w=
STUDIES ON THE ORGANIC HALOGEN COMPOUNDS
IN SEA WATER
by
Alice Chung-chau Tang
B.S. National Taiwan Universityr
(1963)
SUBMITTED IN PARTIAL FULFILLMENT OF THE
REQUIREMENTS FOR THE DEGREE OF
MASTER OF SCIENCE
at the
MASSACHUSETTS INST2TUTE OF TECHNOLOGY
August, 1965
Signature of Author
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Department of"Geology and Geophysics
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Certified by ......
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Thesis Supervisor
Accepted by
Chairman, Departmental committee
on Graduate Students
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ACKNOWLEDGMENTS
The author wishes to thank Professor John W. Winchester
whose ensusiasm and advice has made all this work possible.
She also wishes to thank especially Dr. Robert A. Duce,
Dr. Yosh Hashimoto, Mr. Ferren MacIntyre, and Mr. Lester
Walters. Their contribution to this work has been most
valuable and their help and kindness will never be forgotten.
The encouragment and help from the numerous members of
the staff and students of the Department of Geology and
Geophysics, the M.I.T. Reactor, are also greatly appreciated.
Special thanks goes to Miss Janet Tyree who helped typing
the manuscript. The author is also grateful for the entire
support of this work through the fund of the Office of
Naval Research.
- 1 SUMMARY
A literature survey as well as an experimental search
to enable better estimation of the possible role of the
organic halogen compounds in the geochemical cycle of the
halogens has been done.
A tentative procedure for measur-
ing organic halogen compounds has been outlined and possible
future experiments suggested.
Thesis Supervisor:
Title:
John W. Winchester
Associate Professor of Geochemistry
TABLE OF CONTENTS
(I)
Introduction
(1) Organic halogen compounds and air-sea halogen
distribution relationship.
(2) Organic iodine compounds and the oxidation state
pf iodine in sea water.
(3) Possible sources of organic halogen compounds.
(4) Previous measurements of organic halogen compounds
in sea water.
(II)
Experiments, Results, Conclusions and suggestions for
future applications.
(III)
Bibliography
(IV)
Appendix
- 3 -
(I) Introduction
The geochemistry of halogens has many unanswered problems.
Especially, the geochemistry of iodine has been found
interesting and complicated.
Knowledge about the minor chem-
ical forms of the halides in the marine environment is extremely desirable in order to understand better the distribution of halogens in the air, sea water and sediments.
The
work this laboratory has carried on (Duce, Winchester, 1963,
1965) urged the necessity of pursuing
the study of organic
halogen compounds in the ocean water.
Also it is hoped that
by measuring the organic halogen compounds, some light can
be thrown on the iodide-iodate distribution problems in sea
water.
(1)
Organic halogen compounds and air-sea halogen rela-
tionships.
As a well-known and interesting fact, the iodine to
chlorine ratio is considerably higher in the air, in rain,
and in aerosol particles of marine origin.
The content of
iodine is also higher in air masses from the ocean than those
from inland (Goldschmidt, Rankama and Sahama, 1946;
al., 1963).
Duce et
To explain this phenomenon, either a physical
chemical mechanism for the escape of iodine into the atmosphere or a mechanical mechanism of enriched iodine spray,
or both in combination, must be supposed.
Some thought that
-
4 -
iodine was formed by oxidation of iodide at sea surface and
the free iodine then escaped to the air due to its high volatility.
It has been suggested that the dissolved oxygen in
sea water was responsible for the following oxidation:
1/2 02 + 2 I
+ 2 H+
12 + H20
E 0 = 0.28
However, thermodynamic calculations using pH 8.3 for sea water
and the dissolved oxygen concentration as 0.442 millimoles/l.
at 25 0C and 19%o chlorinity, indicated that the resulting
equilibrium concentration of 12 would only be 10 25 mole/liter.
Photochemical oxidation is another possibility.
The chemical
reaction being,
2 I
+ 1/2 02 + H20 + hv
> 12 + 2 OH"
since the iodide ion in aqueous solution has a rather strong
absorption band in the wave-length range 350 mu to 230 mu.
Miyake and Tsunogai (1953) used radioactive iodine 1 3 1 and
showed the release of free iodine into the air in the presence
of ultraviolet light, and this certainly indicated strongly
that photochemical oxidation of iodide is a possible mechanism
for the escape of iodine into the air.
By integrating the
average evaporation rate and solar radiation, they estimated
11
the total evaporation rate as 4x1Q g/yr. which is close to
the annual precipitation rate of 5x10 1 1 /yr.
Some believed
organic iodine compounds also play an important role in this
enrichment of iodine in oceanic atmosphere.
Loir and Legangneus
(1925) stated that the iodine in sea air is mostly in the organic
- 5 form, and that iodine in subsurface water exists as inorganic iodinebut on the sea surface, it is present in an
organic film and the iodine rich sea air is the result of release by spores and debris of abundant sea weeds and algae.
Aside from this active liberation of iodine by a biological
mechanism, Blanchard and Woodcock (1957) reported that the
aerosol nuclei which originated from the breaking of the sea
water bubbles might be more of the composition of the surface
film layer rather than the bulk of sea water.
Kientzler (1954)
found that the most effective way to clean a surface from an
organic film was to blow air through and remove the injected
bubbles.
Blanchard (1955) measured the surface tension change
before and after small bubbles had been allowed to bubble
through water with an oleic acid film and showed that the film
mechanism
was transferred to the aerosol. This proves the bubbleAis an
efficient way of removing organic components in the solution.
A natural occurrence of this film-removing mechanism was suggested by Woodcock (1948) in his work with "red tide."
Dean
held the opinion that most of the iodine in New Zealand rain
water were derived from disintegrated algae and planktons of
ocean spray.
The high degree of enrichment of organic phos-
phorous and nitrogen in rain was also suggested as an evidence
of this biologically responsible enrichment mechanism.
A
rather clear indication can be seen from the following data,
Dean, 1964 (unpublished):
- 6 -
Cl ppm
Inorg. I
54 pg/l.
Total I
54
% inorg.
100
surface sea water
18.3
Br ppm
62
massive spray
18.9
63
56
"
64
88
fresh foam
18.9
61
64
"
293
22
The organic iodine excess in the breaking bubble particles was
calculated as to be sufficient to account for that in the rain.
A preliminary experiment done by one of our fellow students
MacIntyre (unpublished) in studying the increase in the I/Cl
ratio in the foam formed by drastically bubbling air through
sea water also indicated similar results.
A 30 fold increase
in I/Cl ratio was observed.
In order to be better able to judge the significance of
the different mechanisms, a direct way of measuring the actual
quantity of organic iodine compounds present in sea water
would be the best solution.
(2) Organic iodine compound and the oxidation state of iodine
in sea water
As a well known fact, the only thermodynamically stable
oxidation form of iodine in sea water environment should
be iodate.
The following distribution pattern of the differ-
ent iodine species in sea water conditions was calculated by
Walters (unpublished).
Eh
0.800.
pH
8
-7 -
Cl
Br~
1.
1.
I
0.0
Cl2
0.593x10-20
Br2
0.938x10-
3
13
0.0
C10~
0.907x10-2 3
Br0~
0.225x10-10
12
0.0
HCl 0
0.471x10-2 3
BrO 3
0.115x10~
9
10
O'
C1 02
0.403x10
28
103
1.
Hl 02
0.189x10-2 7
104
0.0
C1 03
0.489x10-1 8
C1 04
0.319x10-
5
HU1 04
Yet the reported data on iodine measurements in sea water
indicated a considerable amount of iodide along with iodate.
Winkler (1916) first reported the value of 0.008 mg/1 iodide
and 0.041 mg/1 iodate in surface sea water.
He postulated
that the ratio of iodide to iodate would probably increase with
depth without perceptible alteration of the total iodine present.
In 1957, Sugawara and Terada did an extensive survey of
iodide/iodate measurement in western Pacific Ocean water.
AgNO 3 solution was used by them to precipitate iodide in sea
water and then the iodate in the filtrate was reduced by sodium
sulfite and then determined using the same method.
Their re-
sults was characteristically random and showed no discernible
trends with both location and depth.
Some typical results of
theirs are plotted in Appendix I to show the striking irregu-
MUFM
- 8 -
larity. The ubiquitously presented iodide in sea water was
again confirmed by Barkley and Thompson (1960). They used an
amperometric method to determine the iodate and then determined the total iodine content spectrophotometrically. Their
results in the North Pacific and Artic Ocean is best represented by the following table.
TOTAL IODINE AND IODATE IODINE FOUND IN SEA-WATER
.SAMPLES ( after Barkley and Thompson)
Position
52006 N,167 39 W
48035 N,122 51 W
Depth,
meters
Chlorinity
0/00
Total
Iodine
r/Liter
Iodate
iodine,
r/Liter
Iodate/
iodide
18.10
57
30.2
1.12
100
18.30
58
25.6
0.79
200
18.77
68
32.5
0.915
500
18.94
61
29.7
0.736
1100
19.07
62
30.3
0.97
10
15.92
42
20.5
0.95
60
-
9 -
Yonehara (1965) recently proposed a method for the determination of ultramicro quantities of iodine in the form of
both iodide and iodate.
The principle used was their cataly-
tic effect on the color fading of ferric thiocyanate.
By
their method, the sensitivity with maximum error of + 0.0003
pg/l was reported and the chloride ion would have no interference at 200 ppm.
In their results, -randomly distributed iodide/
iodate value of a few surface sea water samples were again
found.
All these previous informations point to the question of
what is the determing factor for the oxidation state of
iodine in sea water.
Shaw and Cooper (1957) proposed the
hypothesis that the oxidized form of iodine in sea water was
hypoiodous acid rather than iodate to account for the facts.
They assumed that the oxidation of hypoiodous acid to iodate
was slow and that the effect of powerful reducing biological
material was present.
Sugawara and Terada (1958) later ques-
tioned the stability of hypoiodous acid and measured the rate
of disproportionation for
3 IO~
)
21
+ 103
and proved it to be rather rapid. The reaction rate can be
clearly indicated in the following curves
0
1
o
U
-10-15
20
25
a
iodate curve
b
hypoiodite curve
-
10
-
and pointed to the unlikelihood of hypoiodite ion as the main
iodine species in sea water.
They attributed the presence of
iodide to the extreme slowness of oxidation of iodide to
iodate.
Johannesson also claimed the oxidized form being
iodate from bacteriological evidence.
In spite of the evidence
and general agreement for iodate to be the oxidized form, the
question of what is the controling factor for the random distribution of iodide/iodate ratio remains unanswered.
It
could not be explained by the terrestrial contribution of iodide
by river water because of the insufficient amount of the latter
and also for lack of any geographical correlation.
If slow
oxidation rate of iodide was the reason, then even the minimum
turbulent mixing should be expected to have eliminated the
striking differences in the iodide/iodate ratios between neighbouring portions of sea water as have been cited.
As Goldberg
(1963) pointed out, the marine biosphere which was so intimately involved in the iodine cycle, must have some significance
in giving rise to the existence and maintainence of the reduced form of iodine.
The interaction between biosphere and io-
dine in sea will be discussed in the next section.
Also, it
is conceivably possible that organic compounds in the ocean
which are highly reducing might be the real cause of this
"slowness" of iodide oxidation.
Over the past time, the little
consideration received for the role of organic halogen compounds in the whole halogen transformation cycle problem undoubtedly has to do with the enormous difficulties in measuring the organic halogen compounds in sea water because of the
WIP-M
-
11
-
low concentrations present as well as the high inorganic contaimination.
A schematic drawing showing the possible picture of the
iodine cycle can be outlined as follows:
Air ( enriched in iodine )
precipitation{
evaporation through oxidation
iodine excape to the ocean air through
biosphere and mechanical mechanism
( see text )
river,
mainly
iodide
-
Ocean
thermodynamic oxidation
2
I
3
biological reduction
reduction through participation of organic compounds
other unknown redox reactions
coprecipitation of iodine by metal hydroxides,
Al(OH) , etc.
such as Fe(OH)
precipitation hrough ofganisms
Sediments
( enriched in iodine )
-
12 -
(3) Possible sources of organic halogen compounds
Very interestingly, both the element itself and the first
organic iodine compound were recognized first in marine plant
even before its discovery as a constituent in the thyroid
gland.
Vinogradov (1953) reviewed the determinations of io-
dine in marine organisms.
Many organisms were reported to
concentrate iodine very efficiently.
For instance, Phycophyta
would have iodine concentration 30,000 times as much as that
in sea water.
Seasonal as well as life-cycle variations exist.
The most effective iodine scavenging algae can remove iodine
from 30 times its own volume hourly.
A summary concentration
factors for iodine together with phosphorous in marine biosphere is as below (after krumholz, Goldberg, Borough, 1957).
Element
conc. in s.w.
pg/l.
algae
Invert.
skeletal
soft
Vertebrate
I
50
10,000
100
50
10
P
70
10,000
10,000
10,000
40,000
There is disagreement as to what extent the iodine absorbed
is transformed into organic form, but it was shown that iodate
is not absorbed by algae.
The enzyme "iodide oxidase" is
responsible for the oxidation of iodide to iodine and I 2 was
shown by tracer experiment to be the form which algae absorbs.
According to Tong's (1959) study on Nereocystis using I 31,
after 4 hours of incubation, two thirds of the iodide would be
in organically bonded molecules.
They also tested the reaction
-
13 -
of non-enzymatic iodination by incubating 0.001 M. hydrogen
peroxide with 0.001 M. 1-tyrosine dissolved in bicarbonateRinger solution and 25% of the added radioactive Il31 was
incorporated into monoiodotyrosine.
It is also possible
that with the presence of peroxidase type enzyme in the
medium, even lower Eh value will be sufficient.
In his sta-
bility and exchangeability study, Scott (1954) obtained radioactive iodo-compounds after treatment of different tyrosine
and thyronine type compounds with Il31- iodides.
The presence of organic compounds in sea water has an
approximate average of 1 mg C/l.
It also has wide concentra-
tion variations both horizontally and vertically.
Hence if
it were the controlling compounds for the iodine oxidation
state in sea water, an irregular distribution of iodine forms
would be expected.
Among the many organic matter investigated,
near La Jolla, California, Blaser (1959) found the presence
of threonine, as well as uracil, isoleucine, glycine, biotin,
purine and tryptophan.
He used strains of a mutant bacterium,
Serratia marinorubrum, and detected the presence of those compounds by a bioassay method.
Koyama and Thompson (1956) ident-
ified organic acids of low molecular weight in sea water, such
as acetic, oxalic, and glycolic acid in the range of less than
0.1 pg/liter.
Slowery et al. (1959) estimated quantitatively
the fatty acids in a vertical profile of sea water.
Neuberg
et al. (1959) studied the proteinaceous material in sea water.
-
14 -
Evidence for proteins in sea water has also been reported
Anderson et al. (1954).
by
Tatsumoto and Hood (1961) used ion ex-
change analysis and reported a partial quantitative estimation of the amino acids in surface sea water.
Among them,
tyrosine was estimated to be 3 mg/m3 . i.e. 3x10 6g/l
2x100 8mole/l. which is 4 x 1I8 mole/l. potentially as diiodotyrosine.
This is roughly
4x0-8
_xl- - 10% of the molar
4.1 x 10
equivalents of iodine in sea water.
Since in the laboratory,
the iodination of tyrosine can proceed in alkaline solution
by just shaking tyrosine with inorganic iodine under ordinary
conditions, iodotyrosine type compounds would be able to be
formed simply through chemical reactions in sea water.
A
representative reaction can be written as follows:.
At 11,;
4H,2
~A0
_
-
O~h) ~
~HO
-o
-
Other possible chemical reactions between halogens and organic compounds reactions in sea water are:
1. Substitution of halogen in alkanes:
The reaction
is homolytic and is catalysed by sun light.
The
chemical reaction sequences are,
X
+
light quantum
X*
+
alkane
>
2X*
-
HX
+ free radical
of alkane free radical of alkane + X2
halide
+ X'
The reaction proceeds slower with iodine and can only be
Alkyl
15 -
-
carried out to a significant extent when HI is continuously
removed.
Otherwise, HI being a much stronger reducing agent,
would cause the back reaction
+
HI
alkylhalide
--
~~~->
Alkane
+
12
to occur.
2. Addition of halogens on alkenes:
The rate of reaction
is rather fast and a typical reaction can be written as
follows:
X
X
+ X
k
H
H
Since the addition is via a heterolytic nucleophilic mechanX
2 + RCH = CHR
--
>R
C - C X
ism, the reactivity order is
Cl> Br> I
But the addition of hydrogen halide has the reactivity sequence of
HI> HBr> HCl
3. Reactions with ketones and aldehydes; chlorine, bromine,
and iodine substitute readily in ketones having hydrogen on
the carbon atom adjacent to the ketonic group.
is catalysed by either
H+ or OH
ions.
The reaction
The rate of the
halogenation reactions has been studied as independent of the
concentration of the halogens and that at a given acidity and
concentration of ketone is the same for all three halogens.
4. V -halogenation of acids:
Because of the electron-withdraw-
ing effect of the carboxylic acid group, the C4 -
hydrogen of
the acid is more susceptable to nucleophylic substitution of
-
halogens.
16 -
The reaction can be expressed as:
RCH2 CooH + X
-
2 RCX 2 CooH + H2
5. Halogenation of macromolecular compounds in sea water:
Very little has been studied as to this possibility, yet
conceivably, the incorporation of halogens, especially iodine, into macromolecules of such as proteinaceous or cellulose or liped type compounds should be possible.
The above mentioned reactions all have reasonably fast
reaction rates and at extremely dilute environment over long
periods of equilibriate time such as that in sea water,
They probably could contribute significantly to the determination of halogen form as well as oxidation state in a
large scale.
Based on the above information, the total dis-
regard of the contribution of organic halogen compounds to the
mechanism of air-sea transportation of halogens as well as the
iodine form control-ing mechanism certainly requires further
investigation before it can be taken as justified.
(4) Previous Measurements of Organic halogen compounds.
No conclusive and clear-cut measurement of organic halogen
compounds in sea water has been satisfactorily reported yet.
Winkler (1916) concluded the absence of organic I compound,
but in his method, the procedure for determining both inorganic iodide and organic iodine are by no means non-destructive
and the sensitivity in his colorimetric determination seems
unable to detect any small amount of organic iodine compounds.
- 17 -
Loir and Legangneux (1925) emphasized the importance of organic iodine both in sea water and in air.
The organic com-
bined iodine was separated from inorganic ones by evaporating
water to dryness and repeatedly rubbing the residue with 90%
alcohol which removed the inorganic fraction away.
Sugawara
and Terada (1957) reported absence of organic iodine compound
in their investigation, but the analytical procedure they used
was rather non-specific.
They precipitated iodide by silver
nitrate in acidic solution and decided the amount of iodide
by weighing the precipitate formed.
But the reaction condi-
tion umployed might cause the destruction of the aliphatic halides according to the following reaction:
00C
C2H5I + AgNO3
> AgI + C2H 5NO3
This reaction can proceed rather smoothly at ordinary temperature* therefore, the determination of inorganic iodide
by this gravimetric method can not be a strictly specific
one.
Furthermore, the scavenging of organic compounds by
AgCl flock also may cause great error (see experimental part 2).
The ceric-Arsenid catalytic method used by recent investigators is also not entirely discriminative for organic or inorganic iodines.Because this reagent also produces color
reactions with organic halogen compounds such as thyroxine
and hence is also used as a method in determination of organic iodine compounds.
reported by Dean.
Measurement using this method has been
He attributed the catalytically determined
differences before and after chloric acid digestion as the
organic iodine and it'was reported to be as high as 40% of the
-
18 -
total iodine.
Other worthwhile noticing facts are that the exact form
of iodine in air is still not well understood.
Erickson (1959)
and Bolin (1959) concluded from the plant-atmosphere interchange experiments that most of the iodine in air was in organic form. Also Gulyayeva and Itkina (1962) found enrichment of iodine and bromine in some organic-rich sediments.
(II)
Experiment
(1) Introduction
Neutron activation analysis is one of the most sensitive
ways of analysing halogen compounds.
The sensitivity limit
for the different halogens are as follows:
*Sensitivity limit here is defined as the amount of
element which would give rise to 10 disintegrations per second after being irradiated in a neutron flux of 1013 neutron/
cm2 . sec. for 20 minutes.
The cross section data was taken
from G. E. Chart of the nuclides, 6th edition, 1962.
Element
Sensitivity (in nanograms)
C1
1.4
Br
0.058
1
0.077
Previous work in this laboratory gave good precision and
proved the chemical procedure reasonably easy to do.
The
disadvantage of this method is its being non-specific for
-
organic or inorganic forms.
19
-
With this in mind, attempts were
made to develop a pre-irradiation procedure for separating the
inorganic and organic halogens and then use the facilities
available to determine the amount of organic halogens by neutron activation analysis.
(1)
Coprecipitation with ferric hydroxide
Jeffrey and Hood (1958),
Park et al. (1962),
Tatsumoto
et al. (1961) reported the effective coprecipitation of organic material in sea water by ferric hydroxide precipitate.
Recovery of 52-95% of the soluble organic matter on Fe(OH)
3
and a concentrating factor of 104 was reported on a single ferric
hydroxide precipitation.
Usually, the presence of ferric hy-
droxide is a serious interference in the subsequent determin-
ation of organic compound, But neutron activation analysis has
the advantage of not being much interfered by the presence
of Fe+++, since it would only produce very little activity
in comparison with the halogen activities interested, because
of the relatively small abundance (0.33% for Fe58) and long
half life (45 days) of the important parent and daughter isotopes.
C136, Br 82, Iodide - I131, and Thyroxine-I131 tracers
were used to determine their efficiency of coprecipitation
with ferric hydroxide.
In each experiment, 0.232 g. NaCl was
added in 5 ml. demineralized water 50 A
5x10-6 g/ml. iodide
solution was added to make it about the sea water concentration. The bromine tracer had a carrier concentration of 3.0
mg/ml. and no further adjustment was made.
Usually 10-105 cpm
-
20
-
tracer was used. 1 mg. Fe(NO3 )3 was then added followed by
1 drop of 6 N NH4 OH. After standing for about 20 minutes,
the ferric hydroxide was filtered through a 0.45% millipore
filter and washed with demineralized water.
The efficiency
forcoprecipitation was calculated as:
cpm on ferric hydroxide
total activity used
For determining the second or third coprecipitation coefficient, the Fe(OH) 3 was dissolved in 2 ml. 1.5 N. HNO 3 and
diluted to 5 ml and then brought to alkalinic condition by
NH4 OH again.
activity in cpm on second ppt.
2
activity in cpm on first ppt.
The E' (s) are the coprecipitation coefficients obtained by
precipitating ferric hydroxide from the filtrate.
The results are summarized in the following table:
-
TABLE I
Species
21 -
COPRECIPITATION COEFFICIENT FOR DIFFERENT HALIDES
E,
Remarks
E2
Cl"M
8xlO5
from sea water
8xlO5
it
4.5x10-5
from artificial s.w.
3.lxl0~ 4
5x10
Br
4
10%
1.7x10-3
1x10-.3
1x10- 3
6%
52% (?)
2.2x10- 3
4x10-
3
4x10-
3
47
6.9x10- 3
1.3x10-2
"
1.5x10-3
417
8.5x10-3
28%
IO3
1.6x10
3
33%
5.6x10- 3
6.4x10-
3
6.9x10-
3
3.4x10- 2
31%
28%
If
2.4x10- 2
12
1.25x10'
1
60.2.
Thyroxine -I131
8%
64%
Thyroxine
12%
57%
"
E1 overnight
77
of
35%
"f
21%
67%
E1 overnight
-
22
-
The following results are obtained by adding 100 mg
Fe(NO3 )3 to 1100 ml. sea water and then adjusting the pH
by 6 N NH4 OH to pH 10-12.
The precipitate was collected
and washed by filtering through a 0.45
Millipore filter.
The
solid sample Fe(OH) 3 was irradiated in M.I.T. reactor for 20
minutes.
After irradiationthe solid Fe(OH) 3 was dissolved
in concentrated HNO 3 and diluted to 25 ml.
The post-irradia-
tion chemical procedure is largely based on that of Duce
and Winchester (1963) and hence will not be repeated here.
Only minor modification because of the presence of Fe+++ was
made and a flow chart procedure is included in the appendix
II
to indicate them.
TABLE II
NEUTRON ACTIVATION DATA ON
FERRIC HYDROXIDE COPRECIPITABLE HALOGENS
ILg/l
I/Cl
Br/Cl
C1,t.g/l
Br Lg/l
10+0.5
1.05+0.053
0.875+0.044
0.105
0.0875
2
24.8+1.2
0.71+0.036
0.905+0.045
0.029
0.037
6
34.7+1.8
0.946+0.048
0.94 +0.047
0.027
0.027
6
20+1.0
0.487+0.025
0.405+0.020
0.024
0.02
4
22.3+1.1
1.14+0.057
0.03 +0.0015
0.051
0.00134
0.0024
0.002
Times of
coprecip.
3
Blank 3
times
16.+0.80
0.038+0.0019 0.03 +0.0015
* Concentration accuracy= t5%
Ratio accuracy= +7%
Confidence level=
67%
C6nfidence level=
67%
6
While the Br/Cl and I/Cl values in sea water are 0.0035 and 2.7x10respectively.
-
23 -
From Table I, taking the average E1 for thyroxine and average E1 for iodide and iodate (assuming negligible amount of
12 present is sea water, see calculation above in part I)
a separation factor of
9 x 102
13
6.6 x 10-3
is obtained.
By using the average coprecipitation coeficients
-
for:
Inorganic Iodine
El
=
6.7 x 103
E2 = 0.4
Organic Iodine
E
E3 = 1 (See discussion)
- 9 x 10-2
E2 = 0.6
E3 M
Coprecipitated total iodine (average) = o.78
wg/l
Background from 100 mg Fe(OH) 3 = 0.03 pg.
Assuming that the total iodine in sea water was 50
pg.
Then
we can calculate the fraction of organic iodine, x%.
50x6.7x10-3x0.4(1-xo) + 0.6x9x10-2x5Ox
x
- 0.78-0.03
= 24
If we use the average El = 0.5 for total organic compounds.
(After Hood and Tatsumoto) which should be a closer estimation
since unfiltered s.w. was treated here.
The same calculation
leads to:
50x6.7x10-3 x0.4 (1-%) + 0.6x0.5x50x x% = 0.78,,-0.03
x = 4
Using the same supposition, the total bromine content in sea
water being 0.066g., the organic Br. fraction can be calculated
-
24 -
as follows:
0.066x2x10-3 x0.lx (1-x%) + 0.6x0.5x0.066x x% = 6.7x10i 7
x = 3x10-3
Since the chlorine value obtained was through a large correction factor from iodine and bromine activity, and also the
background was rather high, the calculation of organic chlorine fraction probably would not have too much significance.
However, the value
x = 1.2 x l4
was obtained though the
same calculation.
Obviously, these calculations are only a very rough estimation and probably should only be served as a qualitative
rather than a quantitative estimation.
However, it does in-
dicate that of the three organic halogen compounds, organic iodine compounds are probably the only kind which contribute to a significant fraction of the halogen.
(2) Silver nitrate precipitation
Some silver chloride scavenging experiments were carried out.
The consistent bringing down of a considerable fraction of
Thyroxine - I131 indicated that this method was not suitable
for applying to the separation of organic halogen compounds.
The results are summarized in the following table.
TABLE III
SCAVENGING OF ORGANIC
HALIDES BY SILVER CHLORIDE
Chemical yield measured
by weighing AgC1
Percentage thyroxine
scavenged by AgC1
92.4%
19.3%
99. 7%
49%
92. 37%
32.5%
-
25 -
(3) Activated Charcoal Adsorption
Different amount of charcoal was put into 1 liter of synthetic
sea water containing either iodide-I 1 3 1 or Thyroxine-I 1 3 1
The solution was let stand for 30 min. and then filtered
through a 0.45
w
millipore filter.
To wash the charcoal, it
was redispersed in 500 ml. demineralized water and then refiltered.
The activity on the charcoal was counted and the ad-
sorption coefficient was calculated as:
Activity on charcoal
E
=
=
Adsorption
coef.
initial total activity
10 ml. of 5x10
6
g/l. iodide solution was added to each liter
of water.
TABLE IV.
ACTIVATED CHARCOAL ADSORPTIVITY
OF IODIDE AND THYROXINE
Species
*
Amnt. Charc.
Description
E
used
I
60 mg
I~
120 mg
Thyroxine-I 1 3 1
Thyroxine-I 1 3 1
*
120 mg
60 mg
not washed
4.1%
washed
2%
washed
22%
washed &
dried*
18.3%
washed
99.6%
washed &
dried*
99.3%
washed &
dried*
94.1%
For drying the charcoal, it was put in a vacuum decicator.
Gentle heating was applied at approximately 600C.
The volatility
-
26
-
loss of inorganic-I is rather high (22% to 18.3%).
From the above results, it could be seen that activated charcoal was able to concentrate efficiently
the organic halogen
compound and hence rendered them into a more convenient form
to be handled.
Suitable procedure was searched for further
separation of the organic halide from the inorganic ones.
The following tests were made:
(A) The activated charcoal was packed into a column
and the adsorbed organic or inorganic iodine eluted
with 500 ml. demineralized water followed by 500 ml.
0.015 N. HNO 3 .
The charcoal was then counted.
E = retentivity - Activity remained on charcoal
Original activity on charcoal
over-all percentage of
E
Species
halide compounds left on charc.
Thyroxine-I 1 3 1
Iodide-I 1 3 1
94.1% x 61% = 57.5%
61%
2% x 9.45% = 1.89%
9.45%
for organic halide v.s. inorg. halide
Enrichment factor = 57.5% / 1.89% = 30
(B) The following experiments were carried out using organic
solvents to try to extract out thyroxine.
A 50 ml
microsoxhlet was used and each time the 60 mg. adsorbed charcoal was extracted with 25 ml. organic solvent at boiling
point for 30 min.
The organic solvents were then concentrated
under reduced pressure to a volumne of approximately 2-3 ml.
The results are summarized in below:
-
27
-
E - Activity left in the final 2 ml. organic solvent
Original activity on dried charcoal
-
Extraction coefficient
Specied
Solvent
Over-all recovery of halides
E
from s.w. in the final 2 ml
soln.
I~
Benzene'
I~
I
Thyroxine
it
I~
15 ml. C H
6 6
15%
2% x 15% = 0.3%
2% x 20%
207%*2
=
0.4%
43.5%
94.1% x 43.3%
22.7%
2% x 22.7%
63.2%
94.1. x 63.2%
=
=
41%
0.45%
10 ml. Ethyl
acetate
Thyroxine
*1
"
=
The benzene used was purified by extracting the reagent
grade benzene twice with drierite and then distilled at its
b.p. 80.3 0 C.
*2
Of the 20% and 15% inorganic iodine extracted, about 1/3
of them were found to be very volatile and was in the organic
distilate portion in the concentrating step.
The separation factor through this adsorption-extraction proc-ess would be:
41
Using Benzene
c =
=
100
=
132
0.4
59.5
Using Benzene +
ethyl acetate
c =
0.45
Taking a conservative estimation of less than 1% iodine in sea
water present as organic iodine compounds, with the above separation factor, inorganic iodine would still give rise to almost 507. of the total activity in the subsequent neutron
59.5%
-
activation analysis.
28 -
A separation factor of 103 is desired
in order to reduce the interfering inorganic acitvity down
to less than 107% of the total halide activity produced.
(4) Electrolysis using silver electrodes
If electrolysis using silver anode and platinum cathode is
carried out in a solution containing I and Cl,
the anode
reaction would be
Ag + Cl"
Ag +
->
AgCl + e-
AgI + em
I-
and the cathode reaction would be
H
+ e~
Since (Ag+)
>
(-)
1/2 H 2
=
8.5 x 10~17 , so that
Theoretically, we could bring the (I") down to less than
1015 mole in the system.
Experiments were carried out us-
ing the following set-up:
A silver plate with surface area
approximately 2 cm2 was used as an anode.
A platinum wire
connected to a calomel electrode was used as cathode. Different voltages were used and direct current were passed through
The solution contained 0.99x10
a 10 ml. sample cell.
5x10- 6
IM,
and I131 or Thyroxine-I 1 3 1.
3
g. C1 .
Successive aliquots
were taken and counted to determine the iodide or thyroxine
concentration still left in the solution.
sults were obtained.
The following re-
The percentage remaining in the solu-
tion was calculated as:
-
R =
29
-
Activity left in the electrolysis soln.
Activity originally in the soln.
Species
131
I
Voltage used
time of electrolysis
R
1.5v.
30 min.
74.
"t
i
Thyroxine-Il31*
10 min.
6v.
98. 67%@
11.1
3 hr. 10 min.
2.
6 hr.
1.C
!0/
3
1. 3x10-
10 hr.
6v.
Thyroxine
2 hr.
42% 5%M
5 hr.
19.1
5.
6 days
300-600 mv.
4 hr.
35%
8 hr.
3.
28 hr.
*
2%
In the case of determing thyroxine removed, 0.01 mg tyro-
sine was added as a supporting compound.
At the optimum cond-
ition among the above few trials, at 6v. after 5 hrs., a separation factor of
19.5 = 13 can be expected.
1.5
Combining the act-
ivated charcoal adsorption, benzene plus ethyl acetate extraction, and the electrolysis, a separation factor of more
than 732 x 13 = 1.7 x 103 can be obtained.
Further investiga-
tions seem to be worthwhile to enable better recovery of organic
fraction using this principle.
Smaller current as well as lower
voltage applied in the system might be more suitable.
(4) Electrodialysis
Martin (1947) reported a method of electrodialysis for
-
30 -
separating organic compounds and with salts.
More than 90%
recovery for most amino acids including glutamic acid and
glycine, and more than 98% recovery for average organic compounds were reported. The membrane for dialysis that he used
was cellophane membrane.
Attempts were made by the author
using a Fisher electric desalter which1+ssentially based on
Martin's principle in further separating the inorganic and
organic halogen compounds.
The principal set-up can be
shown in the following diagram.
dilute H 2So
4
Water
water
dellophane
sample solution
Hg
principle and diagram for electrodialysis
-
31 -
6 ml of concentrated sulfuric acid in 1 liter of distilled water was used as the anode circulating electrolyte.
The circulating mercury cathode was continuously washed with
tape water at a flow rate of 300 ml./min. The dialyzing membrane used was Fisher cellulose dialyzing membrane and the
testing solution used contained 5 x 106 g. I
,
10" g. Cl,
10-2mg. tyrosine supporting compound and tracer iodide as
well as Thyroxine-I 131 in a volume of 10 ml.
The following
results were obtained.
activity left in the solution
E= recovery coefficient
Species
=
activity originally present in soln.
current change
time of elec.
dialyzing
E
I
10 min.
0.6 - 0.2 amp.
3%
I
25 min.
0.2 - 0.14 amp.
1.5%
Thyroxine-I
10 min.
0.6 - 0.2 amp.
16%.
The separation factor between organic compound and inorganic
compound thus obtained was approximately 14 = 5 and was less
than
that obtained using direct silver electrode.
But organic
halogen compounds of less polarity than tyrosine and thyroxine
would certainly have bettera recovery rate.
(6)
Conclusion
An outline of the tentative procedure can be indicated in
the following schematic diagram.
iodine fraction to be 17,
By assuming the organic
the calculated concentration is
-
32 -
put under each step.
1 liter sea water
(inorg I: 50x10-6g.
Org I: 5x10 7g)
activated charcoal
Adsorbed charcoal
(Inorg I: 10- 6g.
Org I:
5 x 10 7 g)
wash M'ith demineralized water,
organic solvent extraction,
concentration to 2 ml.
adjust to 5 ml. solution
(Inorg I: 3x10~ 7 g
Org I: 3x10'7 g)
electrolysis
Final solution of irradiation
(Inorg I: 9x10 9g
Org I: 1.2x10 7g)
(7) Discussion
1. Non-ionic properties of iodine at extremely low concentration:
Chamberlain and Wiffen (1950), Chamberlain (1958),
stated that when the amount of carrier is small, 1131 vapor
exhibited peculiar properties and was readily adsorbed on a
wide variety of surfaces.
May made experiments and calculated
that the maximum adsorption on a clean copper surface was
about 0.4
wxg.
iodine per cm 2. which was equivalent to a
monomolecular layer of moleculea of 4A0 diameter.
In this
study, complementary results were obtained; both the ferric
hydroxide coprecipitation and the activated charcoal adsorption experiments indicated the likely presence of 12 as a component when the concentration was very low. The large surface are used in the precipitation might be the cause for this
formation of 12 which appeared to be responsible for the large
-
33
-
adsorptivity and high volatility it showed in the subsequent
steps.
Sugawara and Terada (1957) suggested that coprecipi-
tation of iodide by metal hydroxides in water to be one possible mechanism for the removal of iodide ions selectively
from the environment water and our present data in this study
seem to support the view.
2. Comparison of silver electrode electrolysis and electrodialysis:
From the experiments carried out here, high re-
covery of organic polar compounds such as amino acids could
not be obtained by electrodialysis as reported by Martin.
Yet the method itself has the advantage of being able to remove most other inorganic ions at the same time and thus gave
a lower background counting in the subsequent neutron activaAnother advantage was that the interfering ions
tion analysis.
were actually taken away from the sample solution, so that
after this step, the samples could be directly irradiated without going through further procedures such as filtration,etc.
Electrolysis applying silver electrode is an unlimited method
theoretically, yet the disadvantage comes from the fact that
silver halide precipitate would be in the system and requires
further removal.
3. Comparison of the present outlined procedures for the
determination of organically bound halogens with other possible methods:
Among the other possible methods in measuring
organically bonded halogens.
Owing to the low concentration
-
34 -
of organic halides, only the following two methods seem to
be potentially useful.
a. Gas chromatography using an electron detection device.
b. Paper chromatography using internal tracer to spot the
compound positions and then followed by neutron activation analysis.
Yet the problem and difficulties would arise since a much more
exact knowledge which is now lacking as to what are the organic compounds present would be
these methods.
Very critical in applying
Also, the fact that the organic halogens pre-
sent might be in many different forms and therefore the sensi-
tivity limit required for detection would be even higher and
this might be the limiting factors in the chromatographic methods,
approach.
(SB)
Suggestions for applications of the determination of or-
ganic halogen compounds.
By measuring the separate quantities of iodide, iodate, and
organic iodine compounds respectively on sets of sample sea
water with difference in biological activities, significant
information probably can be expected to help evaluating the
contribution of biological activity to the iodied-iodate ratio.
By measuring the organic iodine content of the surface sea
water, a better evaluation of the organic contribution to the
atmospheric iodine enrichment should be possible.
-
35
-
BIBLIOGRAPHY
Barkley, R. A. and T. G. Thompson (1960), Determination of chemically combined iodine in sea water by amperometric catalytic
methods, Anal. Chem. 32, 154.
Barkley, R. A. and T. G. Thompson (1960), The total iodine and i
iodate-iodine content of sea water, Deep Sea Res. 7, 24.
Blanchard, D. C. and A. H. Woodcock (1957), Bubble formation
and idodification in the sea and its meteorological significance, Tellus, 9, 145.
Bolin, B. (1959), Note on the exchange of iodine between the
atmosphere, land and sea.
Int. J. Air Poll. Vol. 2,
127.
Chamberlain, A. C. (1960), Aspects of the deposition of radioactive and other gases and particles, Aerodynadmic Capture
of Particles, E. G. Richardson, Ed., Pergamon Press,
London.
Chamberlain, A. C., and H. J. Dunster, (1958), Depositibn of
radioactivity in morth-west England from the accident at
Windscale, Nature, 82_, 629.
Chamberlain, A. C. and R. D. Wiffin (1959), Some obsdrvations
on the behavior of radioiodine vapor in the atmosphere,
Geofisica Pura E Apjlicata-Milano, 42,
42.
Dean, G. A. (1963), The iodine content of some New Zealand
dringing waters with a note on the contribution from
sea spray to the iodine in rain, New Zealand J. Sci.
-
6.,
36 -
208.
Duce, R. A., J.T. Wasson, J. W. Winchester, and F. Burns (1963),
Atmospheric iodine, bromine, and chlorine, J. Geophys.
Res., 68, 3943.
Duce, R. A. and J. W. Winchester, (1965)
Determination of
iodine, bromine and chlorine in atmospheric samples by
J. Geophys. Res., 7Q, 1775.
neutron activation.
Composition of Atmospheric precipitation.
Eriksson, E. (1952)
Tellus, 4,
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Eriksson, E. (1960)
Sulfur,
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Tellus,
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Goldberg E. (1963), The Sea, Vol.
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Jeffrey, L. M., and D. W. Hood (1958), Organic matter in sea
water; an evaluation of various methods for isolation,
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Johnass9n, J. K. (1958), Oxidized iodine in sea water.
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Koyama, T. and T. G. Thompson (1959), Organic acids of sea
water, Preprints Intern. Oceanogr. Congr.,New York.
Loir, A. and H. H. Legangneux (1925a), Iodine in sea air,
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Am. Med.
Assoc.,
84,
1531.
Miyake, Y. S., Tsunogai (1963), Evaporation of iodine from
the ocean, J. Geophys. Res., 68, 3989.
-
37 -
Park, K., W. T. Williams, J. M. Prescott and D. W. Hood (1962),
Amino acids in deep-sea water, Sci., 13., 531.
Scott, R. (1954), Observations on the Iodo-amino-acids of marine
algae using iodine-131. Nature, 173, 4414.
Slowey, J. F., L. M. Jeffrey and D. W. Hood (1959), Characterization of the ethyl acetate extractable organic
material of sea water.
Preprints Intern. Oceanogr. Congr.,
New York, 935.
Shaw, T. I., Cooper, (1957), itate of iodine in sea water,
Nature, 18Q, 250.
Shaw, T. I., L. N. H. Cooper,, (L958), Oxidized iodine in sea
water, Nature, 162,
251.
Sugawara, K., D. Terada (1957), Iodine distribution in the
western Pacific Ocean, J. Earth Sci., Univ. Nagoya,
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81.
Sugawara, K. and D. Terada (1958), Oxidized iodine in dea
water, Nature, 182, 250.
Tatsumoto, M., and W. T. Williams, J. M. Prescott and D. Hood
(1961), Amino acids in samples of surface sea water, J.
Mar. Res, 19, 89.
Tong, W., and I. L. Chaikoff, Metabolism of 1-131 by the marine alga,
algae, Nereocystis luetkeana.
Winkler, L. W., (1916), Der Iodid- und Iodate- Iongehalt des
Meerwassers, Angew. Chem., 29, I, 205.
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-
Woodcock, A. H., Blanchard D. C., Tests of the salt-nuclei
hypothesis of rain formation,
Yonehara, N.
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(1964), The colorimetric determination of
minute amounts of iodide and iodate in sea water by means of
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37, No. 8, 1101.
Ehem. Soc, of Japan, Bulletin
-
39
-
APPENDIX
I
DISTRIBUTION OF IODATE/IODIDE IN SEA WATER:
IT'S CHARACTERISTIC RANDOMNESS.
( after Sugawara and Terada )
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APPENDIX II
FLOW CHART DIAGRAM OF THE POST-IRRADIATION
CHEMICAL PROCEDURES FOR
THE
NEUTRON ACTIVATION ANALYSIS
OF HALOGENS
-
47
-
100 mg. Fe(OH)3 precipitate from sea water
irradiation(20 min.)
dissolve in conc. HNO
3'
adjust volume to 25 ml.
Aliquot 2 ml.
Aliquot 10 ml.
Ad8 5ml. Br~+ I~ carriers
Add 5 ml. Cl'carrier
Add 0.05M NaSO0
+ 25 ml. H20
;Add 5 ml. 0.1 M AgNO3
Ppt. Ag'l
Wash with H20, EtOH, Acetone
filter
AgC1
Count, weigh
!12 N. NaOH to phenolphthalein
;end point. + 12 drops 5% NaClO
Iswirl 1 min.
acidify with 16 M. HNO 3
tAdd 15 drops 0.5 M Na2 S 0
2 5
swirl 30 sec.
Add NaOH to phenolphthalein
basic, + 3 ml. glycial acetic
acid. + 5drops 1 M NaNO
2
Extract with 20 ml. CC1
4
-1l
CC' 4
Aqueous
Br,
Add a few more drops glycial
acetic acid,
+ 5 drops conc. HNO
wash with 50 ml.
0.04% (NHOH Su4
twice
3
+ 0.1 M=KMnO
to solution persistantly
purple
Extract with CC
4/4
aq.
(discard)
I2
S2 05 ~I~ in aqueous
4
Br2 ( in CC
4
)
AkI
Wash with H20 + KMnO.
Br
Red. to I. with
Ppt. with AgNO
3
Add 16 M HNO3
2
Back extract wihh aq.
(NH3 OH) 2 S0
4
Aq. - Br"
Filter (wash with
H0 EtOH, Acdcone)
Count , weigh
I[ Ppt. with AgN 0 q
AgBr
' wash with H 0 EtoHAcetone
filter, count, weigA