Water Res. Vol. 18. No. 4, pp. 501-504. 1984 0043-1354 84 53.00+0.

00
Printed in Great Britain. All rights reserved Copyright c~ 1984 Pergamon Press Ltd

DISSOLVED O R G A N I C MATTER AND THE

DISSIPATION OF C H L O R I N E IN ESTUARINE
WATER AND SEAWATER

GEORGE T. F. WONG* and THOMAS J. OATTS

Department of Oceanography, Old Dominion University, Norfolk. VA 23508. U.S.A.

(Receired July 1982)

Abstract--Dissolved organic matter in estuarine water and seawater collected in the summers of 1980 and
1981 in the James River, Virginia and the mouth of Chesapeake Bay were separated into fractions
according to their nominal molecular weights (NMW) by ultrafiltration. Estuarine waters contained higher
concentrations of dissolved organic carbon (DOC). Among the fractions, between 66-89°~ of the DOC
was found in the fraction with NMW below 10,000. Estuarine waters also had higher chlorine demands.
At a dose of 5 mg I -~, in 23 h, about 90Uoof the added chlorine disappeared in estuarine waters, whereas,
in seawater, only 60-75,°,o of the chlorine had dissipated. At least two-thirds of the chlorine demand
occurred in the first 5 h. About 10-30~ of the chlorine demand may be attributed to the fraction with
NMW above 10,000. The remaining chlorine demand was distributed almost equally between the fractions
with ranges of N MW of 1000--10,000 and below 1000. If reactivity is measured in terms of organic chlorine
demand (ACIo) per unit weight of DOC. the fractions with lower NMW ( < 1000 and 1000-10,000) always
had a higher reactivity towards chlorine. Between these two fractions, the one with NMW between I000
and 10,000 exhibited higher reactivity more frequently. The highest reactivity found was 1.4 mg ACIo mg-
DOC.

Key words---chlorination, estuarine water, seawater, dissolved organic matter

INTRODUCTION lar weights (NMW) of 1000, 10,000, 30,000 and 100,000,

When chlorine is added to seawater, the concen-
tration of residual chlorine decreases with time in two
phases (Eppley et al., 1976; Wong and Davidson,
t977). In the first few hours, the concentration de-
creases rapidly. This is followed by a much slower but
steady decrease in concentration with time. The rate
o f dissipation of chlorine is affected by temperature,
the presence of light or bromide (Wong, 1980a, b,
1982a). A significant fraction of the chlorine demand,
especially in the first phase of reactions, is caused by
the reaction between the added chlorine and naturally
occurring organic compounds (Glaze and Peyton,
1978; Helz et al., 1978; Jolley et al., 1978). Helz et al.
(1978) suggested that the removal of organic matter
by ultrafiltration can reduce the chlorine demand of
seawater significantly. In this paper, the reactivity of
various fractions of organic compounds, separated
by ultrafiltration, in estuarine water and seawater
towards chlorine will be examined.
respectively, were used in 1980. In 1981, the filters UM02,
YM5, YMI0, PMI0, XM50 and XMI00A with
cutoff-points at NMW of 1000, 5000, 10,000 10,000. 50,000
and 100,000 were used. The dissolved organic carbon
(DOC) concentration of each filtrate was determined by the
wet digestion method of Menzel and Vaccaro (1968) in
triplicate. The precision was about + 10~o. A quantitative
amount of a stock sodium hypochlorite solution was added
to each filtrate to give an initial concentration of added
chlorine of about 5mgI-L The time course of disap-
pearance of residual chlorine in each of these solutions was
followed by measuring the total residual chlorine concen-
tration by amperometric titrations at pH 4 (Rand et al.,
1976) and iodometric titrations at pH 1.4 (Wong and
Davidson, 1977) with uncertainties of +5% and +3%,
respectively in 1980. In 1981, concentrations of total
residual chlorine were determined only with iodometric
titrations. The limitations and the actual species that may be
detected by these analytical methods have been discussed in
greater details previously (Wong and Davidson, 1977;
Wong, 1980c, 1982b).
RESULTS AND DISCUSSION

EXPERIMENTAL The concentrations of D O C in the various filtrates

Estuarine water and seawater were collected from the
James River. Virginia and at the mouth of Chesapeake Bay
in the summers of 1980 and 1981. The samples were filtered
through pre-combusted glass fiber filters. Then, subsamples
of each filtrate were filtered through an Amicon model
TCFI0 ultrafiltration system. The filters UM02, UMI0,
PM30 and XM 100A with cutoff-points at nominal molecu-
*To whom correspondence should be addressed.
501
and the salinities of the samples are listed in Table 1.
The concentrations of total D O C in the samples are
similar to those observed in similar environments and
higher concentrations were found in estuarine waters
as expected (Head, 1976). Similar concentrations
were observed in James River water in 1980 and 1981.
In the filtrates which had been passed through the
ultrafilters, 66-89% of D O C was found in the fraction
with N M W below 10,000. The filters P M I 0 and
502 GEORGE T. F. WO~G a n d TI-IO~AS J. OATTS

YM 10 were used to fractionate organic material at 1981

this NMW in one of the studies and both kinds of River wofer
filters yielded similar results within the uncertainty of • Gloss rider
XM I00
the analyses. The dominance of DOC with lower XM 50
5 ~' P M I O
molecular weights has also been reported by Wheeler o YMIO
~O YM 5
(1976) in Georgia coastal waters. Below a N M W of AUM2
E
10,000, dissolved organic matter was further fraction- 4 ÷
o
ated into those with N M W less than I000 in the
samples collected in 1980 and less than 1000 and less ,ii+~ °
3 ll. ,,
than 5000 in the samples collected in 1981. The
IAo {3
amount of DOC at N M W between 5000 and 10,000
was small. The amounts of DOC at N M W below o
I000 and between I000 and 10,000 were quite similar
in most cases. /x
Iodometric titrations yielded slightly higher con-
centrations of total residual chlorine than am-
perometric titrations (Wong and Davidson. 1977).
O 5 0' 0 '
rOOO 15'o o 2 o
The discussions are based on the results obtained
Time (mini
from iodometric titrations since more data are avail-
able. However, since the shapes of the curves de- Fig. 1. T h e time c o u r s e o f c h a n g e o f chlorine d e m a n d in
filtrates o f J a m e s R i v e r w a t e r collected in 1981 which has
scribing the time course of change of concentration
been passed t h r o u g h glass fiber filter ( A ) a n d the ultrafilters
are similar for both methods, the conclusions can be X M 100 ( O ) . X M S 0 (11), P M I 0 ( + ), Y M I 0 ( © ) , Y M 5 (t-q)
applied equally well qualitatively to data obtained and UM2 (A).
from either method. A two-phase dissipation of
chlorine was again observed. The time courses of small. In waters filtered only through the glass fiber
change of chlorine demand in estuarine water and filter, more than 9 0 ~ of the added chlorine was
seawater collected in 1981 are shown in Figs I and 2. consumed in the estuarine waters by the end of the
The data obtained in 1980 are qualitatively similar. experiments whereas only 60-75% of the added chlo-
The time course of change of residual chlorine con- rine had dissipated in seawater. Wong (1982a) has
centration was followed for 46 or 23 h. The amount reported higher chlorine demands in estuarine waters
of chlorine lost between 23 and 46 h was relatively which may be caused by their higher concentrations

Table I, The doses of chlorine added (Clo), organic chlorine demands (ACIo) and dissolved organic carbon (DOC) in the various
subsamplcs of estuarine water and seawater
Sample Year of NMW DOC CIo ACIo (mg I-t) ACI'o/DOC
tsalinity) collection range (mg 1-c) (rag 1-~) A,T. I.T. A.T, I.T.
Seawater (26 pot) 1980 Dissolved* 4.24 5.95 2.5 2.5 0.6 0.6
< 105 4.09 5.95 2.8 2.1 0,7 0.5
<3 x 104 3.18 5.95 2.0 1.8 0.6 0.6
< 104 3.44 5.33 2,5 1.9 0.7 0.6
< 10~ 2.46 5.08 1.3 0.8 0.5 0.3
103-104 0,98 -- 1.2 I.I 1.3 1.1
104-dissolved 0.80 -- 0 0.6 0 0.7
Seawater (27.5 pptl 1981 Dissolved 2.89 4,93 -- 1.9 -- 0.7
< 105 2.41 4.80 -- 1.8 -- 0.7
<5 × 104 2.17 4.40 -- 1.8 -- 0.8
< 104 1.91 4.40 -- 2.0 -- 1,0
<5 × 103 2.28 5,14 -- 2.0 -- 0.9
< 103 0.97 5.t4 -- 1.4 -- 1.4
10LI0 "+ 0.94 -- -- 0,6 -- 0.6
10Ldissolved 0.98 -- -- -0.1 -- -0.1

James River Water (5 ppt) 1980 Dissolved 5,63 5.29 3.8 3.9 0.7 0.7
< 105 5.59 5.30 3.5 3.0 0.6 0.5
<3 x 10'+ 5.06 4,94 3.9 3.9 0.8 0.8
< 10+ 4,02 5.29 3,8 3.7 1.0 0,9
< 103 1.94 5.02 1.5 1,5 0.8 0.8
103-104 2.08 -- 2.3 2.2 1.1 I.l
10+~lissolved 1.61 -- -0.1 0.2 0 0.1
James River Water (0 ppt) 1981 Dissolved 5.66 4.69 -- 2.8 -- 0.5
<10 ~ 5.18 5.48 -- 2.9 -- 0.6

<5 x 10~ 5.05 5.48 -- 3.2 -- 0.6

< 10"s 5.05 5.34 -- 2.7 -- 0.5

<5 x 103 4.22 4.61 -- 1.9 -- 0.4

< 10~ 2.31 5,01 -- 0.9 -- 0.4

103-10~ 2.74 -- -- 1.8 -- 0.7
10"Ldissolved 0.61 -- -- 0.1 -- 0.2
CIo--dose o f chlorine added: A.T.--amperometric titration: I.T.--iodometric titration: ACIo--organic chlorine demand: *"Dissolved" is
defined as material that passes through a Gelman AE glass fiber filter.
 DOC and the dissipation of chlorine
1981
B a y wa~er
• Glass rider
• XM lO0
5 • XM 50
o YM I 0
+ YM5
A UM2
E ,
"o
E 3
"o
== ~t
2
(J /x
0 5 0' 0 I o OO 1 5 'O O
Time (min)
Fig. 2. The time course of change of chlorine demand in
filtrates of Chesapeake Bay water collected in 1981 which
has been passed through glass fiber filter (A) and the
ultrafilters XMI00 (Q), XM50 ( i ) , YMI0 (O), YM5 ( + )
and UM2 (/\).
of dissolved organic matter. At least two-thirds of the
chlorine demand was reached during the first 5 h.
Chlorine demand was reduced if the water was
filtered through the ultrafilters. The reduction was
small or undetectable when membranes with
cutoff-points of NMW of 100,000, 30,000, 10,000 and
5000 were used. Whether a reduction may be ob-
served is limited by a combination of analytical
uncertainties, standardization errors of the various
standard thiosulfate solutions used for the titrations,
slight variations in the amount of chlorine added to
the solutions and possible differences in the proper-
ties of the four series of filters, namely UM, PM, YM
and XM, used in the experiments. In general, at a
given contact time, about 10-30~ of the chlorine
demand may be attributed to the fraction with NMW
above 10,000. The remaining chlorine demand may
be attributed about equally between the fractions
with NMW between 1000 and 10,000, and below
I000. This preferential consumption of chlorine by
the fractions with lower NMW may be caused by a
combination of higher reactivities of these com-
pounds towards chlorine and the higher concen-
trations of DOC in these fractions.
If the first phase of reactions is primarily due to
reactions with organic compounds, this organic chlo-
rine demand (ACIo) may be estimated as the intercept
of a linear line fitted to the time course of change of
chlorine demand after the first 5 h. A similar pro-
cedure has been used in several previous studies
(Wong and Davidson, 1976; Wong, 1980a, b, 1982a).
The ratios of organic chlorine demand to the concen-
tration of DOC were calculated for the filtrates at the
NMW ranges of < 1000, 1000-10,000 and > 100,000
since these NMW ranges represent the major con-
tributors to chlorine demand and more data are
503
available within these NMW ranges. The results are
shown in Fig. 3 and Table 1. This ratio represents a
measure of the relative reactivity of the organic
material in each fraction towards chlorine. The ratios
for these three fractions ranged from 0.4 to 1.4, 0.6
to l.l and undetectable to 0.7 mg AClo mg -* DOC,
respectively. The data are not abundant nor precise
enough for studying temporal differences or
differences between estuarine water and seawater.
However, the highest reactivity was always found in
one of the two fractions with lower NMW. In three
cases, the fraction with an NMW range of 1000 to
10,000 was the most reactive. Data obtained by
amperometric titrations yielded similar results.
It has been well recognized that the DOC in natural
waters such as seawater is dominated by polymeric
2OO
high molecular weight compounds (Williams, 1975).
' O ,
This humic material has a range of molecular weights
of 2000-300,000 (Stevenson and Butler, 1969) and is
further subdivided into two main chemically defined
components: fulvic and humic acids. Each com-
ponent may contain a large number of compounds,
and the chemical structures of these compounds are
not yet known. Moreover, fulvic and humic acids
collected from different environments, such as river-
ine and marine environments, may not contain the
same compounds. In general, fulvic acid is believed to
have lower molecular weight although the cutoff
between these two fractions is not well defined. The
NMW cutoff-points of the membranes for
ultrafiltration are also inexact. Thus, an exact corre-
spondence of the operationally defined fractions ob-
tained by ultrafiltration and these chemically defined
fractions cannot be made. Nevertheless, it is likely
that the lower molecular weight fractions may con-
tain more fulvic acids whereas the high molecular
weight fractions may be dominated by humic acids.
The results of this study would then suggest that
fulvic acids are more abundant than humic acids.
1.5
[7 NMW < I0 3
[ ] 103<NMW < I04
[ ] NMW > 104
T
E LO
E
05
o 0
~y River ~y Rivet
wat~- v~te¢ waf~"
1980 1981
Fig. 3. The ratios of organic chlorine demand to dissolved
organic carbon (ACIo/DOC) in various fractions of the
samples.
50o, GEORGE T. F. WONG and THOMASJ. OAT-rs
They are also more reactive. Thus. most of the
organic chlorine demand may be caused by reactions
with fulvic acids. R o o k (1977) reported that fulvic
acids constitute the bulk of the organic matter in
some surface and ground waters and they react with
chlorine to produce haloforms and other chlorinated
byproducts. Schnoor et al. (1979) also found that
most of the organics in the Iowa River are of low
molecular weights and that most of the tri-
halomethanes are derived from this fraction of com-
pounds. These studies are not designed to investigate
the relative reactivity of various kinds of organic
material in natural waters. However, these obser-
vations are consistent with the results reported here.
Acknowledgements--This research was supported by the
Department of Energy Grant No. EE-77-S-05-5572. C. S.
Moy and K. Takayanagi participated in the analyses.
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