Partial precipitation of these salts has been suggested as
This permits the anion
an effective procedure for carrying a number of transition
elements ( I O ) ; however, this has not to our knowledge
been exploited for study of trace amounts of transuranic
elements.
From Tables I1 and 111, it can be seen that partial pre-
cipitation induced by small amounts of sodium hydroxide
is an effective and reproducible concentration step in the
assay of plutonium in large volumes of sea water. Working
recoveries of plutonium tracer, averaging 74% for 50 liters
of sea water, are significantly better than the 3-6870 re-
coveries (averaging about 40%) generally experienced with
the iron hydroxide and bismuth phosphate coprecipitation
procedures (1-4). Moreover, americium, uranium, and po-
lonium are also effectively carried. It should be empha-
sized that recoveries in Table III include losses due to ion
exchange and plating techniques.
Our experience suggests that these losses are-(see
Table 1V)- for plutonium 16%, for americium 15%, for
uranium 2570,and for polonium 33%. Thus, when the av-
erage working recoveries are corrected for such losses, the
partial precipitation of the alkaline earth hydroxides and
carbonates from sea water appears to carry these four ele-
ments with an efficiency of about 90%.
Besides the high recoveries and ease with which the
precipitate settles, the sodium hydroxide procedure has
another distinct advantage over the ferric hydroxide pro-
H. L. Healy, D. Chakravarte, and T . Koyanagi. fnviron.
(10) T . Joyner,
Sci. Techno/..1, 417 (1967).
Dichromate Reflux Chemical Oxygen Demand
A Proposed Method for Chloride Correction in Highly Saline Wastes
Frank J. Baumann
Pomeroy. Johnston and Bailey. a Division of Jacobs Engineering Company. 660 South Fair Oaks Avenue. Pasadena. Caiif. 91 105
Any method that attempts to determine chemical oxy-
gen demand (COD) by strong wet oxidative means in sa-
line wastes encounters the problem of chloride interfer-
ence. Chloride oxidation can be avoided by using mild ox-
idizing conditions but only a t the expense of inefficient
oxidation of organic matter.
The standard procedure ( I ) for the determination of
COD by the dichromate reflux method utilizes acid con-
centrations and heating times which will oxidize roughly
85-95’70 of the organic matter present but will also oxidize
essentially 100% of the chloride ion ( 2 ) .
In the standard procedure, interference by chloride ion,
a t moderate concentrations, is largely prevented through
the addition of mercuric sulfate to form unionized mercu-
ric chloride ( 3 ) . The complexing method, as currently
practiced, using a weight ratio of HgS04:Cl equal to 1 O : l
will yield reproducible results a t chloride concentrations
up to 5,000 mg/l. Problems due to chloride interference
arise in wastes of low to moderate COD with chloride con-
centrations approaching that of sea water.
( 1 ) American Public Health Association Standard Methods for the Ex-
amination of Water and Waste Water 13th ed 1971 pp 495 et
seq
( 2 ) W A Moore R C Kroner and C C Ruchhoft A n a / Chem
953 (1949)
(3) R A Dobbsand R T Williams Ana/ Chem 35, 1064 (1963)
1336 A N A L Y T I C A L C H E M I S T R Y , V O L . 46, N O . 9 . AUGUST 1974
cedure: no iron carrier is added.
exchange chromatography to be carried out in a hydro-
chloric acid media in which many other metals of interest
to oceanographers are absorbed onto th’e Dowex-1 resin
and can be selectively eluted (6). For example. the iron
fraction could be analyzed for 55Fe, an important indica-
tor of new weapons fallout and also of much biological im-
portance.
Although the sodium hydroxide procedure is a simple
method for attaining high yields, no special attempt was
made to achieve perfect equilibrium between the environ-
mental nuclides and the added tracers. It is possible that
refractory particulate radionuclides, collected with the
precipitate, may escape detection without special treat-
ment of the dried precipitate, for example fusion. That
important study is continuing separately.
ACRNOWLEDG.MENT
We gratefully acknowledge the courtesy of John Harley
of the U.S. Atomic Energy Commission, Health and Safe-
t y Laboratory of New York for the 236Pu,243Am, 232U,
and 20sPo tracer solutions and also for a 239Pu standard
solution (Pu-239-001-XLIV) against which the 236Pu was
compared.
Received for review January 7 , 1974. Accepted April 15,
1974. The work was supported by the US.Atomic Energy
Commission and the Office of Naval Research of the U S .
Navy.
Moore e t a1 (2) noted that quantitative oxidation of
chloride depended, among other parameters, on the acid
concentration and the amount of dichromate present. Ex-
periments have shown that the degree of oxidation of
chloride is not predictable under practical conditions.
This unpredictability causes the determination of small
amounts of organic matter in the presence of high chloride
concentrations (such as in estuarine waters) to be unreli-
able. It has been stated that a t the present time, COD
cannot be accurately measured in samples containing
more than 2000 mg/l of C1- ( 4 ) . The chlorine-chloramine
cycle, as suggested by Moore ( I ) , may well be a contribut-
ing factor to this unpredictability.
In light of increasingly more stringent discharge re-
quirements being enacted by State and Federal agencies,
many of which base a discharge fee, tax, or surcharge on
the relative “strength” (L.e., COD) of the discharge, the
need for an accurate and reproducible method of deter-
mining the oxygen demand of the waste without positive
interference due to oxidation of chloride becomes evident.
In experiments conducted by the author with known
COD and chloride concentrations, as well as with un-
known highly saline wastes, it has been shown that chlo-
ride oxidized in the dichromate reflux procedure may be
21.
( 4 ) ’ ASTM Annual Book of Standards, Method D1-252-67, (1972).” p
219
T a b l e I. Apparent and Corrected COD Values on
S y n t h e t i c COD-Chloride Mixtures Using
Various H g S O I :C1- R a t i o s [COD = 500 mg/l. ]
Cor-
rected
Apparent COD,
C 1 - Concn HgSO4:Cl- COD, mg 1. C1- correction mg/l.

None None 501 None 501 500 ML

1,000 None 722 215 507 ERLENMEYER
FLASK
1,000 10: 1 501 None 501
5,000 None 1,467 934 533
DISTILLING TUBE W I T H
5,000 10: 1 486 None 486 SIDE ARM
10,000 None 2,749 2,225 524
10,000 10: 1 650 150 500
10,000 20: 1 632 108 524 - 5 0 0 ML FLAT BOTTOMED
BOILING FLASK
20,000 None 2,450 1,941 509
20,000 10: 1 646 152 494
20,000 20: 1 622 130 49 2
Figure 1. Chlorine-collection apparatus for chloride correction in
highly saline wastes COD

quantitated and accounted for. Chlorine liberated in the

oxidation of chloride is collected in acid potassium iodide
Table 11. Apparent and Corrected COD
solution and back-titrated us. standard sodium thiosulfate Values in Sea Water
solution t o arrive a t a chloride correction.
Chemical oxygen demand,
EXPERIMENTAL HgSOd: C1
mg/l.

A p p a r a t u s . The all-glass apparatus, readily assembled from Method ratio Apparent Corrected
standard laboratory glassware, is shown in Figure 1. A controlla-
ble source of nitrogen gas is required. Std. 10: 1 149
Procedure. To the sample and dichromate in a flat-bottom Std. 10: 1 144
boiling flask, add mercuric sulfate. The exact amount is not criti- Std. 20: 1 163
cal though the mercuric ion should constitute a n excess over chlo- Std. 20: 1 176
ride ion. Slowly, and with cooling. add the required volume of Std. + recovery 10: 1 152 58
sulfuric acid containing silver sulfate. Connect to the apparatus Std. + recovery 10: 1 147 48
as in Figure 1. Immerse the tip of the delivery tube in ea. 200 ml Std. + recovery 20: 1 168 66
of aqueous K I solution (approximately 2 to 3 grams of KI) acidi- Std. + recovery 20: 1 165 54
fied with 10 ml 1:2 acetic acid. Begin heating and reflux the mix-
ture as outlined in “Standard Methods”. While refluxing. blow a
gentle stream (1 to 2 hubbles per second) of nitrogen through the
apparatus.
Upon cessation of heating, increase the flow of nitrogen to
sweep out the apparatus and prevent back-siphoning of the KI Table 111. Apparent and Corrected COD Values on
solution. Continue the flow of nitrogen until the mixture has T u n a - C a n n i n g Wastes [HgSO:: C1- R a t i o 1O:l)
cooled. Disconnect and rinse the delivery tube. Titrate the liber- Chemical oxygen demand, mg, I.
ated iodine against standard thiosulfate solution, using starch in- Sample
dicator. Titrate reflux mixture as in normal COD determination. Run Chloride size,
Calculation. No. Chloride, m g i l Apparent correction Corrected ml.

Apparent COD =
(a - b) c 8000 1 12,900 567 199 368 25
ml sample 2 12,500 1,710 814 896 25
3 17,700 1,220 698 522 23
8000 ( d ) ( e ) 4 15,700 541 141 400 23
Corrected COD = Apparent COD - ml sample
5 18,500 460 98 362 25
6 Unknownu 3,000 778 2,222 25
Where Apparent COD = apparent chemical oxygen demand from 7 Unknown,’ 612 430 182 25
dichromate, mg,’l.; a = Fe(NH4)2(S04)2 used for blank, ml; b = 8 18,300 474 218 256 25
F e ( N H 4 ) 2 ( S 0 4 ) 2used for sample, ml; c = Normality of ferrous 9 18,700 480 307 173 25
ammonium sulfate; d = Thiosulfate used for titrating the iodine, 10 14,500 1,115 85 1,030 25
ml; e = Normality of the thiosulfate. Corrected COD = Apparent 11 16,800 554 180 374 25
COD - Chloride correction, mg/l. (K2Cr207 = 0.25N). 12 18,600 69 1 131 560 25
13 16,000 762 176 586 25
RESULTS AND DISCUSSION 14 18,300 830 209 621 25
15 14,750 474 102 372 25
Table I shows some typical results obtained with known 16 18,200 672 195 477 25
COD and chloride mixtures using the recovery method 17 15,660 812 95 717 25
described. 18 17,300 895 45 850 25
Known COD’S were obtained from standardized potassi- 19 18,700 250 186 64 50
um acid phthalate solutions; sodium chloride was used to 20 18,750 445 365 80’ 50
21 11,280 320 61 259 50
obtain chloride concentrations. 22 18,400 142 89 53 50
No significant interference, due to chloride, is encoun- 23 18,700 147 73 74 50
tered a t chloride concentrations of 5000 mg/l. or less in 24 14,700 2,896 1,520 1,376 10
the presence of excess mercury.
a Chloride concentration unknown. Sample assumed to be sea water, HgS04
Conversely. a t chloride concentrations of 10,000 mg/l. added accordingly.
or more, even a 20:l ratio of HgS04:Cl (twice the nor-

ANALYTICAL C H E M I S T R Y , VOL. 46, NO. 9, A U G U S T 1974 1337

mal ratio and a 4.8:l theoretical Hg:Cl ratio) did not
prevent the oxidation of some chloride, thereby yielding
erroneously high COD results. These results, however, can
be corrected by collecting, and accounting for, the liberat-
ed chlorine.
Table I data would indicate the feasibility of determin-
ing dichromate reflux COD in salt water without chloride
sequestration by mercuric sulfate. While this possibility is
intriguing, the care and extra trouble required in the ma-
nipulations would render this variation unsuitable for rou-
tine COD determination.
Table I1 illustrates the serious error to which the stan-
dard method is prone. COD was determined in samples of
sea water obtained from Marineland of the Pacific, Palos
Verdes Peninsula, Calif.
Having established the repeatability of the recovery
method on synthetic COD and chloride mixtures as well
as on sea water, we used the method to determine COD
on waste water from a tuna-canning operation.
Table I11 shows some apparent and corrected COD
values covering chloride concentrations between approxi-
Use of a Potentiometric Sulfur Dioxide Electrode for
Lamp Sulfur Determinations
John A. Krueger
Orion Research lncorporated, I 1 Blackstone Street, Cambridge, Mass. 02139
Sulfur in petroleum is commonly determined by the
Lamp Combustion Method ( I ) , in which the sample is
burned under controlled conditions and the gaseous sulfur
combustion products are collected and analyzed. In the
past, the instability of sulfur dioxide solutions and the
unavailability of interference-free methods for sulfur diox-
ide measurement have made it more convenient to use a
hydrogen peroxide absorbing solution, and to measure the
sulfate formed by oxidation of sulfur oxides by acidimetric
titration or gravimetric determination of precipitated bar-
ium sulfate.
The recent introduction of a gas-sensing electrode which
is selective for sulfur dioxide makes possible the measure-
ment of sulfur combustion products directly as sulfur
dioxide in the absorbent.
The theory of gas sensing electrodes has been discussed
in another publication (2). Briefly, the sulfur dioxide elec-
trode is a gas detecting device which senses the level of
dissolved sulfur dioxide in aqueous solutions. A gas per-
meable membrane separates the sample solution from an
internal filling solution in contact with a pH-sensing elec-
trode. As the partial pressure on each side of the mem-
brane equilibrates, the pH of the filling solution varies.
The internal filling solution contains a high level of bisul-
fite, so that the variation in pH is reversible and repro-
ducible. The electrode has a slope of 58 mV per decade
over a concentration range of 10-6 to 2 x 10-2M.
(1) "Sulfur in Petroleum Products by Lamp Combustion,'' in "Standard
Methods of Chemical Analysis," F. J. Welcher. Ed , (Abstracted
from former ASTM Methods D90-55T) p p 2031-33, Vol. 2. part B.
1963
( 2 ) J W . Ross, J r . , J H Riseman, and J. A . Krueger. "Potentiometric
Gas Sensing Electrodes," J Pure Appi. Chem., 36, 473-387 (1973)
(paper presented at the IUPAC Conference in Wales. 1973).
1338 A N A L Y T I C A L C H E M I S T R Y , VOL. 46, N O . 9, A U G U S T 1974
mately 12,000 and 19,000 mg/l. Table III also shows that a
10:1 ratio of HgS04:C1 will not entirely prevent some
chloride from being oxidized. The fraction of chloride oxi-
dized does not appear to be dependent on chloride con-
centration, sample us. dichromate and acid volumes, nor
the amount of mercuric salt added; rather, it appears to
vary with the substrate.
True values for oxygen consumed from dichromate can
be determined in highly saline wastes and sea water by
the use of the chlorine-recovery method outlined herein
without the need for prior chloride determination or de-
pendence upon a large excess of mercury which, as dem-
onstrated, will not achieve complete sequestration of chlo-
ride.
ACKNOWLEDGMENT
For inspiration and guidance in the conduct of this
study, the author is indebted t o Richard D. Pomeroy.
Received for review January 7, 1974. Accepted March 25,
1974.
This paper describes a method of collection and analy-
sis of oxidized sulfur products which is considerably faster
than earlier methods. The sulfur is measured directly as
sulfur dioxide in the absorbing solution-particulate and
ionic by-products of the lamp combustion do not interfere.
EXPERIMENTAL
Apparatus. A VWR Scientific Lamp Sulfur Apparatus, Cat.
No. 51934-000, was used for sample combustion, with a single ab-
sorber or, in later experiments. two absorbers in series. Air was
drawn through the system a t about 300 ml/minute using a vacu-
um pump; the air flow was controlled by a 5-turn stainless steel
valve.
Sulfur dioxide measurements were made using a n Orion Model
95-64 sulfur dioxide electrode and Orion Model 801 digital
pH/mV meter, reading to 0.1 mV.
A liquid membrane chloride electrode, Orion Model 92-17, p H
electrode, Orion Model 90-01, and double junction reference elec-
trode, Orion Model 91-02, with 10% K N 0 3 in the outer chamber,
were also used.
Reagents. Sulfur dioxide standards were made by appropriate
dilution of Orion sulfur dioxide molarity standard, Cat. No. 95-
64-06. Osmolality and p H of samples were adjusted using Orion
"SO2 buffer," made by adding 190 grams of anhydrous N a ~ S 0 4to
about 800 ml of water in a 1-liter volumetric flask, mixing thor-
oughly, then adding 53 ml of concentrated (96-9770) and
diluting to the mark with distilled water. The p H of the buffer
was about p H 1.2 after 1 + 10 dilution. All other chemicals were
Fisher Certified Reagents. The sodium hydroxide used was tested
and found to be free of sulfur dioxide.
Procedure. Electrode Operation and Storage. Correct operation
of the electrode was confirmed by preparing a calibration curve
(3).Between measurements, the electrode was kept in the recom-
niended storage solution to reduce changes in osmolality inside
the electrode. The storage solution was prepared by adding about
(3) Sulfur Dioxide Instruction Manual, Orion Research Incorporated,
1973