Marine Chemistry, 7(1979) 133--139

© Elsevier Scientific Publishing Company, Amsterdam -- Printed in The Netherlands

A COMPARATIVE STUDY OF THREE METHODS FOR THE DETER-

M I N A T I O N OF I O D A T E IN S E A W A T E R

VICTOR W. TRUESDALE AND CHRISTOPHER J. SMITH

Institute of Hydrology, Crowmarsh, Wallingford, Oxon (England)
(Received May 9, 1978; revision accepted September 11, 1978)

ABSTRACT

Truesdale, V. W. and Smith, C. J., 1979. A comparative study of three methods for
the determination of iodate in seawater. Mar. Chem., 7: 133--139.

A comparative study of three methods for the determination of iodate-iodine in sea-

water is described. In one method the iodate is determined polarographically while in the
others the iodate is determined colorimetrically as iodonium ions. In one of the colori-
metric methods each sample is pre-treated with excess iodine-water in an attempt to
eliminate suspected interference from naturally occurring reducing agents. The tests were
conducted on a selection of open-ocean and near-shore waters with iodate concentrations
ranging from 0 to 60 pg 1-LI. The tests indicated that the polarographic method and the
colorimetric method without iodine-water give the more reliable measurement of iodate
concentration. Also, the method with iodine water was found to be in error especially at
low iodate concentrations. Reducing agents, if present, were found not to interfere
significantly.

INTRODUCTION

This p a p e r describes h o w the a c c u r a c y o f m e t h o d s f o r the d e t e r m i n a t i o n

o f the 0 - - 6 0 p g 1-1 i o d a t e - i o d i n e in seawater, c u r r e n t l y in use in this labora-
t o r y , was tested. O f course, the a b s o l u t e a c c u r a c y o f m e t h o d s c a n n o t be
ascertained a n d one m u s t settle f o r ' c o n s i s t e n c y ' as t h e criterion for a c c u r a c y .
Here, t h e r e f o r e , t h e m o s t effective test available, t h a t o f c o m p a r i n g t h e results
yielded b y o n e m e t h o d with o t h e r s similarly o b t a i n e d , b u t b y a n o t h e r
m e t h o d , has been used. T h e r e is a c o n t i n u i n g n e e d f o r such tests so as to
eliminate p r o b l e m s associated with i n t e r f e r i n g s u b s t a n c e s and the use o f
sample-blanks. L a b o r a t o r y investigations with a single m e t h o d can identify,
and even lead t o t h e suppression of, interfering substances. However, because
o f the e x h a u s t i v e testing n e e d e d , s o m e interfering s u b s t a n c e s can easily be
o v e r l o o k e d . Also, while t h e sample blank (e.g. artificial seawater (ASW))
derived f r o m the use o f t h e single m e t h o d a p p r o a c h m i g h t a p p e a r t o be satis-
f a c t o r y t h e r e r e m a i n s t h e possibility t h a t it is, nevertheless, incorrect.
134

In early work in this laboratory an iodate-procedure developed from

Johannesson's (1958) original method was used. In this m e t h o d the iodate is
converted to iodonium ions by reaction with sulphamic acid and potassium
iodide; the iodonium ions being measured colorimetrically. In later work,
concern that substances capable of reducing iodonium ions might be present
in seawater, led to the development of another procedure in which each
sample is pre-oxidised using excess iodine-water at pH 5.0. It was envisaged
(Truesdale, 1978) t h a t a comparison of results obtained with and without the
iodine-water would identify problematic waters. In this latest work it has
also been possible to use a polarographic method (Herring and Liss, 1974)
for the determination of iodate. The inclusion of this m e t h o d in the compara-
tive exercise is particularly worthwhile since its chemistry is entirely different
to that of the other, colorimetric methods.
The comparative exercise was performed with a mixed sequence of samples
including open-ocean (0 and ~ 4 5 pg 1-~ iodate-iodine) and inshore Irish sea-
waters ( ~ 4 5 t~g 1-~ iodate-iodine).

METHO DS

The colorimetric iodate m e t h o d w i t h o u t iodine-water and the polarographic

m e t h o d were used in their original form (Herring and Liss, 1974; Truesdale,
1978). However, the colorimetric iodate m e t h o d with iodine-water was used
only after the pH of the mixture in which oxidation with iodine water was
to occur, had been reduced to 3.1 from the 5.0 originally recommended.
This change had been f o u n d to be worthwhile when, compared with other
seawaters, a sample of Menai Straits' water had been found to react differently
toward the iodine-water at pH 5.0, but in a similar way at pH 3.1. Thus, in a
series of tests similar to those used in the method's development (Truesdale,
1978), various known amounts of iodine-water (0.0--2.0 ml) were added to
replicate mixtures of seawater (14.0 ml) and acetate buffer (0.25 ml). After
6.0 minutes 20% (w/v) phenol solution (0.25 ml) was added to destroy the
excess iodine, and then the mixtures were analysed for iodate-iodine c o n t e n t
using the iodate m e t h o d without iodine-water. Out o f t w e n t y seawaters tested
in this way nineteen showed an increase in response equivalent to between 0
and 10 pg 1-1 iodate-iodine upon addition of 0.2 ml or more of iodine-water;
whereas artificial and open-ocean seawaters consistently gave increases in
response of less than 2 gg 1-1, inshore waters gave the larger increases. The
exception, the Menai Straits' water sample, yielded a similar effect except
that the responses for the 0.1, 0.2 and 0.3 ml additions of iodine water were
greater than those for subsequent ones by approximately 3 pg 1-1 iodate-iodine.
Nevertheless, when the experiments were repeated at pH 3.1 this unusual
behaviour was not observed. The reason for the unusual behaviour is n o t known.
The change to pH 3.1 was accomplished by substituting a 23% (v/v) acetic
acid solution for the mixed acetate/acetic acid buffer originally recommended.
 135

To compensate for the concomittant alterations in pH at the two later stages

of analysis, i.e., when excess iodine-water is destroyed by phenol, and when
iodonium ions are generated, a 28.8% (w/v) sodium acetate tri-hydrate
solution is introduced immediately after the phenol reagent.
In comparative exercises it is desirable to replicate analyses so that the
precision of each can be quantified. Moreover, replication is necessary if the
most powerful statistical techniques are to be used. However, in this type of
exercise it is also desirable to analyse as wide a variety of samples as is
possible in. the time available, to give the results maximum applicability. As
experience over several months had already shown the three methods to
yield a nearly constant and high reproducibility, it seemed more worthwhile
to allocate the available time to gaining maximum applicability. The standard
deviation for replicate analyses by either colorimetric m e t h o d is approximate-
ly 0.5 pg 1-1 and 1.0 pg 1-1 for the polarographic method. In each exercise the
samples were taken in a randomised sequence to avoid superimposing any
hidden analytical trend (e.g. drift) onto the results.
The colorimetric methods were calibrated with the same artificial seawater.
The polarographic m e t h o d was calibrated by analysing each sample a second
time but after it had been spiked with 40.0 ~g 1-1 of iodate-iodine. The peak
height of each polarogram was measured from a straight line drawn tangen-
tially to the extremities of the peak (Fig.l). The straight line is unlikely to be

dE

-o.s -:o -:s

E (VOLTS)
Fig.1. Differential pulse polarogram of a seawater sample showing alternative base-lines.

correct since it imposes the restriction t h a t the gradient of the undifferenti-

ated polarogram should increase uniformly with applied voltage. The correct
line would probably curve below the straight line. The difference between
these two lines at the half wave potential of iodate, that is the systematic
error made in any determination, decreases with decreasing peak height.
Thus, this straight line which is a chord of the true curve eventually becomes,
at 0 pg 1-1 iodate concentration, a tangent. In the absence of knowledge of
the shape o f the polarogram for iodate-free seawater the straight line offered
the more reproducible solution.
 136

The colorimetric methods have been designed to tolerate up to 143 pM 1-1

of nitrite-N (Truesdale, 1978) by allowing the sulphamic acid reagent to
react with any nitrite for one minute before the iodide reagent is injected.

RESULTS AND DISCUSSION

In this study the colorimetric iodate method w i t h o u t iodine-water treat-

ment was taken as the fiduciary method. Fig.2 shows the result of comparing
#g1-1 (a)

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~ ,,r,p
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<
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o 20

0 20 l.b " 6'0 #g1-1

COLORINETRIC, WITHOUT I,
#g [-1 (b) /

60 ° ~,~

-1- ~

rr
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oEc 20
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0 2b #01-1
COLORIMETRIC, WITHOUT I2
Fig.2. The distribution o f sample concentrations e n c o u n t e r e d in the comparisons of the
colorimetric m e t h o d w i t h o u t iodine with (a) the polarographic m e t h o d and (b) the colori-
m e t r i c m e t h o d with iodine water. F o r convenience the line o f unit gradient is shown in
b o t h cases. In each case the precision (95% c o n f i d e n c e level) for each m e a s u r e m e n t is as
s h o w n for the m o s t c o n c e n t r a t e d sample. In (b) the broken line divides onshore (A) and
o f f s h o r e (r-q) samples.
 137

the o t h e r two me t hods with this fiduciary one; t he line of gradient 1.0 on
each diagram shows the result which would have occurred had agreement
been obtained. The Students t-test (Table I) showed t h a t in bot h exercises

TABLE I
Results of testing the difference in the means obtained by the different iodate methods

No. of mean variance

samples concentration (pgl-1)2
(pgl-1)

(a) Two colorimetric procedures

without iodine 85 40.5 100.7 94.6
with iodine 85 42.4 131.9

(b) Colorimetric/polarographic
procedures
colorimetric 36 31.1 150.5 10.7
polarographic 36 30.3 161.5

the mean c o n c e n t r a t i o n obtained by the fiduciary m e t h o d differed signifi-

cantly at the 0.1% level from t hat obtained by the o t h e r m et hod. In general,
therefore, the colorimetric m e t h o d with iodine-water t r e a t m e n t yielded
higher values than t hat w i t h o u t iodine-water t reat m ent , and the polarographic
m e t h o d yielded, on average, a concent r a t i on lower than t h a t obt ai ned by the
colorimetric procedure w i t hout iodine-water.
T h e average discrepancy of less than 1.0 pg 1-1 between the colorimetric
m e t h o d w i t h o u t iodine and the polarographic m e t h o d is easily a c c o u n t e d for
in terms o f systematic error in either or b o t h o f the methods. Thus, with
artificial seawater there is always the chance t h a t some c o m p o n e n t s will
contain small amount s o f iodate; indeed in this laboratory the apparent
iodate c o n c e n t r a t i o n of different batches has occasionally been f o u n d to
differ by as much as 5 pg 1-1 when analysed by the colorimetric m e t h o d .
Moreover, with polarograms there is the difficulty o f drawing the correct
base-line for each individual sample; a t t e m pt s at using a postulated, curved
base-line, as Herring and Liss (1974) did, pr oduced an increase in iodate
c o ncen tr atio n o f as much as 4 ~g 1-1. It is perhaps worth noting t hat the
polarogram for the artificial seawater used f or calibration of the colorimetric
procedures lay so close to the straight line imposed upon it t h a t an iodate
peak was n o t discernible.
The difference between the results for the two colorimetric m e t h o d s does
n o t appear to be explicable solely in terms of a systematic error in one or
b o t h methods. Thus, as in a previous study (Truesdale, 1978) t he m et hods
are in agreement at the higher iodate concentrations. However, at t he lower
concentrations there is a discrepancy, which appears to correlate with sample
138

type. Thus, whereas points to the left of the dotted line of Fig.2b have an
inshore character, as they relate to samples collected from the Liverpool Bay
of the North Irish Sea during three separate cruises, points to the right of the
line have a more oceanic character, as t h e y relate to the Southern Approaches
to the Irish Sea as well as to the tropical Pacific Ocean. On this basis it seems
likely that the inshore samples lie upon a line parallel to the 'line o f agree-
ment' but having an ordinate intercept of approximately 5 pg 1-~ iodate-I. As
the colorimetric methods differ only in iodine-water pre-treatment the
observed trend must reflect variation in the reaction of different samples to
this pre-treatment. Indeed, this variation has already manifested itself in the
experiments described earlier where the iodate concentration of artificial and
open-ocean waters increased by only 2 pg 1-I upon addition of iodine-water,
but inshore waters increased by 10 #g 1-1. It should be noted that this
behaviour is consistent with that postulated when the iodine-water pre-treat-
ment was introduced, in an a t t e m p t to indicate the presence of reducing
agents in some seawaters (Truesdale, 1978).
From above it is apparent that, as the three methods do not agree, a judge-
m e n t as to the best methods is needed. In our view the most reliable measure-
m e n t of iodate concentration must be taken as that obtained by either the
colorimetric method w i t h o u t iodine-water or the polarographic method.
Thus, the observation of consistency between two methods relying upon
entirely different chemistry seems to carry greater weight than the alternative
one involving methods with similar chemistry. Further, as a result of this, it
now appears unlikely that a significant a m o u n t of the iodonium ion is reduced
in the m e t h o d w i t h o u t iodine water. As previous work (Truesdale, 1974) has
demonstrated t h a t inshore waters can 'reduce' comparable amounts of added
molecular iodine (I2) within 30 min, it appears t h a t the excess of iodide re-
agent added to produce the iodonium ions, is also successful in blocking the
reduction process. Moreover, it now seems that the discrepancy between the
two colorimetric methods associated with inshore waters, originally thought
to indicate an underestimate by the method without iodine-water, in fact,
reflects an overestimate by the method with iodine-water. We believe that
this overestimate is caused by an enhanced rate of disproportionation of
iodine, added as iodine-water, in the samples of low iodate content. As the
bulk chemistry (pH, S ~., etc.) of all of the samples studied was so similar, it
seemed that catalysis of this disproportionation reaction by traces of ter-
rigeneous material, more concentrated in the inshore samples, is likely. As
this has an environmental implication, a preliminary search for a catalyst was
made. However, the search which tested the effect of 20 #g 1-1 of several metals,
i.e., cupric, zinc, ferric, ferrous, manganous, chromic and chromous salts, in
an artificial seawater, has so" far been fruitless.
As a result o f this work a simpler manifold for the automatic determination
of iodate in seawater is recommended (Fig.3); it excludes the glassware and
reagents associated with the pre-oxidation step, but is otherwise unchanged.
 139

Sampler

De- bubbler

Mixing Mixing ;ump,

toll coil \ 0.073[ Artificial seawater]
> I mi,n > I mln k
0.073" Sample
0.030" Air
0.015"10% (w/v) Sulpham,ic acid
0.025" 4.5 "/. (w/v) Sodium Iodide
0.030" I
Waste
j 0.051"

Colorimeter Recorder
~0 mm flow-cell
350 nm filters

Fig.3. The Auto-Analyser manifold now recommended for iodate determination.

ACKNOWLEDGEMENTS

Thanks go to Dr P. Foster of the Marine Science Laboratories, Menai

Bridge; Dr John Gould of the Institute of Oceanographical Sciences,
Wormley; and Dr H. Elderfield of the Earth Sciences Department, University
of Leeds, for supplying seawater samples.

REFERENCES

Herring, J. R. and Liss, P. S., 1974. A new method for the determination of iodine species
in sea water. Deep-Sea Res., 21: 777--783.
Johannesson, J. K., 1958. Nature of the bactericidal agent in sea-water. Nature, 180:
285--286.
Truesdale, V. W., 1974. The chemical reduction of iodine in sea-water. Deep-Sea Res.,
21: 761--766.
Truesdale, V. W., 1978. The automatic determination of iodate- and total-iodine in sea-
water. Mar. Chem., 6: 253--273.