~ Pergamon
PII: S0043-1354(96)00324-7
Wat. Res. Vol. 31, No. 5, pp. 965-972, 1997
© 1997 Elsevier ScienceLtd. All rights reserved
Printed in Great Britain
0043-1354/97$17.00+ 0.00
INFLUENCE OF CHARACTERISED NATURAL ORGANIC
MATERIAL ON ACTIVATED CARBON ADSORPTION: I.
CHARACTERISATION OF CONCENTRATED
RESERVOIR WATER
GAYLE NEWCOMBE l*, MARY DRIKAS I@, SHOELEH ASSEMF
and RONALD BECKETT 2
tAustralia Water Quality Centre, Private Mail Bag, Salisbury, SA 5108, Australia and 2CRC for
Freshwater Ecology, Water Studies Centre and Department of Chemistry, Monash University,
P.O. Box 197, Caulfield East, Victoria 3145, Australia
(Recewed May 1996; accepted & revised form November 1996)
Abstract--Natural organic material (NOM) from Myponga Reservoir in South Australia was
concentrated and fractionated using ultrafiltration into nominal molecular weight fractions < 500, 500--
3000, 3000-10,000, 10,000-30,000 and > 30,000. The fractions were characterised using flow field-flow
fractionation, ~3CNMR, colour determination and potentiometric titration. The ultrafiltration fractions
displayed a gradual transformation from highly coloured, highly branched, high carbohydrate structures
to compounds with a prevalence of long chain aliphatic carbon with much lower carbohydrate content
and colour. There were no clear trends in the carboxyl content of the fractions, as determined by both
NMR and titration. Analysis of the titration data showed evidence of three distinct types of carboxyl
groups and the same types of groups were present in each fraction. © 1997 Elsevier Science Ltd
Key words--dissolved organic material, natural organic material, humic substances, ~3Cnuclear magnetic
resonance, characterisation
INTRODUCTION
Dissolved natural organic material (NOM) is found
in varying concentr~itions in all natural water sources.
It is a complex mixture of compounds formed as a
result of the breakdown of animal and plant materials
in the environment. The composition of the mixture
is strongly dependent on the environmental source
(Aiken and Cotsaris, 1995); however, some generalis-
ations can be made about the structures present
in NOM. A range of compounds, from small
hydrophilic acids, proteins and amino acids to larger
humic and fulvic acids, are constituents in most
NOM (Choudry, 1983). The predominant humic and
fulvic acids have a relatively high molecular weight,
typically in Australian waters from below 500 to
> I0,000, and can have both aliphatic and aromatic
character (Choudry, 1983; Beckett et al., 1987). Most
of the compounds present in NOM carry a charge,
generally attributed to carboxylic acid and phenolic
groups (Perdue and Lytle, 1983; Perdue et al., 1984),
and this causes the larger compounds to behave as
polyelectrolytes in solution (Ephraim et al., 1986).
The mechanism of transport of NOM through soils
into rivers and streams is of importance for
*Author to whom all correspondence should be addressed
[Fax: (+61) 8259 0228].
catchment management strategies, and the effect of
NOM on drinking water treatment is important in
terms of public health and water quality. It is
therefore of value to gain information on the
character of NOM with the aim of determining how
this influences soil transport and water treatment
processes.
The size distribution of the NOM is a significant
characteristic which is often measured using size
exclusion chromatography or ultrafiltration. Neither
technique can fractionate on size alone, and other
factors such as structure, charge and polarity
influence the results (Wershaw and Aiken, 1985). For
example, Kuchler and Miekeley (1994) found that an
ultrafiltration membrane of nominal molecular
weight 1000 retained a fulvic acid in preference to a
humic acid, although the humic acid had a higher
molecular weight. Carbon 13 nuclear magnetic
resonance (~3C NMR) is a very useful tool in
determining the average chemical structure of NOM.
Spectra can be obtained for a concentrated liquid, or
solid, sample and the chemical shifts of the spectral
peaks are assigned to ~3C in different chemical
environments. The areas under the peaks are then
related to the different percentages of carbon in each
of the chemical environments. In this way the per cent
of carbon in aliphatic, O-alkyl, aromatic and
carbonyl groups can be determined. Wershaw et al.
965