80
in
O
CA
Z
70
60
50
40
51 kR
85 kR
34 kR
17 kR
OkR
30
20
10
6 8
TIME (MINUTES)
10
12
Figure 41 Transmittance Curves for Denivat Blue 57
with 80 ppm Chlorine
78
-------
Ul
0
z
<
h
i
0)
z
<
K
h
100
90
80
70
60
50
40
30
20
85 kR
68 kR
51 kR
34 kR
17 kR
OkR
10
DENIVATBLUE
0.25 g/l
160 ppm Chlorine
X = 600 nm
17kR/min.
6 8
TIME (MINUTES)
10
Figure 42 Transmittance Curves for Denivat Blue 57
with 160 ppm Chlorine
12
79
-------
O
z
<
h
H
i
(A
Z
<
K
h
100
90
80
70
60
50
40
30
20
10
DEN I VAT BLUE
0.25 g/l
80,160 ppm Chlorine
X=600nm
Readings Taken
After 6 min.
2
8
10
RADIATION TIME (MINUTES)
12
Figure 43 Transmittance Curves for Denivat Blue 57
for Various Radiation Doses
80
-------
u
o
z
(A
Z
<
K
h
100
90
80
70
60
50
40
30
ACID BLUE 83
(Benzyl Cyanine 6B)
0.25 g/l
40 ppm Chlorine
X = 550 nm
17kR/min.
10
6 8
TIME (MINUTES)
10
12
Figure 44 Transmittance Curves for Acid Blue 83
with 40 ppm Chlorine
81
-------
IU
U
z
(A
Z
100
90 -
80 -
70 -
60 -
50 -
40 -
30 -
20
10 -
34 kR
85 kR
51 kR
17 kR
QkR
ACID BLUE 83
\Deiityi oyaiiuic uu
0.25 g/l
80 ppm Chlorine
17 kR/min.
I i i i I
n 2 4 6 8 10
i
i
12
TIME (MINUTES)
Figure 45 Transmittance Curves for Acid Blue 83
with 80 ppm Chlorine
82
-------
100
90 -
80 -
70 -
IU
U
Z
h
h
i
(R
Z
K
60 -
50 -
40 -
30 -
20
10
OkR
ACID BLUE 83
(Benzyl Cyanine 6B)
0.25 g/l
160 ppm Chlorine
\ = 550 nm
17kR/min.
8
10
Figure 46
TIME (MINUTES)
Transmittance Curves for Acid Blue 83
with 160 ppm Chlorine
12
83
-------
100
90
80
MORDANT BLUE 1
0.25 g/l
80 ppm Chlorine
X = 450 nm
17 kR/min.
UJ
U
h
h
i
(0
z
<
K
I-
70
60
50
40
30
20
10
170 kR
8
10
TIME (MINUTES)
Figure 47 Transtnittance Curves for Mordant Blue 1
with 80 ppm Chlorine
12
84
-------
100
III
u
H
h
i
(0
z
<
K
h
MORDANT BLUE 1
0.25 g/l
160ppm Chlorine
X = 450 nm
17kR/min.
TIME (MINUTES)
Figure 48 Transmittance Curves for Mordant Blue 1
with 160 ppm Chlorine
85
-------
IU
U
z
<
h
h
i
(0
z
<
£
h
100
90 -
80 -
70 •
60 -
DIRECT YELLOW 106
(Lutnicrease Yellow Eful)
0.25 g/l
80 ppm Chlorine
X = 450nm
17 kR/min.
50 •
40 -
30 -
10
85 kR
51 kR
34 kR
17 kR
O OkR
1
1 2
i
4
i
6
i
8
i i
10 12
TIME (MINUTES)
Figure 49 Transmittance Curves for Direct Yellow 106
with 80 ppm Chlorine
86
-------
100
Ill
0
z
h
h
i
(0
z
K
h
90
80
70
60
50
40
30
20
10 -
DIRECT YELLOW 106
(Lumicrease Yellow Eful)
0.25 g/l
160 ppm Chlorine
X = 450 nm
17 kR/min.
12
TIME (MINUTES)
Figure 50 Transmittance Curves for Direct Yellow 106
with 160 ppm Chlorine
87
-------
100
111
o
z
<
h
h
i
IA
Z
90 -
80 -
70
60
50
40
30
20
10
DIRECT BLUE 86
(Pyrazol Fast Turquoise GLL)
0.25 g/l
80 ppm Chlorine
X = 600 nm
17kRmin.
85 kR
51 kR
17 kR
O OkR
8
10
12
TIME (MINUTES)
Figure 51 Transmittance Curves for Direct Blue 86 with
80 ppm Chlorine
88
-------
Ill
o
z
<
h
h
i
(A
z
<
g
h
100
90
80
70
60
50
40
30
20
10
DIRECT BLUE 86
(Pyrazol Fast Turquoise GLL)
0.25 g/l
160 ppm Chlorine
A=600nm
17 kR min.
68 kR
51 kR
8
10
12
TIME (MINUTES)
Figure 52 Transmittance Curves for Direct Blue 86 with
160 ppm Chlorine
89
-------
Ill
o
z
<
I-
h
i
U)
z
<
K
h
100
90
80
70
60
50
40
30
20
10
DALTON SOLUTION NO. 1
(Reddish Brown)
80 ppm Chlorine
X = 400 nm
17 kR/min.
85 kR
51 kR
O 34 kR
17kR
OkR
8
10
12
TIME (MINUTES)
Figure 53 Transmittance Curves for Dalton Solution No. 1
90
-------
u
O
z
<
h
h
i
(0
K
h
100
90
80
70
60
50
40
30
20
10
O OkR
17 kR
34 kR
?5kR
1 kR
DALTON SOLUTION NO. 2
(Light Straw)
40 ppm Chlorine
X = 350 nm
17kR/min.
8
10
12
TIME (MINUTES)
Figure 54 Transmittance Curves for Dalton Solution No. 2
91
-------
ui
O
Z
<
h
I-
i
(0
z
<
K
h
100
90
80
70
60
50
40
30
10
DALTON SOLUTION NO. 3
(Deep Yellowish-Brown)
150 ppm Chlorine
X = 350 nm
17 kR/min.
85 kR
51 kR
34 kR
17 kR
OkR
8
10
12
TIME (MINUTES)
Figure 55 Transmlttance Curves for Dalton Solution No. 3
92
-------
100
111
o
z
<
h
h
i
in
z
<
K
h
DALTON SOLUTION NO. 4
(Very Dark Green-Opaque)
160 ppm Chlorine
400 nm
17kR/min.
10
12
TIME (MINUTES)
Figure 56 Transmittance Curves for Dalton Solution No. 4
93
-------
100
Ul
o
z
<
I-
I-
0)
z
<
K
I-
90
80 -
10
ACID YELLOW 76
(Benzyl Fast Yellow GNC)
0.25 g/l
40 ppm Chlorine
X = 390 nm
8 kR/min.
pH4.0
30
40
50
60
O 10 20
TIME (MINUTES)
Figure 57 Transmittance Curves for Acid Yellow 76 at pH 4.0
94
-------
II!
u
z
<
h
i
0)
z
100
90 -
80 -
70 -
60
50
40
30
20
10
ACID YELLOW 76
(Benzyl Fast Yellow GNC)
0.25 g/l
40 ppm Chlorine
X = 390 nm
8 kR/min.
pH6.5
10
20
30
40
50
60
TIME (MINUTES)
Figure 58 Transmittance Curves for Acid Yellow 76 at pH 6.5
95
-------
Ul
O
z
h
i
CO
K
h
100
90
80
70
60
SO
40
30
20
ACID YELLOW 76
(Benzyl Fast Yellow GNC)
0.25 g/l
40 ppm Chlorine
X = 390 nm
8 kR/min.
pH8.5
40 kR
0
0
<
till II
> 10 20 30 40 50 60
TIME (MINUTES)
Figure 59 Transmittance Curves for Acid Yellow 76 at pH 8.5
96
-------
UJ
U
z
<
h
h
i
(0
z
100
90 -
80 -
70 -
60 -
50 -
40 -
30
20
10
ACID ORANGE 86
(Lanasyn Orange RL)
0.25 g/l
40 ppm Chlorine
X = 450 nm
6 kR/min.
pH4.0
10
20
30
40
50
60
TIME (MINUTES)
Figure 60 Transmittance Curves for Acid Orange 86 at pH 4.0
with 40 ppm Chlorine
97
-------
UJ
U
z
<-
h
h
i
CO
z
<
K
h
100
90
80
70
60
50
40
30
20
10
ACID ORANGE 86
(Lanasyn Orange RL)
0.25 g/l
40 ppm Chlorine
X = 450 nm
6 kR/min.
pH6.7
10
20
30
40
50
60
TIME (MINUTES)
Figure 61 Transmittance Curves for Acid Orange 86 at pH 6.7
with 40 ppm Chlorine
98
-------
Ul
U
z
<
I-
H
i
(A
Z
100
90
80
70
60
50
40
30
20
10
ACID ORANGE 86
(Lanasyn Orange RL)
0,25 g/l
40 ppm Chlorine
X=450nm
6kR/min.
pH8.7
10
20
30
40
50
60
TIME (MINUTES)
Figure 62 Transmittance Curves for Acid Orange 86 at pH 8.7
with 40 ppm Chlorine
99
-------
14
o
z
<
h
h
i
(0
z
100
90 -
80 -
70 -
60 -
50 -
40 -
30
20
10
OkR
ACID ORANGE 86
(Lanasyn Orange RL)
0.25 g/l :-* •
80,160 ppm Chlorine
X = 450 nm
6 kR/min.
pH4.0
10
20
30
40
50
60
TIME (MINUTES)
Figure 63 Transmittance Curves for Acid Orange 86 at pH 4.0
with 80 ppm Chlorine
100
-------
100
111
u
z
<
I-
h
ACID ORANGE 86
(Lanasyn Orange RL)
0.25 g/l
80,160 ppm Chlorine
X = 450nm
6 kR/min.
pH6.7
30
40
50
60
TIME (MINUTES)
Figure 64 Transmit tance Curves for Acid Orange 86 at pH 6.7
with 80 ppm Chlorine
101
-------
UJ
O
z
<
h
h
i
K
I-
100
90 •
80 -
70 -
60 -
50 -
40 -
30
20
10
OkR
ACID ORANGE 86
(Lanasyn Orange RL)
0.25 g/l
80,160 ppm Chlorine
X = 450nm
6 kR/min.
pH8.7
10
20
30
40
TIME (MINUTES)
50
60
Figure 65 Transmittance Curves for Acid Orange 86 at pH 8.7
with 80 ppm Chlorine
102
-------
SECTION VIII
APPENDIX
B. DESIGN STUDY FOR A REACTOR LOOP IRRADIATOR
103
-------
I. Introduction
The Georgia Tech 12,000 curie cesium-137 gamma irradiator produces a
uniform dose over a relatively small volume, and its usefulness is limited
where large volumes require irradiation. The source configuration is such
that an intense radiation field is available only at the bottom of a long
well shielded 2" diameter tube, and it is very difficult to stir, make addi-
tions, or perform any other operation on a sample while it is actually in
the irradiator.
Because of these mechanical limitations, consideration was given to the
construction of a reactor loop irradiator facility (RLIF) in which a solu-
tion containing an appropriate element would be circulated through the
Georgia Tech Research Reactor. Some of the element would become radioactive
while passing through the flux region. The solution would then be passed
through a coil outside the reactor where the gamma rays emitted by the decay
of the radioactive element would be concentrated. This arrangement should
provide a field of satisfactory volume, depending on the dimensions of the
coil. The intensity of the field would then be determined by such matters
as the nuclear properties of the chosen element, the capacity of the loop
system, and the rate of flow.
The nuclear properties needed in the activable element include a large
thermal neutron capture cross section, and the isotope produced should decay
with energetic gamma emission and a short half-life to a short lived or
stable daughter. It is important that no appreciable amount of long-lived
activity be produced so that the facility can be shut down rapidly. The
particular compound of the chosen element must be selected with consideration
104
-------
Of solubility, corrosiveness, and cost. These criteria limit severely the
number of possible elements that could be used, and only aluminum, manganese,
and silver were investigated.
A complete RLIF design would require a study of the theory of operation,
material selection, shielding calculations, cost estimates, and preparation
of engineering specifications. The present study was intended to determine
answers to the fundamental questions concerning possible attainable field
intensities and time to attain steady state conditions, for several poten-
tially useable elements. A mathematical solution to the cyclic activation
problem has been derived, and the usefulness of computer techniques in a
parametric search for optimum operating conditions has been demonstrated.
i.
This computer program can serve not only in a feasibility study of an
RLIF, but can also be used to predict the resultant activity of any solute
in conjunction with flow through a volume of approximately uniform neutron
flux.
II. Theory
0 ^ t *
INTERNAL
BRANCH
region where
0 2: const
Reactor
Shield
aSL
0 ^ t *
ex
ex
EXTERNAL
BRANCH
FIG. Bl.
105
-------
At any given time after the loop has been in operation, three types of
nuclei will be present: (1) the original element, A , (2) the activated
element, A , and (3) the decay product, B
A* + n - A - B (Bl)
By considering an arbitrarily small volume, AV, of the circulating fluid,
and following its path throughout the loop, a solution to the problem can be
approximated at any position of the k loop. The general equations govern-
ing the activity during any loop k at time t are:
dA.
—iSitS = - XA. . + (^ A n - A. , - B. ) o0 (B2)
dt in,k \V o in,k k/ v '
dAex k
—If2~= • XAex,k k= 1»2,3,...cycles
A. , = number activated atoms in AV (internal branch)
A . = number activated atoms in AV (external branch)
cX j K.
n = total number of moles of original element in system
X = decay constant
B. - number atoms of decay product in AV
V = total volume of system
A = Avogadro's number
a = microscopic absorption cross section
0 = average neutron flux
106
-------
The buildup factor, B, , was neglected since it is always small compared to
the amount of original material present and results in an integral differen-
tial equation with no straightforward method of solution. After this ap-
proximation, the equations are solved simultaneously under the appropriate
initial and boundary conditions, and an iterative solution is found that
approaches a steady state value after a large number of cycles.
r ,aJL N AV S 0n ,.^ ... AV Z 0
A. .(t) - [A . . (-^} -- 1-1 e-(X+CT$)t + - !- (B3)
in,kv L ex,k-l \ Q / x+o -1
f. v A f j-n \ "At /^ ^ j. GX
:(t) - Ain,kV—J6 °'sts —
k = 1,2,3,—cycles
Q = flow rate
a = cross sectional area of pipe
S.. = pipe length internal
*in r r &
A - pipe length external
Z a macroscopic absorption cross section
Such a solution is difficult to work with since the activity at any point
depends on the solution to the previous branch of the loop. This necessi-
tates a great deal of calculation to investigate each particular loop
configuration.
107
-------
III. Program
In order to vary parameters such as geometry, type and concentration
of solute, and flow rate, a computer program was written that would facili-
tate rapid accumulation of the large quantity of data required. This program
allows the user the option to change any of 12 input parameters and, for
each set of input specifications, will perform a survey over a given array
of element quantity (expressed in moles) and flow rates.
Briefly, the program operates as follows: Equations B3 are first
used to determine the linear activity at the loop boundaries throughout the
cycle. Hence, the solution can be found for any point and time by the re-
application of Eq. B3 with the appropriate boundary solution over the pre-
vious loop branch. The dose rate at the center of the irradiator coil is
then estimated by calculating the contribution from each unit length of pipe
in the coil at an effective radius from the center. This procedure is then
repeated for the next cycle and is continued until the linear activity at a
point in the k cycle differs by less than 0.1% with that in the k-1 cycle.
When this condition is reached, the system is said to have reached steady
state.
A complete history of the activation .levels and radiation field strengths
up to steady state is compiled by the computer and presented in tabular form
in the output. AIN(I) and AEX(I) are the linear activity levels (Ln curies/
cm) at the internal and external boundaries, respectively. TIME is the time
in seconds and DOSE RATE gives the dose rate at the center of the coil in
rad/hr. In addition, several other informative calculations are made after
steady state is reached for purposes of comparison and later use. For ex-
ample, the total activity in the pipe region external to the reactor is
needed for use in shielding calculations.
108
-------
INPUT CARD FORMATS
Card No.
1
2
4
5
37-67
Format
80A1
80A1
I1,5X,I4
Use
10E8.4
E8.4
E8.4
First two cards contain 80 spaces each of alphanu-
meric information to be used as a problem heading.
NN,NI
NN is an integer optional output number. NN = 0
or 1. If NN = 0, the table of dose rate buildup
is not printed and only the results after steady
state are given. NI is the number of maximum
iterations permitted if steady state is not
reached. If exceeded, an internal error message
is printed.
The 12 fixed input parameters are read in the
order they appear under output heading.
Two cards: 10 on first, 2 on second.
Any number of cards, less than 30, containing
the values of the number of moles for element
used in parametric survey, A negative number key
card must be added at end.
Same as cards 6-36 except the values are now for
flow rates.
IV. Conclusions
1. Aluminum in the form of A1(NO_) '6H_0 was found to be the most
suitable of the elements investigated. In a system of 5000 cm3 containing
9 moles of the material, a steady state dose rate of 1.73 X 103 rad/hr was
indicated after 20.4 minutes. This represents 32.2% of the saturation
activity and only 14.7 curies of activity outside the reactor.
In comparison, manganese in the form of Mn(NO_)2-6H20 was capable of
a higher dose rate in an identical facility, 7.05 x 104 rad/hr, but the
steady state time was almost 430 minutes. This represents 24.1% of the
saturation activity; however, with over 700 curies in the external branch
at steady state, there would be definite shielding and safety problems.
109
-------
AgNO_ was Investigated and found to give a high dose rate of almost
2 X 10s rad/hr, but appreciable buildup of the long-lived, 255 day, Ag
precludes the use of silver in an RLIF.
2. Except for activation products with half-lives less than about one
minute, the flow rate is not a critical parameter. In general, the dose
rate will be greater at the coil as the flow rate increases but there comes
a point where a small increase in dose rate does not warrant additional pump
size. For aluminum, ti » 2.27 min, a flow rate of 1 gal/min is acceptable
while for Ag , ti = 24.4 sec, a rate of 4.5 gal/min brings the dose rate
to within 8070 of the maximum steady state dose rate.
3. The dose rate always increased as the number of moles increased.
The computer program follows this appendix and several pages of the
printout for A1(NO_)3 are included for reference.
110
-------
BSYSTEMS*ALTPRO.FOR*-BtIS IRRAD*
FOK OBL-05/05-20;il 1,01
00101
"OOlOS"
00103
'OOIOT
0010S
!• DIMENSION >15XJ.BnAl/3x.'0: ' ,EB.».1X, • INCHES* • 16X»
1«OIAK'ETER OF PIPE VlX»'LlN= • tEB.HtlX, • INCHES" ,16X, 'PIPE LENGTH «i
"2THIN FLUX REoION'/lX.«LEX= • .EB.U, ix. «IMCHESi ,16X.'PIPE LtNGTH EXT
3ERNAL TO FLUX REGIOMV1X, >LOS= ' »E8.*, IX, i INCMES'il6X, 'PIPE LENGTn
"1 OUTSIDE REALTOR SHIELD'/2X.'FL= '.Eb.*, IX, 'U£UTS/7X. •«"
_5VERAGtU:Ly<'/2J^ilSA=^,EB.«*.IX.'CM2'. J9X.«MICKOSCOPIC ABSORPTION X
00106
'00106
13*
"
6=SECf •/2X.«M»=~TrEft.<»,lx.«G/6MOLE«.T5X.'t MOLECULAR liEIGHT'/2<»~«HL=
7',E8.«».lX,tStC»_»19X, 'HALF LIFEVJXt'Er ' ,E8.<», IX. 'MEV . 19X. 'GAMMA
6ENER6TM ...... ~ . ----- ......... - ---
MO 01
~M002
MOOJ
'F001
F002
TB65
F00«
"FOOS
FOOb
"FOOT
FOO»
F009
F010
927 FORMATdX. «MUR= ' >E8.i».lX> >CM2/G> 1 17X> 'MASS-ABS COEF IN AIR'/iX.'c F011
1D= '. £8. », IX. 'INCHES'. IbX, 'COIL PlAMETEf /ZX, 'CH= ' .EB.trlXt 'INCH& F012 _
2S'fl6X,'COIL HEIGHT'f " F0l»
928 FOHMATIE8.UI _ _______ . __ ____ _ F01» _
92<"~FORMAT('0* ^'SEQUENCE NUMBER (' .12. '.'. 12. •»• .SX. 'FOR CALCULATIONS F015
miTH;'/'o',5i>x,'i',ia.t|»,i x , 'SOLUTE IN SYSTEM .= '.E8.«nix» 'HOLES*
'
_
00111 5T- 2/ShX,» (I.I2,I)<>SX>>FLOH RA'TE = • .Efl.K.lX. 'G4L/M1NM F017
00112 _ 22^ _ 93H FORMAT I • 0* .IfcX, 'ITERATION I ' ,7X. »*IN( I) ' >7X- *AEX< I) ' »9X» 'TIME' ,»X. F01V
"00112 23» ""1'DOSE" HATE.«/^7Xi • l'r"H5X»E8.m ) - ' ............. F020
00113 _ 2«»* _ 931 FORMAT<2<»X,I<»,4(5X,E0.i»J> ___ ____ __ __ F021
~00m 85« 932 'FORMATl '0*. 'STEADY-STATE ACHIEVEP AT Tl"*E"T s • »E8.t, JX» 'MIN« .2X. • F022
C011H 26* LA/JEP >»I'»>l*»'CYCLE5*/'0'.g5X,'rCNCEHTPATION'.22X.' = '»E,8.». IX. » F023
"
_
00114 27* F&HAMSVLlf£.R'/2bX. «SATURATlONlfCt"l VITT' . lik.'s • .Ett.t, IX, •cUMICS/Crt F02»
0011* _ 28» _ 3'KAX ACTIVITY AT EXIT OF FLUX REGION = • tE8.«,lX»«CURlES/CM«__F025
~00ll« 29* 4/2bX,*AVG ACTIVITY AT LOCATION OF COIL = t ,E8.<*. IX, 'CUKItS/CMV F02b
0011* _ 30» _ 52bX. 'TOTAL ACTIVITY IN REGION'/3lX. 'EXTERNAL TO REACTOR SiiltLO'.SA__FO*7
'0011* 31* <,,'= "•.ES.U. IX, •CURIES'/'O'.ZSX, 'CALCULATED DOSE RATE AT CtNTEK OF F028
0011<» 32* 7COIL IS;'>20»»'R = ' .£8. ». 1X> 'RAP/HP' ,2X>5( *B«0' )/«0'/lX>120l '«')/ FA2d
00 IT*
00115
00116"
00116
00116
00116
35*
3H«
3-,*
36*
37-
00117
00117
00117
00120
00138
<»0*
«»3»'
«*t»
0015« «b*
0015* — »7*
00177 «8*
0020* "~ »9«
00205 50
81X.1?U( •«•) > Ft»2(J
935 FORMAT(Il,5X»l<»l_ _ _ _ _ FC2tt
93fc FORMAT««0'.120('-O/?0»»3&Xr'REFrBENCE VOLl^E s ' .fcX.Ea.1*. IX.'CM31 FD28
1/37X.'TOTAL VOLUME OF SYSTEM = • .E8.»,IX.«C«"3«/37X.'DECAY COMSTANl FE28
2 - '.BX.Ea.u.lX.'SEC-l'/'O'/lX.'npTION NUMREM = •.ll/'O'/lX.'MAX n'*FF2B
3UMHEK OF ITEMATIO>IS_sj^.I»/'0'/lXil20r»>l/lX.1.2Q«'»f )J FG2fl
93« FORMA"tTrO'^'-«»FAILUH£ T'O CONVERr-E»»«'/«0'>2i>A»'CYCLES'»l"»X. •= «t» F02»
l«/?6X»'TlME'.lbX,<= '. EB.». IX, «MTN«/26X. 'PRESENT ACTIVITY*. »X,'= • F030
~~ 2.E8.«.. IX,'CUH1ES/CM'/26X»'SATURATION ACTIVITY = • ,£S.<»»1X> 'COHIES/"" FOS1
3CM« /'O'/IX. 120 (•••1/1X.120 (•••II F032
READ (5>92,935I MI.NI HAOH
M0"55
PEAD (5,9251 D,LIIJ,LEX.LDS«FL,5».MW,HL,E,MUH,CDtCH
WRITE (b.9261 (ALP{ I) .1 = 1,60) ^CALPJ^I), I_=81, IfcO) ,O.LIN,LEX,LOS.FLf>_ M006
1A,MW,HL,C " " " M007~
WRITE (6.927) MUR.CO.CH M008
- • M009"
D=(2.b*OI«0
LIN=<2.5uO)«LlN
MOlO
00206
00207
00210
00211
00212
00213
0021*
00215
00216
00225
00230
00233
00236
00201
002«»
002*7
31*
52*
53«
5«*
55*
56*
57»
56*
59*
60*
61*
62*
63*
b**
6b*
6b*
00252 67*
00255 68*
ouisr
00261
00262
b*»*
70*
^1*
L£x=«2.5*CU
CH=t2.540)*CM
L=LIN»LEX
VL=I3.1»159I*I (D/2.I**2I
V=VL»L
6=ALOG(2.»/HL
WRITE 16.936) VL.V.G.NN.M
DO 151 1=1.30
READ 15,9281 Nil)
151 IF INID.LT.U.I CO TO 152
15? DO 153 1=1. 3U
READ (5,928) 0(1)
153" IF (G(I).LT.O.) 60 TO IS*
150 DO 155 J=l,30
00 156 1=1. 30
IF (O(I).LT.O.) GO TO 155
IF (N(J) .LT.U.I STOP
W=(B0.3)*U(I)/(D**2I
P=(7.«>fcE.»i3)*N(J)/(L*D**2)
M011
M012
H013
M01*
MOlb
MOlb
MAlB
M017
MA17
M018
M019
M020
M021
M022
M023
M02H
K02&
N02b
M027
M028
H030
111
-------
00263
00260
00265"
00266
00276
00277
O036i~
00302
00303
0030*
00312
0031S
00316
00316
00317"
00320
00321
00322
DO 324
00325
00326
00327
00336
00337
00340^
003*2
003*5
00347
-~ 00350
003S1
OD35Z-
00353
' " 0035»
003b5
00367
P0371
UOJ7Z
00373
00374
00402
00404
00406
00407
72*
73*
7»*
75*
76*
77*
78*
79*
80*
SI*
82*
83*
04*
as*
86*
87*
• 88*
89*
90*
91*
92*
93*
94*
95*
9e*
97*
* 96* ' '
99*
"100* '
101*
102*
103*
104* ~
1 Ob-
' 106*"
107*
106*
109*
110*
111*
112- '"~
113*
114-
AINl=VL«P*SA*FI_*U.-tXP|-G«LlN/»O»/{3.70£+lO|
AEXl=AINl-EXPt-G*LEX/«>
RF=CC/4.tCD/l4.«COSUTAN
WRITE (6.929) J. I. J.NU1 . I r Ot 1 1
C=PW>NCJ)*10.»*3/V
IF (M..EQ.O) GO TO Ib8
AC=AIin-EXP(-G-LEX/|2.»W) )
R=t5.33E*05)-AC*E*CH*CD*MUR/|D*RF**2)
T=LIH/W»LEX/J2.*«I
MRITE (6.930) AINl.AEXlfT.R
158 DO 147 K=2.N1
,M=K-1
AIN2=AEXl*CXPC-6*LIN/*>»VL*CP/(3.70E+10>-AEXl/(e*VL»*SA*FL*(l.-CA
IPI-G-LIN/n))
AEX2=AIN2*EXP(-6*LEX/M>
C1=(AIIJ2-AIN1)/AIN2
C2=IAE.X2-AEX1)/AEX2
IF INh.EO.O) GO TO 1«B
T=M«L/**L1N/»«LEX/(2.»W)
AC=AIN2»EXP(-G*LEX/(2.*HI1 ^
R=(5.33E*05)*AC«E*CH*CO*HUR/|D*RF*»2I
WRITE 16.9311 K.AIN2.AEX2.T.R
1«R AIM1=AIN2
AEX1=AEX2
IF (C1.LE..OU1.ANO.C^.LE..001) GO TO 149
147 IF (K.EO.NI) GO TO ISO
149 IF (NN.NC.O) GO TO Ib7
T=M«L/li«LI»l/«i«LEX/l2.»lll
AC=AIia>EXPI-G*LLX/(2.*MI)
P=l5.33E*OS)*AC*E*CH»CD*HUR/tD*RF**2|
T.57 T=T/60.
SAT=VL*P»bA*FL/(3.70E«10l
AXrRIU I6.93<») K.T.AIN1.SAT
156 CONTINUE
155 CONTINUE
STOP
END
M031
M032
Mb94
HA34
MB 34
MC34
MOSS
M036
MD37
H038
H039
MU40
M0*l
M042
N043
K04H
M04b
HA45
M046
K047
H048
M049
MA49
MB49
MOSU
M051
KA52
H»52
MC52
M0b2
ME52
M053
M05b
MOS7
MOS8
MA58.
Mt>5u
MCb8
MOSo
Mtsa
M059
M060
M063
NO DIAGNOSTICS.'
112
-------
FACILITY DESIGN INCORPORATING AUIN03>3»9H20
0=
LIN=
LEX=
LOS =
F-L=
.'; SA-
1 HL=
•MURS
"a
.1080+03
.16BO+D3
.3500+13
.2340-24
.3752+03
.13o2+03
.1778+01
.4500-Ul
AVERAGE FLUX
MICROSCOPIC ABSORPTION X-SECT
MOLECULAR HEIGHT
HALF LIFE
GAMMA LNERGY
MASS-A3S COEF IN AIR
COIL DIAMETER
COIL HEIGHT
REFERENCE VOLUME = .5067+01 CM3
TOTAL VOLJME OF SYSTEM = .4942+04 CH3
DECAY CONSTANT = .5089-03 SEC-1
~S"£OU£NC~
FOR C~ALCULATiONS~*ITH:
< 1) SOLUTE IN SYSTEM = .5000+01 MOLES
( 1) FLOW RATE = .2700+01 GAL/MIN
ITERATION I
1
2
3
4
5
6
7
8
9
10
11
12
13
m
15
16
17
IS
19
20
21
22
23
2
-------
SEQUENCE NUMBER < If 2)
ITERATION I
1
Z
3
14
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
AINU) -
.9505-03
.1855-02
.2715-02
.3533-02
.4312-02
.5053-02
.5758-02
.6428-02
.7066-02
.7673-02
.8250-02
.3799-02
.9322-02
.9819-02
.1029-01
.1074-ul
.1117-01
.1158-01
.1196-01
.1233-01
.1266-01
.1302-01
.1334-01
.1364-01
.1392-01
.1420-01
.1446-01
.1471-01
.1494-01
.1516-Ul
.1538-01
.1558-01
.1577-01
.1596-01
.1613-01
.1630-01
.1645-01
.1661-01
.1675-01
.1688-01
.1701-01
.1714-ul
.1725-01
.1737-01
.I7i»7-01
.1757-01
.1767-ul
.1776-01
.1785-01
FOR CALCULATIONS WITH:
A£x
.9170-03
.1789-02
.2619-02
.3409-02
.4160-02
.4875-02
.5555-02
.6202-02
.6817-02
.7403-02
.7960-02
.8490-02
.8994-02
^.9473-02
.9930-02
.1036-01
.1078-01
.1117-01
.1154-01
.1190-01
.1224-01
.12b6-0l
.12B7-01
.1316-01
.1343-01
.1370-01
.1395-01
.1419-01
.1441-01
.1463-01
.14«<4-Ul
.1503-01
.1522-01
.1539-01
.I5b6-0l
.1572-01
.15418-01
.1602-01
.1616-01
.1629-01
.1641-01
.1653-01
.1665-01
.1675-01
.16B6-01
.1695-01
.1705-01
.1713-01
.1722-01
( 1) SOLUTE
( 2)
TIME
.6275+01
.1607+02
.2587+02
.3566+02
.4546+02
.5525+02
.6505+02
.7484+02
.8464+02
.9443+U2
.1042+03
.1140+03
.1238+03
.1336+03
.1434+03
.1532+03
.1630+03
.1728+03
.1826+03
.1924+03
.2022+03
.2120+03
.2218+03
.2316+03
.2414+03
.2512+03
.2610+03
.2708+03
.2605+03
.2903+03
.3001+03
.3099+03
.3197+03
.3295+03
.3393+03
.3491+03
.3569+03
.3687+03
.3785+03
.3883+03
.3981+U3
.4079+03
.4177+03
.4275+03
.4373+03
.4471+03
.4569+03
.4667+03
.4765+03
IN SYSTEM = .5000+01 wOLES
FLOW RATE = .8000+01 SAL/MIN
DOSE RATE
.4702+02
.9176+02
.1343+03
.1748+03
.2133+03
.2500+03
.2848+03
.3180+03
.3496+03
.3796+03
.4082+03
.4353+03
.4612+03
.4858+03
.5092+03
.5314+03
.5526+03
.5728+03
.5919+03
.6102+03
. .6275+03
.641*0+03
.6597+03
.6747+03
.6889+03
.7024+03
.7153+03
.7275+03
.7392+03
.7502+03
.7608+03
.7708+03
.7804+03
.7894+03
.7981+03
=8063+03
.8141+03
.8215+03
.8286+03
.8353+03
.8417+03
.8478+03
.8536*03
.8591+03
.8644+03
.8694+03
.8741+03
.8786+03
.8829+03
llU
-------
50
51
52
53
54
55
56
57
56
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
.1793-01
.1601-01
.1808-0'
.1815-01
.1822-01
.1B29-01
.183S-U1
.1840-01
.1846-01
.1851-01
.1856-01
.1861-01
.1866-01
.1870-01
.1874-01
.1878-01
.1862-01
.1885-01
,1889-01
.1892-01
.1895-01
.1898-01
.1901-01
.1903-01
.1906-01
.1908-01
.1910-01
.1912-01
.1914-01
.191b-0i
.1730-01
.1737-01
.1745-01
.17bl-01
.175B-01
.1764-01
.1770-01
.1776-01
.1781-01
.1766-01
.1791-01
.1796-01
.1800-01
.1804-01
.1808-Q*
.1812-01
.1815-01
.1819-01
.1822-01
.1825-01
.1828-01
.1831-01
.1834-01
.1836-01
.1839-Ul
.1841-01
.1843-01
.1845-01
.1847-01
.1849-01
.4863+03
.4961+03
.5058+03
.5156+03
.5254+03
.5352+03
.5450+03
.5548+03
.5646+03
.5744*03
.5842+03
.5940+03
.6038+03
.6136+03
.6234+03
.6332+03
.6430+03
.6528+03
.6626+03
.6724+03
.6822+03
.6920+03
.7018+03
.7116+03
.7213+03
.7311+03
,7409+03
.7507+03
.7605+03
.7703+03
.8870+03
.8909+03
.8946+03
•8981+03
.9015+03
.9047+03
.9077+03
.9106+03
.9133+03
.9159+03
.9184+03
.9208+03
.9230+0-
.9251+03
.9272+03
.9291+03
.9310+03
.9327+03
.9344+03
.9360+03
.9375+03
.9389+02
.9403+03
.9416+03
.9428+03
.9440+03
.9451+03
.9462+03
.9472+03
.9481+03
80
.1918-01
.IBbl-Ol
.7801+03
.9491+03
~5TcAE>Y-bTATE ACHIEVED AT TIME T = .l3bO+02 MlN AFTER 80~CYCLES
CONCENTRATION
SATURATION ACTIVITY
=".3796+03 GRAMS/LITER
= .6827-01 CURIES/CM
JMAX ACTIVITY AT EXIT OP FLUX REGION = .1918-01 CURIES/CH
AVG ACTIVITY AT LOCATION OF_COIL_ _=_ .1884-01 CUR1ES/CM_
"TOTAL ACTIVITY IN REGION
EXTERNAL TO REACTOR SHIELD = ,8040+01 CURIES
DOSE RATE AT CENTER OF COIL
= .9491+03 RAP/HR «»»«»«
115
-------
SE3UENCE NJMdER t 2» 1)
FOR CALCULATIONS WITH:
< 2) SOLUTE IN SYSTEM = .9000+01 MOLES
( l_> . FLO* RATE = .2700*01 SAL/KIN
ITERATION I
1
2
3
4
5
6
7
8
9
10
11
12
13
It
15
16
17
IB
19
20
21
22
23
2
.4497-02
.8376-02
.1172-01
.1461-01
.1710-01
.1925-01
.2110-01
.2270-01
.2408-01
.2527-01
.2630-01
.2710-01
.2795-01
.2860-01
.2917-01
.2966-01
.3009-01
.3045-01
.3077-01
.3104-01
.3127-01
.3148-01
.3165-01
.31UO-01
.3193-01
.3204-01
.3214-01
.3222-01
.3229-01 .
.3236-01
.3241-01
.3246-01
.3250-01
.3253-01
.3256-01
TIME
.1859+02
.4762+02
.7664+02
.1057+03
.1347+03
.1637+03
.1927+03
.2218+03
.2508+03
.2798+03
.3088+03
.3379+03
.3669+03
.3959+03
.4249+03
.4539+03
.4830+03
.5120+03
.5410+03
.5700+03
" .5991+03
.6281+03
.6571+03
.6861+03
.7152+03
.7442+03
.7732+03
.8022+03
.8313+03
.8603+03
.8893+03
.9183+03
.9474+03
.9764+03
.1005+04
DOSE RATE
.2388+03
.4449+03
.6226+03
.7759+03
.9082+03
.1022+04
.1121+04
.1206+04
.1279+04
.1342+04
.1397+04
.1444+04
.1484+04
.1519+04
.1550+04
.1576+04
•1598+04
.1617+04
.1634+04
.1649+04
.1661+04
.1672+04
.1681+04
.1689+04
.1696+0**
.1702+04
.1707+04
.1711+04
.1715+04
.1719+0*
.1721+04
.1724+04
.1726+Ot
.1728+04
.1729+04
STEADY-<,TATE ACHIEVED AT TIME T~= •1676+02 MlN AFTER"
CYCLES
CONCENTRATION
SATURATION ACTIVITY
= .6833+03 GRAMS/LITER
= .1229+00 CURIES/CH
MAX ACTIVITY AT EXIT OF FLUX RESIGN = .3621-01 CURIES/CM
_AVG ACTIVITY AT LOCATION OF_COIL __J= .3433-0l_CURIES/CM_
TOTAL ACTIVITY IN RESION
EXTERNAL TO KEACTOR SHIELD
= .1465*02 CURIES
DOSE RATE AT CENTER OF COIL
= .1729+0» RAD/HR »•«»«•
116
-------
SEQUENCE NUMBER ( 2» 2)
ITERATION I
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
IS
19
20
21
22
23
24
25
26
27
23
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
AINd)
.1711-02
.3338-02
.4887-02
.6360-02
.7762-02
.9095-02
.1036-01
.1157-01
.1272-01
.1381-01
.1485-01
.1584-01
.1678-01
.1767-01
.1853-01
.1934-01
.2011-01
.2084-01
.2154-01
.2220-01
.2283-01
.2343-01
.2400-01
.2455-01
.2506-01
.2556-01
.2602-01
.2647-01
.2689-01
.2730-01
.2768-01
.2804-01
.2839-01
.2872-01
.2904-01
.2933-01
.2962-01
.2989-01
.3015-01
.3039-01
.3062-01
.3085-01
.3106-01
.3126-01
.3145-01
.3163-01
.3180-01
.3197-01
.3212-01
FOR CALCULATIONS WITH:
AEXdl
.1651-02
.3221-02
.4715-02
.6136-02
.7408-02
.8775-02
.9999-02
.1116-01
.1227-01
.1332-01
.1433-01
.1528-01
.1619-01
.1705-01
.1787-01
.1865-01
.1940-01
.2011-01
.2078-01
.2142-01
.2203-01
.2261-01
.2316-01
.2368-01
.2418-01
.2466-01
.2511-01
.255>
-------
- So
51
52
53
54
55
56
57
58
59
60
61
62
63
6*
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
60
.3227-01
.32K1-01
.3255-01
.3266-01
.3280-01
.3291-01
.3302-01
.3313-01
.3323-01
.3332-01
.3341-01
.3350-01
.3358-01
.3366-01
.3373-01
.3380-01
.33B7-01
.3393-01
.31*00-01
.3105-01
.3411-01
.3416-01
.3421-01
. 3426-01
.3430-Ul
.3434-01
.3439-01
.3442-01
.3446-01
.3450-01
.3453-01
.3114-01
.3127-01
.3140-01
.3153-01
,3164-01
.3176-01
.3166-01
,3196-01
.3206-01
.3215-01
,3224-01
.3232-01
.3240-01
.3247-01
. 3255-01
.3261-01
.3268-01
.3274-01
.3280-01
. 3285-0 1_
.3291-01
.3296-01
.3301-01
.3305-01
.3309-01
.3314-01
.3317-01
.3321-01
.3325-01
.3329-01
.3331-01
.48634-03
.49614-03
.50584-03
.51564-03
.52544-03
.53524-03
.5*504-03
.5548*03
.56464-03
.57444-03
.58424-03
.59404-03
.6038*03
.61364-03
.62344-03
.63324-03
.64304-03
.6528*03
.6626*03
.67244-03
.6822*03
.6920*03
.7018*03
.7116*03
.7213*03
.7311*03
.7409*03
.7507*03
.7605*03
.7703*03
.7801*03
.1597*0"*
.1604*01*
.1610*04
.1617*0<»
.1623*01*
.162B*q4
.1634*0'*
.1639*01*
.1644*01*
.1649*04
.1653*04
.1657*04
.1661*04
.1665+04
.1669*04
.1672*04
.1676+04
.1679*04
.1682+04
.1695*04
.1687+04
.1690*04
.1692*04
.1695+04
.1697*04
.1699+04
.1701+04
.1703+04
.1705+04
.1707+04
.1708+04
fEAOY-bTATE~~ACHiEVED AT"TIME t = .1300+02~MIN" "AFTER 80 CYCLES
CONCETl'TRATibM
SATURATION ACTIVITY
= .6833+03 GRAMS/LITER
= .12 29*0 P_CURiES/C«
VIAX ACTIVITY AT EXIT OF FLUX REtlON = .3453-01 CURIES/CM
AVG ACTIVITY AT LOCATION OF_C01L 5 .3392-01_CURIES/CM
TOTAL ACTIVITY IN REGION
EXTERNAL TO REACTOR_SHIELD _=__.i447+02_cyRiEs
DOSE RATE AT CENTER OF CQlL
= .1708*04 RAD/HR »*«»»«
118
U.S. GOVERNMENT PRINTING OFFICE:1973 5H-154/255 1-3
-------
SELECTED WATER
RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
Accession No,
•5, Till*
Dyestuff Color Removal By Ionizing Radiation and
Chemical Oxidation
Craft, T. F.
Eichhola, G. 6.
Engineering Experiment Station
Georgia,'* Institute of Technology
Atlanta^ Georgia
. ;/?« port No.
"' - • '
anization
10. --Project No.
12090 FZB
'II. _ Contract I Grant ffo.
•1$. Type ijf Repoft and .
^( v Period Coveted
Environmental Protection Agency report
number. EPA-R2-73-048, March 1973.
The effects of a combined radiation-oxidation process on solutions of
textile dyes have been studied. It'was found that the combined treatment with
gamma radiation and chlorine causes'more decolorization than the effect of the
two components when they are applied' individually. Several chemical classes
of dyes were tested, including anthraqulnone, azo, metallized azo, sulfur,
stilbene, and triphenylmethane dyes, At a concentration of 0.25 g/1 the
transmittance at the wave-length of maximum absorbance of dye solutions is
greatly increased by treatment with a radiation dose of 60 kR plus 75 ppm
chlorine. Non-optimized cost estimates indicate $0.31/1000 gal. for design
treatment, with normal operating costs potentially lower.
Although the major benefit from this treatment will be~removal of color,
some reduction of chemical oxygen demand will occur, and possibly some
reduction in the biochemical oxygen demand.
17a. Descriptors
Dyes*,
Gamma Rays*, Oxidation, Wastewater Treatment, Industrial Wastes.
17b Identifiers
Dye Wastes*, Textile Finishing Wastes*, Gamma Radiation, Chemical Baidation
//.-. <:')'.VKfi fi,MA Croup•
19.;, ecutyass.
'
32. Price
Send To:
WATBR RS80URCE8 SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OP THE INTERIOR '
WASHINGTON. P. C. 2084O
G. G. Eichholz
I
Georttifl Institute of Technoloav
-------